TOCOEN REPORT
Persistent, Bioaccumulative and Toxic Chemicals in Central
and Eastern European Countries - State-of-the-art Report
Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
TOCOEN REPORT No. 150a
Ivan Holoubek, Ph.D.
Anton Kočan, Ph.D.
Irena Holoubková, M.Sc.
Klára Hilscherová, Ph.D.
Jiří Kohoutek, M.Sc.
Jerzy Falandysz, Ph.D.
Ott Roots, Ph.D.
Brno, Czech Republic, May 2000
PBTs Discussion Club
Report Conception
Table of Content:
List of abbreviations
1.
Persistent, Bioaccumulative, Toxic substances
1.1
1.2
1.3
1.4
2.
Sources of PBT compounds in Central and Eastern European countries
2.1
3.
Introduction
Global distribution of POPs
Trends and environmental recycling of POPs
References
References
Polycyclic aromatic hydrocarbons
3.1
3.2
3.3
3.4
Properties
Sources
Sources and production in CEE countries
Environmental fate
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3.5
3.6
3.7
4.
Exposure pathways and metabolism
Toxicological effects
References
Chlorinated pesticides
4.1
Properties
4.1.1
4.1.2
4.1.3
4.2
4.3
4.4
4.5
Sources
Sources and production in CEE countries
Environmental fate
Exposure pathways and metabolism
4.5.1
4.5.2
4.6
5.
Other chlorinated pesticides with PBT characteristics
References
Properties
Sources
Sources and production in CEE countries
Environmental fate
Exposure pathways and metabolism
Toxicological effects
References
Polychlorinated biphenyls
6.1
6.2
6.3
6.4
6.5
6.6
6.7
7.
DDT
HCB
Hexachlorobenzene and other polychlorinated benzenes
5.1
5.2
5.3
5.4
5.5
5.6
5.7
6.
DDT
HCB
Toxicological effects
4.6.1
4.6.2
4.7
4.8
DDT
HCB
Hexachlorocyclohexanes (HCHs)
Properties
Sources
Sources and production in CEE countries
Environmental fate
Exposure pathways and metabolism
Toxicological effects
References
Polychlorinated dibenzo-p-dioxins and dibenzofurans
7.1
7.2
7.3
Properties
Sources
Sources and production in CEE countries
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7.4
7.5
7.6
7.7
8.
Polychlorinated naphthalenes
8.1
8.2
8.3
8.4
8.5
8.6
8.7
9.
Environmental fate
Exposure pathways and metabolism
Toxicological effects
References
Properties
Sources
Sources and production in CEE countries
Environmental fate
Exposure pathways and metabolism
Toxicological effects
References
Project TOCOEN (Toxic Organic Compounds in the ENvironment)
9.1
9.2
9.3
Introduction
Project TOCOEN model sites
Sites with long-term programme
9.3.1
9.3.2
9.3.3
9.3.4
9.3.5
9.3.6
9.3.7
9.4
Mokrá (model site 1a)
Regional background observatory Košetice (model site 3)
The model source of PAHs - DEZA Valašské Meziříčí (model site 5)
The model source of PAHs - Coal and Gas Fuel Company Vřesová (model
site 10)
Morava river catchment area (model site 11)
Region Zlín - Project IDRIS (model site 12)
Other research areas and projects
References
10. PBTs compounds in CEE countries - pilot studies and monitoring programmes
10.1 Introduction
10.2 Air
10.2.1
10.2.2
10.2.3
Emission inventories
Ambient air levels
References
10.3 Water and sediments
10.3.1
10.3.2
10.3.3
10.3.4
10.3.5
10.3.6
10.3.7
10.3.8
Introduction
The Adriatic Sea
The Baltic Sea
The Black Sea
Danube River projects and studies
Danube Regional Pesticide Studies
Project Elbe
Project Odra
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10.3.9 Vistula River
10.3.10 Lakes
10.3.11 References
10.4 Soils
10.4.1
10.4.2
The contamination of soils in CEE countries
References
10.5 High-mountain ecosystems
10.5.1
References
10.6 Aquatic wildlife
10.6.1
10.6.2
10.6.3
10.6.4
The Adriatic Sea
The Baltic Sea
Inland waters
References
10.7 Terrestrial wildlife
10.7.1
References
10.8 Vegetation
10.8.1
References
10.9 Foods, transfer studies
10.9.1
References
10.10Human exposure
10.10.1 Chlorinated pesticides and PCBs
10.10.2 PCDDs/Fs
10.10.3 References
11. Environmental levels of PBTs compounds in CEE countries
11.1
11.2
11.3
11.4
11.5
11.6
Polycyclic aromatic hydrocarbons
Chlorinated pesticides
Polychlorinated biphenyls
Polychlorinated dibenzo-p-dioxins and dibenzo-furans
Polychlorinated naphthalenes
References
12. Study of fate and effects of PBT compounds
12.1 Environmental fate of PBT compounds
12.2 Study of effects of PBT compounds
12.2.1
12.2.2
12.2.3
Biochemical monitoring
The study of PAH phytotoxicity
References
12.3 Modelling
12.4 Human risk assessment
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12.4.1
References
12.5 Ecological risk assessment
12.5.1
12.5.2
Project IDRIS
References
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Persistent, Bioaccumulative and Toxic Chemicals in Central
and Eastern European Countries - State-of-the-art Report
Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
1.
PERSISTENT, BIOACCUMULATIVE, TOXIC SUBSTANCES
1.1 Introduction
Organic substances that are persistent, bioaccumulative and posses toxic characteristics
likely to cause adverse human health or environmental effects are called PBTs (Persistent,
Bioaccumulative, Toxic substances). In this context, "substance" means a single chemical
species, or a number of chemical species which form a specific group by virtue of (a)
having similar properties and being emitted together into the environment or (b) forming a
mixture normally marketed as a single product. Depending on their mobility in the
environment, PBTs could be of local, regional or global concern (Wallack et al., 1998).
Subclass of PBTs so called POPs (persistent organic pollutants) is group of compounds,
which are prone to long-range atmospheric transport and deposition (Wallack et al., 1998, UN
ECE, 1996). The global extent of POP pollution became apparent with their detection in
areas such as the Arctic, where they have never been used or produced, at levels posing
risks to both wildlife (Barrie et al., 1992) and humans (Mulvad et al., 1996).
UN-ECE initiative, which was started within the UN-ECE region (comprising eastern
and western Europe, Canada and USA) in 1992, had prepared the Protocol on POPs (UN
ECE, 1996). The Protocol includes 16 POPs and the main objective of it is to control, reduce
or eliminate discharges, emissions and losses of POPs. Beside this UN-ECE initiative was
started similar programme of United Nations Environment Programme in the co-operation
with the International Forum for Chemical Safety (UNEP, 1996). This UNEP/IFCS
programme includes 12 POPs.
The expert groups of both international bodies call for new data needs for exposure and
fate assessments. Especially, for data which are available for a particular region and they
should obviously be used in the assessment process. These international experts strongly
recommend to study the fate and distribution of the selected chemicals in different regions
using compartment mass balance models which must be verified by used of real measured
data. The most serious data gap for the prediction of environmental behaviour is
degradation rates and their regional variability based on specific transport conditions, more
data need to be collected in this area. The main topic of further research is study of
deposition/emission processes, transformation processes and bioavailability of POPs and
PBTs in terrestrial ecosystems (Wallack et al., 1998).
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Persistent, Bioaccumulative and Toxic Chemicals in Central
and Eastern European Countries - State-of-the-art Report
Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
2. SOURCES OF PBT COMPOUNDS IN CENTRAL AND EASTERN
EUROPEAN COUNTRIES
In the last decades, PBT compounds and especially polyhalogenated aromatics have
become a major issue of research in order to investigate their ubiquitous environmental
occurrence, biochemical and toxic effects, human exposure and health risk assessment.
Some of these pollutants such as polychlorinated biphenyls, phenols, benzenes and DDT
have been produced intentionally in a wide variety of commercial applications because of
their excellent technological or pesticide properties. Other persistent and very toxic
pollutants such as polychlorinated dibenzo-p-dioxins and dibenzofurans have been formed
as undesirable by-products, e.g., during the manufacture of the chemicals mentioned earlier,
waste combustion, the chlorine bleaching of pulp and paper, some metallurgical processes,
etc.
The region of "Central and Eastern Europe" is in this Report located in the area from the
Baltic Sea to south part of Adriatic Sea and from The Czech Republic to Baltic countries.
All other countries from former Soviet Union are not included there for the lack of available
information.
In general, is a little data on PBT compounds levels in many CEE countries of CEE
region. The better situation in concerning data on the industrial and pesticide chemicals in
Croatia, Czech Republic, Poland and Slovakia. In some others, such as Bulgaria, Hungary,
Slovenia, exist satisfactory information concerning the contamination with pesticides. In the
rest of CEE countries, only limited data on PBT sources and levels are available (UNEP/
IFCS, 1998).
The first complex description of state of environmental pollution with PBT types of
compounds in Central and Eastern European countries was prepared by Prof. Heinisch
(Heinisch et al., 1994). Prof Heinisch and his co-workers continued in this work and
published many other report, for example three volumes study concerning to the
comparison of situation in Germany, mainly in Bavaria and new countries and Czech
Republic (Heinisch et al., 1997a, b, c).
In the field of ambient air concentrations of PBT compounds is little information on the
state of air pollution. In earlier 90ties, an emission inventory of the some POPs releasing
into the atmosphere was carried out in the former Czechoslovakia (Holoubek et al., 1993) and
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the latter on in Czech Republic (Parma et al., 1995, MOE CR 1997) and Slovakia (Kočan et al.,
1994; Kočan et al., 1996). It should be said that much data in this inventories in the first
period (to the 1995) was charged by considerably uncertainty because of unreliability of
emission factors or lack of input parameters, such as amounts of raw materials, fuel, waste,
type of combustion, cleaning of combustion products, etc. Only minimum emission
measurements have been realised within Czech Republic and Slovakia and therefore
published emission factors were applied if available. For these reasons, it was not possible
to include some activities (emissions from fires, landfills, soil, water areas) into the
inventory at all, though they may represent, mainly in the case of pesticides, PCBs, or
PCDDs/Fs, decisive contribution to total emissions. At present time, only Czech Republic
from the CEE countries perform very broad project concerning the measurements of
emissions from typical sources of POPs (MOE CR, 1997).
Because of the position of human beings on the top of the food chain, high
concentrations of these lipophilic and persistent compounds are often found in their tissues
and excretions such as adipose tissue and milk. It has been estimated that more than 90 % of
organochlorines body burden in the general population occurs via diet. Thus the xenobiotics
found is proportional to the dietary intake, i. e. fish, animal fat, dairy products, cereals and
vegetables etc.
As regards females, two additional routes for reduction of the organochlorine body
"pool" can take place elimination through the placenta and excretion with the milk. These
clearance mechanisms may pose a particular risk for developing foetus and breast-fed
infants. Elevated levels of organochlorines compared to other European countries indicated
high exposure of young women in the former Czechoslovakia (Greig and Snith, 1998;
Holoubek et al., 1995; Kočan et al., 1998; Schoula et al., 1998).
The first survey in the field of PBT compounds carried out in the former
Czechoslovakia at the beginning of 60ties was initiated by concerns over serious
contamination of humans caused by widespread use of DDT. Besides measurement of
DDTs in the human adipose tissue later studies paid attention also to hexachlorobenzene
(HCB), hexachlorocyclohexanes isomers (HCHs) and at 80ties to polychlorinated biphenyls
(PCBs). A successive decrease in the concentrations of DDT, HCHs and HCB in human
adipose tissue was observed on connection with the governmental regulations on their
withdrawal from use.
However, considerable differences in residue levels determined in the human fat from
different part of Czech republic have been frequently found. Moreover, in some regions, the
generally recognised decrease is not so pronounced due to the serious contamination of the
foodstuffs produced and distributed within particular area. The very similar situation was/is
in other CEE countries.
The trend results indicate that actual PCB concentrations remain in human adipose fat
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high even after several decades banning on their production.
We have not to forget to the fact that this region has very specific problems of
environmental pollution, which are the results of the recent wars. Destruction of industrial
facilities and spilling of chemicals have the worst effect for the environment (Bosnia and
Herzegovina, Croatia, Serbia and Montenegro). But the bizarre situations like usage of
transformer oil as a diesel fuel and antilace shampoo containing lindane against pests in the
gardens could not be bypassed (Kneževič and Sober, 1998). One potential result of the
pollution of the food, water and whole environment is dramatic increasing in the digestive
system carcinoma, particularly large intestine carcinoma, which has been observed last two
years in Bosnia and Herzegovina.
Beside sources of contamination mentioned above, in Bosnia and Herzegovina (BH)
specific problem is so-called pharmaceutical waste. During the war, huge amount of drugs
has arrived as humanitarian aid. Part of these drugs has arrived expired data, while others
haven´t been used due to various reasons, so whole amount of waste drugs according to the
WHO is estimated to reaches 800 tonnes. The major part of this amount is still not
adequately treated in BH. The various methods of disposal (incineration, legal and illegal
dumps...) can be source of environmental contamination including PBT compounds.
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Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
3.
POLYCYCLIC AROMATIC HYDROCARBONS
3.1 Properties
Polycyclic aromatic hydrocarbons (PAHs), or polyarenes, are probably the largest and
most structurally diverse class of organic compounds known (Harvey, 1997). They are
ubiquitous pollutants, they overall environmental fate depends on several factors such as
atmospheric photolysis, sorption, water and lipid solubility, chemical oxidation,
volatilisation, microbial degradation. The fate of PAHs in nature is of great environmental
concern due to their toxic, mutagenic, and carcinogenic properties (Holoubek et al., 1996).
PAHs are organic molecules consisting of at least three rings, at least two of which are
fused benzene rings. Any two neighboring rings share two adjacent carbon atoms. In some
PAHs, one carbon atom is substituted by an atom of another element, such as nitrogen,
oxygen, sulphur, or halogen (Muller at al., 1997).
PAHs are generally insoluble in water but can be readily solubilized in organic solvents
or organic acids. This means that in aqueous environments, PAHs are generally found
adsorbed on particulates and on huic matter, or solubilized in any oily contaminant that may
be present in water, sediment and soil. The solubility of PAHs in water is inversely
proportional to the number of rings it contains. Thus, three-ring PAHs tend to be more
soluble in water than the five-ring compounds.
PAHs are solids at room temperature. Since PAHs tend to have low vapour pressure,
they are usually adsorbed on particulate matter in the atmosphere. The vapour pressure of a
PAH is inversely proportional to the number of rings it contains. Thus, almost all five-ring
compounds are particulate bound, while three-ring PAHs are also present as vapour in the
atmosphere.
In the presence of sunlight, PAHs undergo photooxidation in the atmosphere.
Photooxidation occurs much faster for particle-free PAHs than particle-bound compounds.
PAHs in the air can also be oxidized by ozone, by reactive compounds adsorbed on the
particles, by NOx and by SOx.
PAHs are highly soluble in lipids and are readily absorbed from gastrointestinal tract of
mammals. They are rapidly distributed to a wide variety of tissues but, despite their high
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lipid solubility, PAHs tend not to bio-concentrate in the adipose tissue of vertebrates,
primarily because they are rapidly and extensively metabolised.
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4.
CHLORINATED PESTICIDES
The organochlorine pesticides that are extremely persistent and very extensively
persistent and were extensively used in many countries through the world.
4.1 Properties
4.1.1 DDT
DDT (or 4,4´-DDT), which is an acronym
for 1,1,1-trichloro-2,2-bis(4-chlorophenyl)
ethane - is a prototype of broad action,
persistent insecticides. Technical grade
DDT is a mixture of three forms, p,p´-DDT
(85 %), o,p´-DDT (15 %), o,o´-DDT (trace
amounts).
Also p,p´-DDE (1,1-dichloro-2,2-bis(4chlorophenyl)ethylene - product of
dehydrogenchlorination) and p,p´-DDD
(1,1-dichloro-2,2-bis(4-chlorophenyl)
ethane - product of dechlorination)
sometimes contaminate technical grade
DDT. DDD was also used to kill pests; one
form of DDD (o,p´-DDD) has surprisingly been used medically to treat cancer of the
adrenal gland. DDE is the main metabolite and degradation product of DDT and its human
levels are currently much higher than those of DDT. DDT and all its derivatives is
considerable stable under most environmental conditions and are resistant to complete
breakdown by the enzymes present in soil microorganisms and higher organisms. DDT and
its derivatives are very soluble in lipids and organic solvents and practically insoluble in
water.
p,p´-DDT and its derivatives are very soluble in lipids and organic solvents and
practically insoluble in water. p,p´-DDT dehydrochlorinates at temperatures above its
melting point or when dissolved in organic solvents in the presence of alkalis or organic
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bases. p,p´-DDT is stable in strong acids and can withstand acid permanganate oxidation.
4.1.2 HCB
Hexachlorobenzene (HCB) is a chlorinated aromatic hydrocarbon
with moderate volatility. It is practically insoluble in water, but is
highly lipid-soluble and bioaccumulative. Technical grade HCB
contains up to 2 % impurities (1.8 % pentachlorobenzene and
0.2 % 1,2,4,5-tetrachlorobenzene), including higher chlorinated
dibenzo-p-dioxins, dibenzofurans and biphenyls.
In a pure state, HCB is a white crystalline solid. Like PCBs,
PCDDs and PCDFs, it is stable in strong acids and its decomposition in alkalis continues
very slowly.
4.1.3 Hexachlorocyclohexanes (HCHs)
Lindane was one of the most widely utilised insecticide on world-wide scale. Its
insecticidal properties were discovered in the early 1940s by ICI Ltd. Lindane excellently
acts for controlling a wide range of sucking and chewing insects attacking foliage and roots.
It also gives a control of grains in storage as well as those found in household and livestock.
Lindane is a chlorinated hydrocarbon with stomach, contact and fumigant actions with a
relatively long residual activity. Lindane is the commercial name for the gamma isomer of
hexachlorocyclohexane. Even this stereoisomer performs the greatest insecticidal activity.
The reaction product of the HCH synthesis contains five stereoisomers of
hexachlorocyclohexane. The chlorination reaction of benzene in order to gain HCH was at
first carried out by M. Faraday in 1825. The isolation method for the active gamma isomer
from the reaction product was discovered by van Linden in 1912.
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5. HEXACHLOROBENZENE AND OTHER POLYCHLORINATED
BENZENES
5.1 Properties
Hexachlorobenzene (HCB) is chlorinated aromatic hydrocarbons with moderate
volatility. It is practically insoluble in water, but is highly lipid-soluble and
bioaccumulative. Technical grade HCB contains up to 2 % impurities (1.8 %
pentachlorobenzene and 0.2 % 1,2,4,5-tetrachlorobenzene), including higher chlorinated
dibenzo-p-dioxins, dibenzofurans and biphenyls.
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6.
POLYCHLORINATED BIPHENYLS (PCBs)
6.1 Properties
PCBs are a group of man-made
chemicals contains 209 individual
compounds (congeners) with varying
harmful effects.
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7. POLYCHLORINATED DIBENZO-p-DIOXINS AND DIBENZOFURANS
(PCDDs/Fs)
7.1 Properties
Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans
(PCDFs) are environmental contaminants detectable in almost all compartments of the
global ecosystem in trace amounts (Fiedler, 1999).
PCDDs/Fs are members of a group of widespread and environmentally stable
chlorinated, tricyclic, planar aromatic hydrocarbons. The term "dioxins" refers to 75
congeners of PCDDs and 135 congeners of PCDFs. Among these 210 compounds, 17
congeners can have chlorine atoms at least in the positions 2, 3, 7 and 8 of the parent
molecule. The molecules containing one to three atoms of chlorine are thought to be of no
toxicological significance.
Those that are very toxic have chlorine atoms at least at the positions 2, 3, 7 and 8. All
the 2,3,7,8-substituted PCDDs and PCDFs plus coplanar PCBs (with no chlorine
substitution at the ortho positions) show the same type of biological and toxic response.
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PCDDs/Fs never were produced intentionally, they are formed as by-products of
numerous industrial activities and all combustion processes (Fiedler, 1999). Almost all 210
individual congeners have been identified in emissions from thermal and industrial
processes and consequently PCDDs/Fs are found as mixtures of individual congeners in
environmental matrices such as soil, sediment, air and plant and lower animals. PCDDs/Fs,
particularly the higher chlorinated, are poorly soluble in water, have a low volatility, and
adsorb strongly to particles and surfaces (high Koc). Thus, PCDDs/Fs can hardly be
identified in water and are immobile in soils. Especially, the 2,3,7,8-chlorine substituted
PCDDs/Fs are extremely stable in the environment and bioaccumulate in fatty tissues (high
Kow) of animals and human.
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8.
POLYCHLORINATED NAPTHALENES (PCNs)
8.1 Properties
Although knowledge on the formation, sources, occurrence, fate and risk of many manmade organohalogens has improved enormously from the time of discovery of
environmental pollution with polychlorinated biphenyls, polychlorinated naphthalenes
(PCNs) still remain a relatively little known group of environmental toxins. Environmental
contamination with PCNs has been confirmed around the whole world (Falandysz, 1998).
PCNs contain one to eight chlorine atoms per naphthalene molecule and form a complex
mixture of 75 congeners. Earlier, as reviewed by Kover (1975), the substance were known
due to their high acnegenic potency and lethality to men when exposed occupationally to
fumes. At least some of few PCN members investigated appear to exhibit high dioxin-like
toxicity (Hanberg et al., 1990; Engwall et al., 1994). The lack of appropriate standards for
individual congeners of chloronaphthalene, coupled with the lack of congener-specific and
highly sensitive analytical method, were for many years the reasons for lack of insight into
the formation, occurrence and fate of these chemicals in the environment.
PCNs have physical and chemical properties largely similar to those of PCBs. Those
compounds are hydrophobic, have high chemical and thermal stability, good weather
resistance, good electrical insulating properties, low flammability and are compatible with
other materials.
Melted naphthalene and chlorine in the presence of a catalyst are substrates involved in
the synthesis of PCNs on a technical scale similarly as PCBs. The synthesis of PCNs via
chlorination of melted naphthalene with gaseous chlorine is nucleophilic and electrophilic
substitution reaction. The temperature of the reaction in the synthesis of PCNs is held from
80 °C to below 200 °C. The electrophilic and nucleophilic substitution reaction favours the
formation of chloronaphthalens with chlorine in alpha-position (1,4,5,8-positions).
Based on the available information, as much as 74 of 75 possible PCN congeners are
formed through the radical attacks in the flame (Imagaea et al., 1993). The radical reactions
depend on kinetic, thermodynamic and steric effects, and the precursor molecules for the
formation of PCNs can be benzene with butadiene, styrene with ethane/ethine or it can
proceed due to a direct chlorination of the naphthalene nucleus by chlorine radicals
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(Weidmann and Ballschmiter, 1993). The most abundant chloronaphthalene congeners found
in the fly ash from the Stoker type incinerators have a predominant substitution in the betapositions (2,3,6,7-positions). The major constituents of the PCNs in fly ash, from the
fluidised bed type incinerators are congeners with two, three or all four carbon atoms
substituted at alpha-positions.
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Persistent, Bioaccumulative and Toxic Chemicals in Central
and Eastern European Countries - State-of-the-art Report
Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
9. PROJECT TOCOEN (Toxic Organic COmpounds in the
ENvironment)
9.1 Introduction
The TOCOEN Project (Toxic Organic COmpounds in the ENvironment) is a long-term
environmental research project involving many Czech and Slovak universities, research
institutions and various companies and at the present time collaboration with some
universities and institutions from other countries.
The TOCOEN Project had its inception in 1988 (Holoubek et al., 1990, 1994). The basic
goal of the project is a detailed understanding of the fate of selected organic pollutants in
the environment. This includes input of these pollutants to various parts of environment
(through emissions), their transport in compartments and between them, their
transformations (photochemical, chemical, thermal, biochemical), their biological effects
(dose exposure analysis), modelling of these processes, and risk assessment, management
and prognosis of contamination development.
Certain groups of POPs such as polycyclic aromatic hydrocarbons (PAHs), chlorinated
pesticides (Cl-PEST), polychlorinated biphenyls (PCBs), dibenzo-p-dioxins (PCDDs) and
dibenzofurans (PCDFs) were selected as model compounds at the beginning of the project.
Currently, other groups of organics such as chlorinated benzenes, phenols, certain other
types of pesticides, chlorinated aliphatic hydrocarbons and other chlorinated aromatic
compounds are also being intensively studied. All the model compounds are determined in
the important parts of environment - air, atmospheric deposition, surface waters, sediments,
soils, aquatic and terrestrial biota.
Biological indicators such as soil biota and plants have been used to monitor regional
patterns of air pollution, as well as atmospheric deposition of pollutants transferred over
long distances. Analyses of earthworms made it possible to constitute an effective
monitoring system in the study of pollutant fluxes to terrestrial ecosystems. Earthworms
have been widely used for studies on the bioaccumulation and chronic toxicity of PAHs,
PCBs, chlorophenols and 2,3,7,8-TCDD. Similarly, mosses, conifer needles and lichens
serve as valuable indicators of contamination in TOCOEN ecotoxicological studies.
During the first period (1988 - 1996) more work was done in the field of basic and
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preliminary measurements and monitoring. During this period, sampling and analytical
design was optimised, and monitoring provided the first information about POP
contamination of important regions in the Czech and Slovak Republic. Monitoring activities
were focused on five types of model sites (Holoubek et al., 1990a):
●
background sites: (GEMS - Global Environmental Monitoring System - observatory
Košetice, south Bohemia) (Holoubek et al., 1992; Váňa et al., 1997);
●
heavily polluted areas - the combination of industrial and urban pollution (Holoubek et
al., 1991, 1992c, 1994b);
●
landscape with typical agricultural production (Holoubek, 1993);
●
river basin areas (Holoubek, 1993; Holoubek et al.,1994a, 1998d);
●
known sources of particular compounds including:
a. PAHs (DEZA Valašské Meziříčí, a chemical factory producing aromatic and
polyaromatic compounds, phthalates and carbon black; Coal and gas fuel
company Vřesová) (Holoubek 1991, 1994b),
b. PCBs, PCDDs/Fs (Municipal waste incinerators: Brno, Bratislava; industrial
waste incinerator: LIAZ Mnichovo Hradistě; Technoplast Chropyně; oil
refinery: OSTRAMO Ostrava) (Holoubek et al., 1994b).
A very important part of studies performed focused on the presence of POPs in
vegetation, soil biota and soil, enabling some conclusions on mechanisms of deposition to
be drawn. Bioindicators of changes in stressed soil environments represent one of the newly
established research activities. During the last 3 years, the TOCOEN Project contributed to
the following four problem areas:
1. survey of soil contamination in the Czech Republic through monitoring type of
projects (Holoubek, 1993; Holoubek et al., 1994, 1998a, b),
2. biomonitoring of stressed soils (Dušek, 1995; Dušek and Tesařová, 1996; Škoda et al.,
1996),
3. study of diversity and activity of soil microbial communities in terrestrial ecosystems
stressed by heterogenous mixtures of POPs (Dušek, 1995; Dušek and Tesařová, 1996;
Škoda et al., 1996; Holoubek, 1998c),
4. the development of methods for ecological risk assessment in contaminated soils
(Holoubek, 1998c; Holoubek et al, 1998a).
The accumulation of PBTs compounds in soil and sediments is a potential risk for the
future, potential "Chemical Time Bombs" (Holoubek, 1993). For example, sediments act as a
sink for many PBTs that enter aquatic ecosystems. Contaminated sediments can be a source
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of contaminants to aquatic organisms even long time after the contamination of the water
body has stopped. In many regions, freshwater sediments were found to be a major
continental reservoir of these harmful organic compounds. Project TOCOEN is focused to
study of sediments from the beginning of research activities in 1988. The sampling network
is formed from TOCOEN model sites (the surroundings of model sources of PBTs) and the
most important tributaries of rivers Morava and Danube (river Morava is the main river in
Moravia and one of the most important tributaries of the Danube).
The sediments were also collected from river Dřevnice, tributary of river Morava. This
sampling area is located in East Moravia in the surroundings of town Zlín, sediments were
collected in sampling period 1995-1998 (Holoubek, 1998; Holoubek et al., 1998d).
In this area of region Zlín, east part of Czech Republic, a model case study as the newest
part of Project TOCOEN was carried out. This long-term research project BETWEEN (The
Relationships BETWEEN Environmental Levels of Pollutants and Their Biological Effects)
is focused on the identification of ecological risks based on study of real environmental
mixtures of persistent environmental pollutants (PBTs) and long-term effects on
ecosystems. Project includes very wide range of chemical and ecotoxicological laboratory
and field methods and compares their results.
It is difficult to provide direct conclusive proof of a causative relationship between
environmental levels of specific PBTs and adverse impacts on a wildlife population.
Linkages between contaminant exposure and effects may nevertheless be identified by
evaluating all available study data and applying a multiple statistical analysis, PCA etc.
These topics are studied from molecular and cell levels to ecosystem. Project has three
levels of basic approaches:
1. hazard identification vs. ecotoxicological properties of environmental compartments,
2. hazard identification and assessment in the field without previous knowledge about
the stress factors involved,
3. risk assessment focused on sites (area) with known influence of stress factors.
On the molecular and cell level, the effects of potential environmental pollutants on cell
proliferation, differentiation, apoptosis and risk/safety assessment of their role in tumour
promotion are studied. Ecosystem level includes the study of effects of anthropogenic and
natural hazards on the population and communities in aquatic and terrestrial ecosystems
(study of biodiversity - aquatic toxicology, in vitro tests of toxicity, biochemical markers in
vivo in fish liver, study of parasites).
This study of potential harmful effects which used very wide laboratory and field
battery of tests, is focused on environmental/ecological risk assessment of various types of
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environmental mixtures of pollutants. Project is realised in present time in Czech Republic
as a example of "from molecular and cell levels to ecosystem type study", and the results
are used for development of methodology of environmental and ecological risk assessment.
Part of present acitivities of R - T & A group is focus on the establishment and
construction of ESF Scientific Network on Persistent, Bioaccumulative and Toxic
Chemicals (PBTs).
Main goal of this Network is to bring together scientists to explore the potential
developing and carrying out research of persistent, bioaccumulative and toxic chemicals at a
European level. This scientific network aims to provide a platform for scientists working in
the field of environmental chemistry, environmental toxicology, ecotoxicology and risk
analysis.
Scientific background of Network (and former EERO Network on Persistent
Environmental Pollutants) is based on the Vancouver Declaration "Towards Global
Action" (Vancouver, Canada, June 04-08, 1995) and the Intergovernmental Forum on
Chemical Safety (IFCS) Meetings on Persistent Organic Pollutants (Manila, Philippines,
June 17-22, 1996), participants of the International Symposium "TOCOEN ´96 - The Fate
and Effects of POPs in the Environment" (Luhačovice, Czech Republic, April 28 - May 01,
1996) and 1st EERO / RECETOX / TOCOEN International Workshop "The Advances and
Trends in Environmental Chemistry of POPs" adopted the so called Luhačovice
Declaration.
Participants concluded that they would establish a complete European research network
on persistent environmental pollutants (PEPs). PEPs have long half-live in the environment
and undergo slow physical, chemical and biological degradation. This group of
environmental harmful compounds includes many classes of organic compounds
(semivolatile persistent organic pollutants, volatile persistent organic compounds), as well
as heavy metals, natural toxins, etc.
The main topics of former EERO Network on the Fate and Effects on PEPs were
focused on the following research problems:
●
the fate of PEPs in the European region;
●
the sampling and analytical procedures for PEPs;
●
the effects of PEPs on various types and levels of biota;
●
the environmental risk assessment.
Scientific background of new ESF Network on Persistent, Bioaccumulative and Toxic
Chemicals has as a basic philosophy based on the conclusions of ETAF Workshop: POPs.
What next ? (York, UK, May 05-09/05/98). Organic substances that are persistent,
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bioaccumulative and posses toxic characteristics likely to cause adverse human health or
environmental effects are called PBTs (Persistent, Bioaccumulative, Toxic substances). In
this context, "substance" means a single chemical species, or a number of chemical species
which form a specific group by virtue of (a) having similar properties and being emitted
together into the environment or (b) forming a mixture normally marketed as a single
product. Depending on their mobility in the environment, PBTs could be of local, regional
or global concern. Under the auspices of the United Nations Economic Commission for
Europe (UN-ECE) Convention on Long-Range Transboundary Air Pollution (CLRTAP), a
protocol on persistent organic pollutants (POPs) has been drawn up in which POPs are
defined as "a set of organic compounds that (i) posses toxic characteristics; (ii) are
persistent; (iii) are liable to bioaccumulate; (iv) are prone to long-range atmospheric
transport and deposition; and (v) can result in adverse environmental and human health
effects at locations near and far from their sources" (UN-ECE). In other words, POPs are a
subclass of PBTs that are prone to long-range atmospheric transport and deposition. The
global extent of POP pollution became apparent with their detection in areas such as the
Arctic, where they have never been used or produced, at levels posing risks to both wildlife
and humans.
Growing concern over recent decades about the potential effects of some man-made
chemical substances on human health and the environment has prompted action at meny
levels from local to global. Some of the international initiatives in order to identify the main
policy issues and management tools that might contribute to more effective regulation and
management of these chemicals.
Scientific areas of ESF Network on PBT chemicals to the following scientific and
research topics:
●
the fate of PBTs in the European region - source inventories, emission/deposition
processes, long-range transport, transformation processes and bioavailability of PBTs
in terrestrial ecosystems, modeling of chemical fate in the environment at the local,
regional and global scale with special attention to new types of chemicals and those
for which inadequate monitoring data exist;
●
the developing of new sampling and analytical methods for PBTs;
●
the study of efffects on various types and levels of biota with special attention to
study of effects of environmental mixtures and study of "unknown" effects - study of
phytotoxic effects, effects on soil microbial populations and soil fauna, effects on
aquatic biota, the developing of mechanism-based biomarkers of effect, study of nongenotoxic carcinogenesis;
●
ecological risk assessment - reliable monitoring data are needed for risk assessment
and model calibrations.
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Persistent, Bioaccumulative and Toxic Chemicals in Central
and Eastern European Countries - State-of-the-art Report
Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
10.
PBTs COMPOUNDS IN CEE COUNTRIES
10.1 Introduction
Few monitoring programmes concerning the PBT environmental levels exist in Czech
Republic (10 years of monitoring of PBT compounds on a regional level - observatory
Košetice Project TOCOEN, some other regional monitoring programmes such as Project
Teplice, Project Silesia, Project Prague). The Czech Ministry of the Environment organises
5 years monitoring of environmental levels of pollutants including some PBTs. The
Ministry of the Health CR organises the fifth year the monitoring of health status of Czech
population (including PBTs) and similarly the Ministry of Agriculture organizes some
monitoring programmes concerning to soils, forests, food again including some PBT
compounds. Slovakia (PHARE Project, PCB Projects), Baltic countries and Poland (Baltic
Sea), Croatia (Adriatic Sea), Slovenia. In general, there is a little knowledge on PBT levels
in various environmental media. Based on the existing monitoring and research data
especially in these countries some estimates on trends of these compounds in environmental
media can be realised. The countries of the region need emission inventories based on real
measurements of emission factors, effective monitoring systems and a scientific, research
and information network focused on PBTs.
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Persistent, Bioaccumulative and Toxic Chemicals in Central
and Eastern European Countries - State-of-the-art Report
Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
11.1 Polycyclic aromatic hydrocarbons
The concentration of PAHs in some environmental matrices
Site
Concentration
Reference
Ambient air [pg.m-3]
Slovakia - industrial, urban areas
(1995/96)
- rural, forest area
104 - 609
Kočan et al.
3.45 - 83.57
(Sum
of 7 carcinogenic)
36
3.89
Slovakia
PHARE
Water [ng.l-1]
Sediments [ng.g-1 dry wt]
Soils [ng.g-1 dry wt]
Estonia - urban areas, 1996
2 220 - 12 390
- rural areas
232 - 770
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The concentrations of PAHs in biota [ng.g-1]
Site
Concentration
Reference
11.2 Chlorinated pesticides
The concentration of chlorinated pesticides in some environmental matrices
Site
Concentration
Reference
Ambient air [pg.m-3]
Slovakia - industrial, urban areas
(1995/96)
- agricultural
- rural, forest area
HCB: 99 - 3 620 Kočan et al.
p,p´-DDE: 35 - 870
HCB: 4 450 - 4 740
p,p´DDE: 105 - 109
HCB: 147
p,p´-DDE: 32
Slovakia
PHARE
Water [ng.l-1]
Sediments [ng.g-1 dry wt]
Soils [ng.g-1 dry wt]
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The concentrations of chlorinated pesticides in biota [ng.g-1]
Site
Concentration
Reference
11.3 Polychlorinated biphenyls
The concentration of PCBs in some environmental matrices
Site
Concentration
Reference
Ambient air [pg.m-3]
Slovakia - industrial, urban areas
(1995/96)
- rural, forest area
160 - 11 310
Kočan et al.
300
Slovakia
PHARE
Water [ng.l-1]
Sediments [ng.g-1 dry wt]
Soils [ng.g-1 dry wt]
The concentrations of PCBs in biota [ng.g-1]
Site
Concentration
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Reference
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11.4 Polychlorinated dibenzo-p-dioxins and dibenzo-furans
The concentration of PCDDs/Fs in some environmental matrices
Site
Concentration
Reference
Ambient air [pg.m-3]
Water [ng.l-1]
Sediments [ng.g-1 dry wt]
Soils [ng.g-1 dry wt]
The concentrations of PCDDs/Fs in biota [ng.g-1]
Site
Concentration
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Reference
TOCOEN REPORT
Persistent, Bioaccumulative and Toxic Chemicals in Central
and Eastern European Countries - State-of-the-art Report
Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
12.
STUDY OF FATE AND EFFECTS OF PBT COMPOUNDS
12.1 Environmental fate of PBT compounds
This chapter will be published during 2000.
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Persistent, Bioaccumulative and Toxic Chemicals in Central
and Eastern European Countries - State-of-the-art Report
Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
Discussion club:
Have you any contribution, note, remark or question to the second up-graded version of
TOCOEN REPORT No. 150: Persistent, Bioaccumulative and Toxic Chemicals in
Central and Eastern European Countries - State-of-the-Art Report ? You can join our
PBTs Discussion Club here.
Other useful informations:
The Czech company TESO Praha have prepared together with the other Czech
specialists the validation of the methods for determination of POPs in emissions. If you
have interest of this or interest to co-operate in this field please contact directly to Mr.
Bures, director of this company - e-mail: [email protected]. You can find the English
version of this method on TESO homepage: www.teso.cz.
Have you any topics for the future common projects including the possible financial
support ? We are looking forward to your any remarks, notes, questions, contributions and
confirmation. All of them you can send on e-mail address [email protected].
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Persistent, Bioaccumulative and Toxic Chemicals in Central
and Eastern European Countries - State-of-the-art Report
Report Conception:
RECETOX - TOCOEN & Associates
RECETOX (Research centre for Environmental Chemistry and
EcoTOXicology) http://www.recetox.muni.cz/
Phare Project EU/21/AIR
Project TOCOEN
(Toxic Organic COmpounds
in the ENvironment)
Project BETWEEN
(The relationships
BETWEEN the
environmental levels
of pollutants and
their biological
effects)
Project IDRIS
(The IDentification of
ecological RISks)
Persistent, Bioaccumulative and Toxic Chemicals in Central and Eastern
European Countries - State-of-the-art Report
(TOCOEN REPORT No. 150)
Environment - Carcinogenesis - Oncology
(Ministry of Education, CR)
Research Intention No. CEZ: J07/98:141100003
University Oncological Centre Brno
http://www.uoc.muni.cz/
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Persistent, Bioaccumulative and Toxic Chemicals in Central
and Eastern European Countries - State-of-the-art Report
Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
List of abbreviations
PBTs
Persistent, Bioaccumulative, Toxic compounds
POPs
Persistent Organic Pollutants
OCCs
Organochlorine Compounds
OCPs
Organochlorinated pesticides
PAHs
Polyclic Aromatic Hydrocarbons
NAP
Naphthalene
ACL
Acenaphthylene
ACE
Acenaphthene
FLR
Fluorene
PHE
Phenanthrene
ANT
Anthracene
FLU
Fluoranthene
PYR
Pyrene
BaA
Benzo[a]anthracene
CHR
Chrysene
BbF
Benzo[b]fluoranthene
BkF
Benzo[k]fluoranthene
BaP
Benzo[a]pyrene
INP
Indeno[1,2,3-cd]pyrene
DBA
Dibenzo[a,h]anthracene
BPE
Benzo[g,h,i]perylene
PCBzs
Polychlorinated benzenes
PCPs
Polychlorinated phenols
PeCP
Pentachlorophenol
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HCHs
Hexachlorocyclohexanes
HCB
Hexachlorobenzene
PCBs
Polychlorinated biphenyls
PCDDs
Polychlorinated dibenzo-p-dioxins
PCDFs
Polychlorinated dibenzofurans
D - Di, Tr - Tri, T - Tetra, Pe - Penta, Hx - Hexa, Hp - Hepta,
O - Octa
TEFs
Toxic Equivalent Factors
I-TEQs
International Toxic Equivalents
UNEP
United Nations Environmental Programme
UN ECE
United Nations European Commission for Economy
CLRTAP
Convention on Long-Range Transboudary Air Pollution
CEE
Central and Eastern European
RECETOX
Research Centre for Environmental Chemistry and
EcoTOXicology
MU
Masaryk University of Brno, Czech Republic
TOCOEN
Research Project - Toxic Organic COmpounds in the
ENvironment
TOCOEN, s.r.
Consultant company (Ltd.), Brno, Czech Republic
o.
R-T&A
RECETOX - TOCOEN & Associates
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Persistent, Bioaccumulative and Toxic Chemicals in Central
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Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
1.2 Global distribution of POPs
During the past three decades, analytical data have revealed global contamination of
aquatic and terrestrial environments (Tanabe et al., 1994; Brydon et al., 1995). In large
measure, this is the logical consequence of the physical and chemical properties of POPs:
●
POPs are highly resistant to chemical and biological degradation. Polychlorinated
biphenyls (PCBs) and other chlorinated pollutants, particularly the highly chlorinated
ones, have been known for some time to persist in soils, water, sediment and biota for
long periods of time (IPCS, 1993);
●
POPs are non-polar molecules that can accumulate in fatty tissues. This results in
their biomagnification in the higher trophic levels of the food chain (Shaw and
Connell, 1986a, b);
●
Many from various POPs were/are found in pristine areas where there are no known
sources of release to the environment, demonstrating that POPs are subject to longlarge transport from their initial source.
Researchers have concluded that the major mechanism for this mobility is a cyclical
evaporation from soil and water surfaces in which winds lift POPs into the air along with
water vapor and dust, eventually depositing them with rain, snow, or adsorbed to particles.
With repeated evaporation and deposition, the net result is movement of POPs such as
PCBs and some organochlorinated pesticides (OCPs) over long distances in the direction of
atmospheric air movements. Models of this mobile behavior correlate well with the
measured POP concentrations in the northern hemisphere (Delzell et al., 1994).
For example, Tanabe et al. (1994) measured PCB concentrations in southern and eastern
Asia and the surrounding seas, and pin-pointed the contribution of various PCB sources.
From their work, in addition to data gathered from North America and Europe, it is possible
to draw some general conclusions:
●
Because of their environmental mobility, PCBs eventually enter a global pool of
these contaminants and are available for recycling and redistribution (Iwata et al.,
1993; Tanabe, 1988);
●
Because of the mobility and persistence of PCBs, environmental concentrations of
PCBs tend to be uniform throughout the globe (Tanabe et al., 1994);
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●
Based on monitoring data, the polar regions appear to be an environmental sink for
PCBs (Muir et al., 1992).
Similar results were measured for many other POPs from various regions round the
world.
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Persistent, Bioaccumulative and Toxic Chemicals in Central
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Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
1.3 Trends and environmental re-cycling of POPs
The basic trends of usage and emission to the environment consist from the following
steps - they are common for many other POPs (Jones and de Voogt, 1999):
1. synthesis and development for use earlier in this century, in this case in the 1930s;
2. increasingly widespread use in Europe and North America and other industrialized
regions through the 1950s and 1960s;
3. concerns over environmental persistence and foodchain accumulation in the 1960s/
early 1970s, resulting in restrictions in usage in Europe and North America; and
4. reductions in emissions in Europe, North America and other industrialized regions
arising from the bans/controls in the 1970s through the 1980s and 1990s.
This general pattern may be unrepresentative of the global emission profile when the
chemical is used extensively outside of Europe and North America (following a global shift
in the place of manufacture).
These trends in emission have had fundamental implications for concentration trends in
air, soil, water and sediments and for magnitude and direction of fluxes between these
compartments for POPs capable of dynamic, multimedia exchange. Likely he response to
the maximum of emission phase in the 1950s and 1960s has been deposition from the
atmosphere to greatly exceed volatilization to it in the 1940-60/70s and for reverse to have
applied in the more recent past. Base on these approaches we can describe the hypothetical
responses of the air and the soil compartments to the emission pulse. Air concentration can
be expected to respond rapidly to the increasing emission (1940-60s) and to reflect it.
However, as the primary sources became controlled/reduced air concentrations initially
reduced, but in more recent times may actually have been "maintained" by volatilization
("outgassing") of recyclable POP compounds from the terrestrial and aquatic compartments.
The time over which they are maintained will be dependent on a number of factors, such as
the size of the "reservoir" of compound in the soil/sediment/water compartments,
persistence in the soil/sediment compartments, physical-chemical properties of the
compound and whether there is free exchange of the compound which has been deposited in
the past (i.e. is adsorption/desorption of the POP completely reversible?). For some
compounds, which may have entered the soil or water body primarily associated with
particulate deposition, outgassing will be limited and concentrations/burdens in these
compartments will tend to remain high/increase.
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For others, which readily enter the gas phase, outgassing will result in the soil/water
body concentration/burden declining. Research in the Great Lakes area provides powerful
evidence for these long-term trends and reversals of the air-surface exchange flux (Jones
and de Voogt, 1999). Sediments cores show deposition of POPs to the lakes reflecting the
hypothetical emission trend, whilst mass balance calculations, analysis of paired air-water
samples and monitoring of air concentrations all provide evidence that volatilization now
exceeds deposition, i.e. the water bodies now act as sources to atmosphere, rather than as
sinks. Historical reconstructions of soil and air concentrations for PCBs in the U.K. also
suggest a reversal in the long-term net flux (Harner et al., 1995). Several researcher have
shown atmospheric concentrations of re-cyclable POPs respond to seasonal or diurnal
changes in temperature (Halsall et al., 1995; Hillery et al., 1997; Lee et al., 1998). When this
happens, it suggests that the air concentration is "controlled by" secondary re-cycling rather
than fresh/ongoing primary emissions (e.g. as for PCBs).
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and Eastern European Countries - State-of-the-art Report
Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
1.4 References
Barrie L. A., Gregor D., Hargrave B., Lake R., Muir D., Shearer R., Tracey B.,
Bidleman T. F. (1992): Arctic contaminants: sources, occurrence and pathways. Sci. Total
Environ. 122, 1-74.
Brydon J., Herod D., Thomson J., Szenasy-Boch E., Deocadiz E. S. (1995):
Polychlorinated biphenyls: overview and selected case studies. In: MBR (1995), III/62-77.
Delzell E., Giesy J. P., Munro I., Doull J., Mackay D., Williams G. (1994): Regulatory
Toxicol. Pharmacol. Eddited by F. Coulston and A. C. Kolbey, Jr. Academic Press, Inc.,
San Diego, CA, Ch. 5, 187-307.
Hallsall C. J., Lee R. G. M., Coleman P.J., Burnett V., Harding-Jones P., Jones K. C.
(1995): PCBs in UK urban air. Environ. Sci. Technol. 29, 2368-2376.
Harner T., Mackay D., Jones K. C. (1995): Model of the long-term exchange of PCBs
between soil and the atmosphere in the southern UK. Environ. Sci. Technol. 29, 1200-1209.
Hillery B. R., Basu I., Sweet C. W., Hites R. A. (1997): Temporal and spatial trends in a
long-term study of gas-phase PCB concentrations near the Great Lakes. Environ. Sci.
Technol. 31, 1811-1816.
Iwata H., Tanabe S., Ueda K., Tatsukawa R. (1995): Persistent organochlorine residues
in air, water, sediments, and soil from Lake Baikal, region Russia. Environ. Sci. Technol.
29, 792-801.
Jones K. C., de Voogt P. (1999): Persistent organic pollutants (POPs): state of the science.
Environ. Pollut. 100, 209-221.
Lee R. G. M., Hung H., Mackay D., Jones K. C. (1998): Measurement and modelling of
the diurnal cycling of atmospheric PCBs and PAHs. Environ. Sci. Technol. 32, 2172-2179.
Mulvad G., Pederson H. S., Hansen J. C., Dewaily E., Jul E., Pedersen M. B.,
Bjerregaard P., Malcom G. T., Deguchi Y., Middaugh J. P. (1996): Exposure of
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Greenlandic Inuit to organochlorines and heavy metals through the marine food-chain: an
international study. Sci. Total Environ. 186, 137-139.
Muir D. C. G., Wagemann R., Hargrave B. T., Thomas D. J., Peakall D. B., Norstrom
R. J. (1992): Arctic Ecosystem contamination. Sci. Total Environ. 122, 75-134.
Shaw G. R., Connell D. W. (1986a): Factors controlling bioaccumulation of PCBs. In:
PCBs and the Environment. Vol. 1 (J. S. Waid, ed.). CRC Press, Boca Raton, 121-133.
Shaw G. R., Connell D. W. (1986b): Factors controlling bioaccumulation of PCBs. In:
PCBs and the Environment. Vol. 1 (J. S. Waid, ed.). CRC Press, Boca Raton, 135-141.
Tanabe S. (1988): PCB problems in the future: foresight from current knowledge. Environ.
Pollut. 50, 5-28.
Tanabe S., Iwata H., Tatsukawa R. (1994): Global contamination by persistent
organochlorines and their ecotoxicological impact on marine mammals. Sci. Total Environ.
154, 163-177.
UN-ECE (1998): Draft Protocol to the Convention on Long-range Air Pollution on
Persistent Organic Pollutants (EB.AIR/1998/2), The Convention on Long-range
Transboundary Air Pollution. United Nations Economic and Social Council, Economic
Commission for Europe, 1998.
UNEP (1996): UNEP Survey on sources of POPs. A report prepared for an IFCS expert
meeting on POPs. Manila, Philippines, 17-19 June 1996, UNEP, Geneva.
UNEP (1999): GEF PDF-B Regionally based assessment of persistent toxic substances.
Draft Report 1st Scientific and technical evaluation Workshop on persistent manufactured
chemicals produced for non-agricultural applications, persistent toxic and persistent
unintentional by-products of industrial and combustion processes, Geneva, January 11-15,
1999.
Wallack H. W., Bakker D.J., Brandt I., Brostrom-Lundén E., Brouwer A., Bull K. R.,
Gough C., Guardans R., Holoubek I., Jansson B., Koch R., Kuylenstirna J., Lecloux
A., Mackay D., McCutcheon P., Mocarelli P., Taalman R. D. F. (1998): Controlling
persistent organic pollutants - what next ? Environ. Toxicol. Pharmacol. 6, 143-175.
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and Eastern European Countries - State-of-the-art Report
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2.1 References
Bratanová Z., Kovačičová J., Gopina G. (1998): A review of existing data on the
occurrence of pesticides in water of the river Danube and its tributaries. Fresenius Environ.
Bull. 7, 495-501.
Greig J.B., Smith A.G. (Co-ordinators) (1998): Environmental Research Programme.
Assessment of early signs of biological action following human exposure to
polyhalogenated dibenzo-p-dioxins and related substances. EV5V-CT92-0204. Final
Report. 1998.
Heinisch E., Kettrup, A., Wenzel-Klein B. (eds.) (1994): Schaddstoffatlas Osteuropa.
Okologisch-chemische undokotoxikologische Fallstudien uber organische Spurenstoffe und
Schwermetalle in Ost-Mitteleuropa. Ecomed, Landsberg/Lech..337 p.
Heinisch E., Kettrup A., Holoubek I., Matoušek J., Podlešáková E., Hecht H., Wenzel
S. (1997a): Persistente organische Verbindugen in Nahrugsketten 7 von Bayern und
Tschechien. Teil 1: Terrestrische Systeme. GSF-Berichte 10/97, Munich, FRG, 371 p.
Heinisch E., Kettrup A., Holoubek I., Langstädtler M., Podlešáková E., Svobodová Z.,
Wenzel S. (1997b): Persistente organische Verbindugen in Nahrugsketten 7 von Bayern
und Tschechien. Teil 2. Aquatische Systeme. GSF-Berichte 11/97, Munich, FRG, 318 p.
Heinisch E., Kettrup A., Holoubek I., Wenzel S. (1997c): Persistente organische
Verbindugen in Nahrugsketten 7 von Bayern und Tschechien. Teil 3: Persistente organische
Verbindugen in Unteren Teil der Troposphäre in Bayern und Tschechien - Zusammenhänge
von Emission und Kontamination. GSF-Berichte 12/97, Munich, FRG, 189 p.
Holoubek I., Čáslavský J., Nondek L., Kočan A., Pokorný B., Leníček J., Hająlová J.,
Kocourek V., Matoušek M. (1993): The compilation of emission factors for persistent
organic pollutants. Report for External Affairs Canada. AXYS Ltd., Sidney, Canada/
TOCOEN MU Brno, March 1993, 200 pp.
Holoubek I., Dušek L., Mátlová L., Čáslavský J., Patterson D. G., Turner W. E.,
Pokorný B., Bencko V., Hajšlová J., Kocourek V., Schoula R., Kočan A., Chovancová
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J., Petrik J., Drobná B. (1995): The fate of selected organic compounds in the
environment Part XXVI. The contents of PCBs and PCDDs/Fs in human fat in Czech and
Slovak Republics. Organohalogen compounds, 26, 257 - 260.
Kneževič A., Sober M.(1998): Treatment of medical waste in Bosnia and Herzegovina. In:
UNEP/IFCS, 175-186.
Kočan A., Petrik J., Chovancová J., Drobná B., Uhrinová H., Holoubek I., Magulová
K., Sulovec D., Keppertová Z., Spišáková K. (1994): The ambient air pollution by
emissions of persistent organic pollutants in the Slovak Republic. Report. Slovak
Hydrometeorological Institute, Bratislava, Slovakia, November 1994, 119 pp. (in Slovak).
Kočan A., Ursinyová M., Reichertová E., Hladíková V., Petrik J., Chovancová J.,
Uhrinová H., Randová L., Drobná B., Rosíval L. (1996): Occurence of selected toxic and
carcinogenic organic and inorganic compounds in ambient air in selected locations of the
Slovak Republic. Report. Institute of Preventive and Clinical Medicine, Bratislava,
Slovakia, PHARE EC/93/AIR/22 project. June 1996, 61 pp.
Kočan A., Patterson D. G., Petrik J., Chovancová J., Needham L. L., Barr J. R., Barr
D. L. (1998): Polyhalogenated dibenzp-p-dioxins, dibenzofurans, biphenyls, and dioxin-like
PCBs in the human population of the Slovak Republic: an analysis and health risk
assessment. Final Report (Project No. 94023). US - Slovak Science and Technology
Program. Atlanta, US/Bratislava, Slovakia 1998, 60 pp.
Ministry of the Environment CR (1999): Emission inventory of persistent organic
pollutants. Research project, Prague, Czech Republic, 1997-1999.
Parma Z., Vošta J., Hořejš J., Pacyna J. M., Thomas D. (1995): Atmospheric emission
inventory guidelines for persistent organic pollutants. Report for External Affairs Canada.
AXYS Ltd, Sidney, Canada/Prague, CR.
PHARE (ZZ911/0106) (1997): Environmental Programme for the Danube River Basin:
Danube Regional Pesticide Study. Final Report. April 1997, 40 pp.
Schoula R., Hajšlová J., Gregor P., Kocourek V., Bencko V. (1998): Persistent
organochlorine contaminants in human tissues of the Czech and Slovak populations.
Toxicol. Environ. Chem. 67, 263-274.
Šimko G. (1992): A present state of usage and liquidation of dangerous industrial wastes
including PCBs in Slovakia. Veterinary 42, 183-185 (in Slovak).
UNEP/IFCS (1998): Proceedings of the Subregional Awareness Raising Workshop on
Persistent Organic Pollutants (POPs). Krajnska Gora, Slovenia, 11-14 May 1998, 360 pp.
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3.2 Sources
The major source of PAHs are crude oil, coal, and oil shale (Harvey, 1997). The fuels
produced from these fossil sources constitute the primary source of energy for the industrial
nations of the world, and the petrochemicals producedd from these raw materials are the
basis of the synthetic fibers and plastics industries. Coal tars and petroleum residues
produced in the refining process contain high percentages of polyarenes, representing a
wide range of molecular sizes and structural types. Also present in these sources are large
quantities of the equally diverse polycyclic aromatic heterocyclic analogs containing one or
more nitrogen, oxygen, or sulphur atoms. Together the polyarenes and their heterocyclic
analogs constitute an enormous resource of chemical raw materials that remain relatively
underutilized in relation to their potential.
The patterns of PAHs produced in pyrolytic reactions vary considerably with
temperature (Harvey, 1997). At high temperature under anaerobic conditions, the products
consist of relatively simple mixtures of unsubstituted PAHs. At intermediate temperatures, e.
g. in smoldering wood, complex mixtures of alkyl-substituted and unsubstituted PAHs are
formed. At still lower temperatures, reaction rates decrease markedly and the predominant
products are methyl- and other alkyl-substituted PAHs. Crude oils formed from the decay of
plants over millions of years exhibit characteristic patterns of aromatic hydrocarbons
components in which alkyl-subbstituted PAHs far exceed the unsubstituted polyarene
components. Crude oils also contains high ratios of hydrocarbons with saturated fivemembered rings, including highly strained methylene-bridged PAHs. The mechanisms of
formation of PAHs under pyrolysis conditions involve free radicals, but there is also
evidence for alternative modes of PAHs formation involving dimerization of dienes and
polymerization of acetylenic intermediates.
Tobacco smoke is important as a source of PAHs because of its association with cancer
mortality (Harvey, 1997). Numerous studies implicatedd cigarette smoking as the most
important single risk factor for cancers of the respiratory tract. Tobacco smoke is a complex
mixture shown to contain more than 150 compounds in the gas phase and more than 2 000
identified components in the particulate phase. The latter include numerous PAHs, some of
which are carcinogenic in experimental animals. Marijuana smoke has a similar
composition of PAH components to tobacco smoke.
PAHs also occur as minerals in association with mercury ores (idrialite, curtisite). Other
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PAH-containing minerals include karpatite from Trans-carpatia and pendletonite from
California which consists of almost pure coronene (99 %). A number of asbestos minerals
also occur in association with polyarenes including benzo[a]pyrene. It can be significant
with respect to the tumorogenic properties of some forms of asbestos. PAHs have been
detected in meteorites, and there is substantial spectroscopic evidence that they are also
present in interstellar space.
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3.3 Sources and production in CEE countries
Main sources of polycyclic aromatic hydrocarbons (PAHs) in the region are presented
by electric and thermal energy production, waste incineration, road traffic and some
industrial technologies (e. g. high-temperature coal carbonation, catalytic cracking of crude
oil, aluminium production).
A limited amount of non-carcinogenic PAHs (naphthalene, anthracene, phenanthrene,
pyrene and carbazole) is produced industrially in pure form (DEZA Valaąské Meziříčí, CR).
They usually serve as starting material for synthesis of dyes, pesticides and pharmaceuticals
(Holoubek et al., 1993).
Major source of PAHs in Czech Republic include: PAHs production and their use as
intermediates, production of carbon black, metallurgy, production and use of coke, asphalt,
and coal tars, catalytic cracking, heat coal conversion processes, waste waters, landfills,
combustion of wastes and fossil fuels, cement production in dry or wet process kilns,
petroleum refineries, crematoria, forest fires, and smoking. The situation in other CEE
countries is very similar. Annual emissions of PAHs around 215 (Warmenhoven et al., 1989)
or 378 tons (Holoubek et al., 1994) were estimated in former Czechoslovakia.
One of the major sources of PAHs in CR are coal-fired stations where mainly lower
quality brown coal is combusted. The coal used in CR has in some cases low heat capacity,
high content of water and ash and content of sulphur can be higher than 2 % (brown coal
from northwest Bohemia). The average emission factor of SPAHs estimated in CR power
plants (44.98 mg.kg-1 with range 24.92 - 59.99 mg.kg-1) is practically identical with the
value of 41.9 mg.kg-1 found in UK (Wild and Jones, 1995). Annual emission of 1,380.9 kg
(765 - 1841.7 kg.y-1) represents approximately one third of the amount emitted in UK.
Among different kinds of coal, sorted brown coal, with average heat capacity of 18 MJ.
kg-1, is mostly used in residential heating in CR. Sorted black coal, coke, and brown or
black coal briquettes are combusted less often. The range of emission factor of SPAHs, 250 mg.kg-1, estimated in CR residential heating with brown coal (Stevens et al., 1994) is
comparable with value of 56.4 mg.kg-1 (Wild and Jones, 1995) and the range of 1.8-30 mg.kg1 reported in UK (IEA, 1993) and with the range 3-70 mg.kg-1 found in The Netherlands
(Duiser and Veldt, 1989).
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The estimated emission of PAHs from residential heating is about 560 t per annum.
Assuming that the emission caused by residential heating is equal to about 80 % of the
annual emissions of PAHs, a value of approximately 700 t PAHs per annum can be
estimated for CR (IEA, 1993). This value corresponds to the sum of individual major
increments (annual emissions from coal-fired stations, residential heating, PAHs and carbon
production, and coke production) approximately 735 t per annum.
In Hungary, for PAHs, the trend of total annual emissions was the decrease from
137.1 kt to 61.7 kt between 1980 and 1996. The crucial point was totally liquidation of the
coke production in 1993 (Kovacs, 1998).
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and Eastern European Countries - State-of-the-art Report
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3.4 Environmental fate
PAHs are ubiquitous environmental contaminants which significant levels are found in
the all environmental compartments. The PAHs present in the atmosphere derive principally
from combustion of fossil fuels in heat and power generation, refuse burning, and coke
ovens (Harvey, 1997). These sources together contribute more than 50 % of the nationwide
enissions of benzo[a]pyrene, a PAH that is widely empoyed as a standard for PAH
emissions. Vehicle emissions are another major source of PAHs, particularly in the urban
areas of industrialized countries, contributing, for example, as much as 35 % to the total
PAH emissions in the USA (Bjorseth and Ramdahl, 1985). Natural sources, such as forest
fires and volvanic activity, also contribute to the overall burden, but anthropogenic sources
are generally acknowledged to be the most important source of PAHs in atmospheric
pollution.
The levels of PAHs in urban atmosphere are variable, dependent upon the density and
types of local emission sources, temperature, local meteorological conditions, and other
factors. Levels tends to be generally higher during the winter, reflecting the increase in
fossil fuel consumption during these months. Airborne hydrocarbons remain in the gas
phase at temperatures above 150 °C and rapidly condense onto fly ash particles at lower
temperatures. Consequently, a high percentage of the airborne hydrrocarbons are associated
with particulate matter. Particles less than 5 µm are said to be respirable because they can
penetrate the upper respiratory tract to enter the lower airways and the alveoli. The majority
of PAHs in the atmosphere may contribute to the potential health risk.
PAHs in the atmosphere undergo various chemical and photochemical transformations
that lead to their degradation (Harvey, 1997). These include reactions with the oxides of
nitrogen and sulphur, oxygen, ozone, hydroxyl and peroxyl radicals, and
peroxyacetylnitrate. Although the majority of these reaction pathways tend to lead to
formation of biologically inert products, there is substantial evidence that nitro-substituted
PAHs formed from reeactions with nitrogen oxide are direct-acting mutagens and
tumorigens in mice.
PAHs are also widely distributed throughout the waters of the Earth. They originate
from fallout of particulate matter carried through the air, from runoff of polluted ground
sources, and from direct pollution of rivers and lakes by municipal and industrial effluents
(Harvey, 1997). They enter the food chain by being taken up by plankton, molusks, and fish,
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and may eventually be consumed by human populations. Treatment of water with chlorine
or ozone reduces the levels of PAHs in urban drinking waters. PAH concentrations in
marine sediments tend to reflect industrialization in the adjacent land area. In contrast, PAH
profiles of marine sediments uncontaminated from anthropogenic sources contain relatively
high ratios of terpene-derived hydroaromatic hydrocarbons, e..g., alkyl-substituted
tetrahydrophenanthrenes, indicative of origin from plant fossilization.
Significant levels of polyarenes are also foundd in the soil in all regions of the Earth.
The concentrations in urban industrialized areas are usually 10-100 times higher than those
in less populous and undeveloped areas. PAHs in the soil in more remote regions derive
predominantly from forest fires and airborne pollution. Biogenesis has been suggested as
another potential source, but the experimental evidence for the synthesis of PAHs by plants
does not support this hypothesis (Harvey, 1997). However, the formation of PAHs by
microorganisms cannot be entirely ruled out at this time. The pattern of PAHs present in
recent sediments uncontaminated by anthropogenic sources tends to correspond to that for
medium-temperature pyrolysis. This suggests origin primarily from natural fires.
Significant levels of PAHs are also detected in many common foods. The highest levels
of PAH contamination are mainly found in leafy plants, such as lettuce, spinach, tea, and
tobacco, and in smoked meats and fish. The relatively high levels in leafy plants apparently
derive from atmospheric deposition. Somewhat lower levels of PAHs are detected in fresh
meats and seafood. Presumably these derive from air and water pollution as well as from
animal feed. Cooking of meats, particularly by frying or charcoal broiling, increases the
total PAH content. These sources may contribute to the causation of cancer in human
populations.
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3.5 Exposure pathways and metabolism
The human contact with PAHs is primarily through ingestion and inhalation. Under
normal circumstances, dermal contact with PAHs is relatively unimportant (Muller et al.,
1997). Similar to other lipid-soluble compounds, PAHs are generally well absorbed, but are
stored only briefly in the body, primarily in the kidney, liver and spleen. Most of the
absorbed dose is then excreted into the bile, and eventually into the faeces, and to a much
lesser extent, the urine. Most of the PAHs are excreted in their metabolized forms and only
very small amounts of the partent compounds find their way into the faeces and urine.
PAHs are highly soluble in fats. They can rapidly enter cells and become virtually
unavailable for excretion. Metabolic processes tend to make PAHs more water soluble,
thereby facilitating excretion. A number of metabolic processes compete to produce a
variety of different metabolites. The competing processes include phase I reactions, which
add one or more hydroxyl groups to the PAH molecule. The phase I reactions are catalyzed
by epoxide hydrolase and by a subset of cytochrome P-450 mixed-function oxidases known
as aryl hydrocarbon hydroxylase (AHH).
Altough the structures of PAHs vary greatly, the compounds have similar metabolic
fate, thus leading to the formation of homologous metabolites. The difference in the
tumorigenicity of different PAHs is due to the difference in the location where metabolic
modification takes place and the difference in the reactivities of intermediate metabolites.
Some metabolites formed are diol epoxides, some of which are in turn converted into
carbonium ions. The carbonium ions can react with DNA and proteins to form adducts, and
induce genotoxic damage. It is these alkylating agents that are thought to be the primary
carcinogens, acting as initiators. Initiation is the first step in the development of cancer.
The enzymes required for the conversion of parent PAH compounds into the reactive
diol epoxides are found mainly in the liver. These enzymes are also present in the lungs, the
skin basal cell layer, the intestinal mucosa and other tissues.
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3.6 Toxicological effects
Some PAHs, such as 7,12-dimethylbenz[a]anthracene (DMBA), are among the most
carcinogenic substances known (Harvey, 1997). The metabolic activation and mechanism(s)
of carcinogenesis of PAHs are surveyd in many papers, reports and books (Harvey, 1991,
1997; Muller et al., 1997).
PAHs have been shown to induce a number of toxic effects. Several PAHs have been
shown to cause death in rodents after short-term exposure to high doses. On the other hand,
no deaths have been reported from short-term occupational exposures in humans (Muller et
al., 1997). Since environmental levels are generally much lower than occupational
exposures, it is extremely unlikely that short-term exposure to PAHs in the environment
would cause death. On the other hand, eye irritation, photophobia, and skin toxicity such as
dermatitis and keratosis, have been demonstrated in workers occupationally exposed to
PAHs. The extreme environmental conditions (e.g. heavy exposure to a forest fire smoke)
may also trigger the same effects.
Addvers respiratory effects, including acute and subacute inflammation, and fibrosis,
have been demonstrated experimentally. With benzo[a]pyrene, severe and long-lasting
hyperplasia and metaplasia were observed. These effects manifest themselves as
precancerous lesions and are consistent with the general assertion that one of the main
targests of PAHs toxicity is the respiratory tract. Available data are insufficient to assess the
effects of PAHs at environmentally relevant concentrations.
Carcinogenic PAHs, but not the noncarcinogenic ones, have been reported to suppress
the immune reaction in rodents. A number of authors have been reported
immunusuppressive effects at a similar dose-range at which carcinogenicity has been
observed. Furthermore, the potency of PAHs as immunosuppressants appears to roughly
correlate with the potency of PAHs as carcinogens. Besides being an important endpoint,
immunosuppression may be involved in the mechanism by which PAHs induce their toxic
effects includding cancer. However, the data on immunosuppression are at present not
sufficient for quantitative assessment.
Exposure to PAHs can have adverse effects on both female and male reproductive
systems and on fetal development. Most of the available data relate to rodent fetal
development. Adverse effects include malformations, stillbirths, resorptions,
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immunosuppression, clastogenicity, and tumorigenicity. The doses required to produce the
reported effects are generally similar or somewhat higher than those required to elicit a
carcinogenic response. Although no human data are available, reproductive and
developmental effects may be important in humans. Unfortunately, available data are
insuffieicent to quantitatively assess both reprodductive and developmental effects.
Genotoxic effects have been repeatedly demonstrated for some PAHs, both in in vivo
tests in rodents, in vitro tests using mammalian (including human) cell lines, as well as in
prokaryotes. On the other hand, some PAHs appear not to be genotoxic. Most of the
unsubstituted PAHs which are categorized as genotoxic in themselves, but need to be
metabolized first by the AHH system. The diol epoxides formed then react with DNA to
form DNA adducts and thus induce genotoxic damage. A genotoxic event is postulated as a
required step in the carcinogenic process and may play a role in some forms of
developmental toxicity.
The tumorigenicity and carcinogenicity of individual PAHs and PAH-containing
mixtures have been well studies in experimental animals. A number od individual PAHs are
carcinogenic, while others have been found to be non-carcinogenic. For the rest of the
PAHs, the available data are insufficient to determine whether they are carcinogenic or not.
In humans, virtually no data exist regarding the carcinogenicity of individual PAHs, and
only a limited amount of data is available for PAH-containing mixtures. However, the
available evidence demonstrates unequivocally that some PAH-containing complex
mixtures are carcinogenic both to humans and experimental animals. The site and the type
of tumors are dependent on both the species and the route of administration.
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Persistent, Bioaccumulative and Toxic Chemicals in Central
and Eastern European Countries - State-of-the-art Report
Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
3.7 References
Bjorseth A., Ramdahl T. (1985): Handbook of Polycyclic Aromatic Hydrocarbons. Vol. 2.
Marcel Dekker, New York.
Duiser J. A., Veldt C. (1989): Emissions into the Atmosphere of Polyaromatic
Hydrocarbons, Polychlorinated Biphenyls, Lindane and Hexachlorobenzene in Europe.
TNO Environmental and Energy Research. TNO Report No. 89-036, The Netherlands,
January 1989.
Harvey R. G. (1991): Polycyclic Aromatic Hydrocarbons: Chemistry and Carcinogenicity.
Ed. M. Coombs, Cambridge University Press, Cambridge 1991.
Harvey R. G. (1997): Polycyclic Aromatic Hydrocarbons. Wiley-VCH, New York Chichester - Weinheim - Brisbane - Singapore - Toronto.
Holoubek I., Čáslavský J., Nondek L., Kočan A., Pokorný B., Leníček J., Hajšlová J.,
Kocourek V., Matoušek M., Pacyna J. M., Thomas D. (1993): The Compilation of
Emission Factors of Persistent Organic Pollutants in Czech and Slovak Republics. Report of
AXYS Ltd., Canada and Masaryk University, Brno, CR.
Holoubek, I., Čáslavský J., Kořínek P., Kohoutek J., Štaffová K., Hrdlička A.,
Pokorný B., Vančura R., Helešic J. (1996): Project TOCOEN. Fate of selected organic
pollutants in the environment. Part XXVII. Main sources, emission factors and input of
PAHs in Czech Republic Polycyclic Aromatic Compounds. 9, 151-157.
IEA (1993): Organic Compounds from Coal Utilisation. Report of IEA Coal Research,
London.
Kovacs G. (1998): Monitoring and releases of POPs in Hungary. In: UNEP/IFCS, 234-246.
Muller P., Leece B., Raha D. (1997): Scientific Criteria Document for Multimedia
Standard Development Polycyclic Aromatic Hydrocarbons (PAH). Ministry of
Environment and Energy, Ontario, Canada.
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Warmenhoven J. P., Duiser J. A., de Leu L. T., Veldt C. (1989): The contribution of the
input from the atmosphere to the contamination of the North Sea and the Dutch Wadden
Sea. TNO Report No. R 89/394A, The Betherlands.
Wild S. R., Jones K. C. (1995): Polynuclear aromatic hydrocarbons in the UK
environment: A preliminary sourrce inventory and budget. Environ. Pollut. 88, 91-105.
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Persistent, Bioaccumulative and Toxic Chemicals in Central
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Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
4.2 Sources
Technical DDT has been made by condensation of chloral hydrate with chlorobenzene
in concentrated sulfuric acid. It was first synthesised in 1874, but it was not used until 1939
when Müller and his co-workers discovered its insecticidal properties (US DHHS 1994a).
It was a widely used chemical to control insects on agricultural crops and insects that
carry diseases like malaria and typhus. DDT does not occur naturally in the environment
and entered the environment after it was produced to use as an insecticide.
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Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
4.3 Sources and production in CEE countries
Most of the countries in the region produce and/or formulate pesticides. The pesticide
registration is a primary requirement for import, production and distribution. During the
period of centralised economy in this region, the import was monopolised by the relevant
state organisation. By the end of the 80s, many private companies and minor distributors
were involved in import and distribution of pesticides (PHARE 1997; Bratanová et al., 1998),
many of which lack the required experience, a large part of the farming population has
insufficient education and training in plant protection (Tasheva, 1998).
Pesticide concentrations in Danube River and its tributaries show significant differences
between countries in the number and the types of pesticides analysed. The cumulative
number of analysed pesticides was 76. Residues of only 36 pesticides and metabolites have
been detected. The most frequently detected pesticides are organochlorine compounds and
triazines. Only DDT and metabolites, HCH and isomers and atrazine and metabolites were
found in more than 50 % of samples.
The special attention must be given to unwanted pesticides. The problem of unwanted
and expired pesticides pose the greatest danger to the natural environment and people which
is brought about by chemization of agriculture in CEE countries. This problem results from
many years of errors in pesticide management and especially in their distribution. In Poland,
the amount of unwanted pesticides is estimated at about 60 000 tonnes - about
10 000 tonnes in the tombs, another 25 000 tonnes at stores and about 25 000 tonnes at
individual farmers (Stobieski, 1998). The inventory of banned organochlorine pesticides in
stocks in Bulgaria in 1996 showed about 35 tonnes, which is relative high quantity for the
small territory of Bulgaria (Tasheva, 1998). Historical changes in these countries caused that
together with the advent of market economy tile problem of storing expired pesticides
ceased to exist. Countries still have not solve the problem of safety storage for pesticides
and other chemicals classified as poisons and they have no information concerning the
quantity of pesticide and chemical (for example PCBs) waste. Many from CEE countries
have no special sites dangerous materials or incinerators in which these types of chemicals
could be safety burnt.
Potential risk is linked with storage of not used PBT pesticides. In this respect, for
example, Poland has evidence of storage more than 10 000 tonnes of unused pesticides
(mixture of different pesticides including other PBT compounds). The situation is probably
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very similar in many other CEE countries (UNEP, 1998). These were identified as possible
hot spots in the region.
In some countries of the region (i.e. in Bulgaria) it was recognised that concentrations of
PBT pesticides in environmental media decreased on such levels that no further systematic
monitoring is needed (Tasheva, 1998). Different situation could be found in Albania (Koci,
1998) or Rumania (PHARE 1997; Bratanová et al., 1998; Toader and Chitimiea, 1998) where still
relatively high concentrations are measured in water and sediments (DDT and other
chlorinated pesticides). In the Slovak Republic measured data shown high exposure to HCB
from unknown source which resulted in fact that critically high concentrations could be
found in human tissues (UNEP, 1998; Kočan et al. 1996, 1998, 1999).
Many of pesticides from UN-ECE list of POPs, never been used in many countries from
this region (aldrin, chlordane, mirex, heptachlor, toxaphen). These were banned, restricted
in several countries from the region similar in some other countries of the world. Hungary
was among the first countries in the world who ban or severely restricted chlorinated
pesticides still in 1966 (UNEP, 1998).
DDT is no longer used in many countries, including CEE countries. It was banned in
former Czechoslovakia in 1974 in Czech part and in Slovakia in 1976. However, it is still
used in some African, Asian and South American states as a cheap and efficient insecticide.
Part of the countries in the region has some inventories of use and import of pesticides. For
example, in 1997 Croatia imported more than 503 tonnes of pesticides containing PBTs as
active substance (UNEP, 1998). Estonia was one from the first countries around the Baltic
Sea, which established import - ban for chlorinated pesticides in 1968 (Roots, 1996). For
example, in 1957 226 tons of pesticides, mainly DDT and lindane were used. Whereas in
relatively cool climate pests do not reproduce as much as in region with warm climate, then
in the middle of the 1960ies the amount of used pesticides in Estonia stayed at low levels,
not exceeding 0.7-1.0 kg per ha (among that 0.03-0.06 kg per ha were chloroorganic
pesticides).
Substance distribution patterns of DDT, DDE, DDD, DDMU, and of α, β, γ, δ, ε-HCH
as well as the IUPAC congeners of PCBs in aquatic and terrestrial ecosystems may give
hints as to the kind of input (i.e. the perpetrator as well as dating of the process. Heinisch
and Kettrup (1997) demonstrated it on examples such as the distribution pattern of DDT
metabolites after massive applications in GDR forests in 1983/4 compared with earlier
applications and the distribution pattern of HCH isomers in the surroundings of factories or
as consequences of lindane applications.
The situation in former GDR is not discusses in this report, but these applications had
the consequences with level of contamination in the former Czechoslovakia and described
approaches is very useful tool for interpretation of history and state of contamination. The
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comparison of level of contamination was published in Report of IOC GSF, Neuherberg,
Germany and we would like prepare the English version as a other parts of these REPORT
(Heinisch et al, 1997a, b, c).
More than 20 years after the worldwide ban of DDT there are still increased
contamination levels in different matrices. Using a simple substance distribution pattern of
DDT parent substance and metabolites it is possible to get hints as to the source. We can
describe two examples.
In 1983/4 on the territory of the former GDR 260 000 ha of forests were treated with
high amounts of DDT/lindane preparations from aircraft to combat the black-arched moth
(Lymanthria monacha). Before that, in 1975 a stepwise ban for DDT was passed, which
mainly worked well. The levels of Sum of DDTs and also the percentage of the parent
substance DDT usually decreased after banning. The decreasing level in former GDR
during the period of 1976 to 1982 had one simple reason - until 1992 no new DDT was
carried into the region.
In 1984 and 1985 not only the Sum of DDTs concentrations increased in many observed
matrices and commodities, but also the percentage of the parent substance DDT. This may
be judged as a hint for the fact that from 1983 on there was new DDT input into the region.
The impact of this new impact was possible to detect not only in the region of applications
but also round whole the former GDR and also in former Czechoslovakia or still in Czech
Republic, 15 years after.
For example the matrix herring from the waters around the Isle of Rűgen as a result of
transport up to the Baltic Sea and its - with a time lag - effects there. In 1986, the observed
value of DDT in herrings had the maximum, higher than years before. After clear decreases
of the Sum of DDTs contamination values and the percentage of the parent substance DDT
during the period 1971-1985, there was a clear increase in 1986 especially of the percentage
of the parent substance DDT.
In the south-east of the GDR - the district of Chemnitz (former Karl-Marx-Stadt)
received about 10 % of the amount of DDT/lindane preparations used for combating
Lymanthria monacha in 1982-1985 - there was apparently a drift leading to "co-treatments"
of North-Bavarian border areas. In 1983 and 1984, used amounts of DDTs were 120 and
480 tones, respectively. Using the analysis of kidney fat of deer and red deer in 1985 a clear
gradient in the Sum of DDTs loads could be found from the north to the south by Hecht in
1996 (Heinisch and Wenzel-Klein, 1994).
Other border-crossing co-treatments have been registered in the former Czechoslovakia,
now the Czech Republic. The Table describes higher levels Sum of DDTs residues with
high percentages of DDT in soil samples from the boundary mountain - Krušné hory
(Erzgebirge Mountains), Krkonoše Mountains, Lužické hory and in the north-east
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Bohemian cities of Ústí nad Labem, Teplice, Karlovy Vary. These levels decreased if we
are coming from the former neighbour, the former GDR towards the inner parts of Czech
Republic (Prague, Kladno, Příbram, South Bohemia, south border mountains (Šumava
Mountains). This trend is evident in the levels of Sum of DDTs and mainly the percentages
of the parent substance markedly decrease that means the Sum of DDTs residues must be of
older origin. Especially low are the Sum of DDTs residues and the percentage of the parent
substance in the south of the Czech Republic, in Šumava Mountains as well as in the towns
Český Krumlov, Prachatice and in the area of TOCOEN/CHMI regional background
observatory Košetice.
Sum of DDTs and percentages of the parent substance DDT
in soil samples from the Czech Republic [ng.g-1]
Sampling site
DDT DDE DDD
8
na
Sum of
% DDT in
References
DDTs Sum of DDTs (*)
Mumlava, Krkonoše,
1 190 m, 1995
33
41
80
Pudlava, Krkonoše,
1 140 m, 1995
179
70
na
249
72
Pašerácký
chodníček, 1 310 m,
1995
99
36
na
135
73
Jedlová, Lužické
hory, 710 m, 1995
302
84
na
386
78
Lesná, Krušné hory,
800 m, 1995
2
390
795
na
3 185
75
Načetín, Krušné
hory, 710 m, 1995
4
013
1
164
na
5 177
78
Ústí nad Labem, M,
1995
1
133
1
1
1 135
100
Teplice, M, 1995
1
207
146
256
1 609
75 (89)
Karlovy Vary, M,
1995
398
122
36
556
72 (77)
Sokolov, M, 1995
522
209
40
771
68 (71)
Cheb, M, 1995
264
167
25
456
58 (61)
Kladno, M, 1995
63
53
7
123
51 (54)
Holoubek et
al., 1996;
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see Chapter
10.5, too
Podlešáková,
1996
TOCOEN REPORT
Praha, M, 1995
1
044
1
054
1
2 099
49 (50)
Mníšek pod Brdy,
M, 1995
651
245
4
900
72 (73)
Příbram, M, 1995
28
31
1
60
47 (47)
Boubín, Šumava,
1995
11
7
na
18
61
Český Krumlov, M,
1995
1
1
1
3
33 (50)
Prachatice, M, 1995
1
1
1
3
33 (50)
0.2
9
0.2
1.3
15
Košetice, 1995
Holoubek et
al., 1996
Podlešáková,
1996
Holoubek et
al., 1996;
see Chapter
10.2.2, too
M - maximal value from 5 - 60 samples
(*) - number without parantheses - original number of Heinisch and Kettrup; number in
parantheses - Sum of DDTs, DDT + DDE - same values for all samples from various authors
The total volume of the technical DDTs used in Poland from 1974 to 1980 was 48 151.7
tones, and the annual rate was up to 3 880.6 tones. HCB was imported and used in the past
in Poland as fungicide, and the application rates were relatively small (total import was
187.6 tones between 1962 and 1972) (Dabrowski et al., 1994).
The soil contamination by hexachlorcyclohexane and consequently the HCH cumulation
in agricultural products were of great interest due to their long persistence in our ecosystem
(Schlosserová, 1993). In the Slovak Republic hexachlorocyclohexane was synthetised in the
former CHZJD factory in Bratislava. During the years 1956-1966 there was produced more
than 13 000 tonnes of gamma-HCH. Some additional raw HCH was imported from the
former Yugoslavia. After isolation of the gama isomer it was formulated into different
pesticides in same factory. Naturally, the produced pesticides were intended partly for
domestic utilisation. A very rough estimate of annual consumption of Lindane containing
pesticides in the Slovak Republic was about 1 tonne per year. This amount has been
gradually decreased. The variety utilised Lindane based formulations has been as well
descended: e.g. in the List of Permitted Pesticides for 1972 were listed 11 pesticides on the
basis of Lindane. These were insecticides into the most important crops (potatoes, beet
roots, rapeseeds, hops), staining agents for treating seeds of cereals, maize, legumes, sugar
beet, cucumber, cotton, hemp, rapeseed, water melon, soil desinsectants for growing beet
roots, sugar beet, cereals, maize, tobacco, hops, young fruit, trees and vines, and fumigant.
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The application of all these pesticides was possible only with some restrictive
precautions. The wide and systematic utilisation of Lindane containing insecticides was
banned in 1974. The year 1992 was the last one when Lindane seed treating agents were
permitted as formulations Lindane WP 80 for rapeseed and Lindane 50/35 WP for flax and
hemp seeds. In the List of Permitted Pesticides for 1993 was given a new Lindane
containing pesticide. Emdenit was intended for controlling pine insects but only for two
years period.
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4.4 Environmental fate
Large amounts of DDT were directly applied to soil. Some DDT may have entered the
soil when it was stored or disposed of in waste sites. DDT has entered surface water and
sediments either by direct spraying of the water during insecticide use or indirectly when
rain-washed soil containing DDT entered surface waters. DDT like all the organochlorine
pollutants has a strong tendency to adsorb on surfaces. Most DDT that enters waters is
already firmly attached to soil particles, and remains attached. In the past, DDT entered the
air directly when used as an insecticide. In the present time, DDT may be released into air
due to evaporation from soil and surface waters, soil erosion and manufacture and use in
developing countries.
Once in the environment, DDT in soil or water sediment persists for a very long time.
Some DDT may evaporate from the soil and may be broken down partially by the sun or
microorganisms. DDT in soil can be absorbed by some growing plants and can expose the
animals and human who eat those crops. DDT in water and sediment can be absorbed by
small aquatic organisms and then concentrate in fish eating these organisms. The level of
DDT in animals and people are higher than in the environment because lipid-containing
cells accumulate DDT and its metabolism is very slow.
Due to the long-lasting systematic application, the hexachlorocyclohexane had slowly
spread in the environment. It became a serious environmental organic compound and
consequently one of the target pollutants. The HCH residues survived in soils for some
tenths of years. The determination of HCH cumulation levels in soils and consequently in
agricultural products has still remained highly actually due to its chemical and biological
stability.
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4.5 Exposure pathways and metabolism
4.5.1 DDT
Human general population is exposed to DDT mainly by eating foods (meat, milk, fish,
eggs) still containing small amounts of this compound. Infants can be exposed with drinking
of breast milk. Generally, the highest DDT levels are being found in human fat.
Because of low solubility, drinking water is a negligible source of DDT exposure. Also,
DDT inhaled with air represents less than 1 % of its total daily intake. DDT does not enter
the body through the skin very easily except direct skin exposure during spraying (Geyer et
al. 1986).
Even though DDT was not used in Slovakia since the late 70s, soil and sediment still
contain DDT, which contaminates agricultural crops (especially root vegetables) and
surface water respectively. Moreover, grazing cattle or poultry can ingest DDT directly
from soil. Although regularly inspected, imported foods from regions, where DDT is still
used, can be more contaminated by this insecticide.
Once inside the body, DDT can slowly break down to form DDE and DDD whose
metabolites leave the body in urine (as hydroxylated DDE and bis(4-chlorophenyl)acetic
acid respectively). Breast-feeding is another way of decreasing DDT levels in mother´s
bodies. DDE can also be metabolized to a persistent and lipid-soluble methylsulphonyl
compounds, which can in some species of experimental animals influence adrenal cortex
activity.
4.5.2 HCB
The general human population is exposed to HCB mainly via food intake (about 92 %),
and much less via breathing (7 %), drinking (1 %) or skin contact. Workers may be exposed
to higher concentrations of HCB than the general population, particularly in the
manufacture of chlorinated solvents, and in the manufacture and application of pesticides
contaminated with HCB.
In animals and humans, HCB accumulates in lipid-rich tissues, such as adipose tissue,
adrenal cortex, bone marrow, skin and some endocrine tissues, and can be transferred to
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offspring both across the placenta and via mothers´ milk. HCB undergoes limited
metabolism, yielding pentachlorophenol, tetrachlorohydroquinone and pentachlorotiophenol
as the major metabolites in urine. Elimination half-lives for HCB range from approximately
one month in rats and rabbits to 2 or 3 years in monkeys.
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4.6 Toxicological effects
4.6.1 DDT
Eating food containing high DDT levels over a short time mostly affects the nervous
system. People who accidentally swallowed large amounts of DDT became excitable and
suffered tremors and seizures (US DHHS, 1994a). These effects on the nervous system went
away once exposure stopped. Tests in laboratory animals confirm the effects of DDT on the
nervous system. Workers manufacturing DDT exposed for a long time to DDT had some
reversible changes in the levels of liver enzymes. However, there was no sign that DDT
caused permanent harmful effects.
Animal studies have shown that long term exposure to DDT may affect the liver and
may adversely influence reproduction. There is sufficient evidence for the carcinogenity of
DDT in experimental animals (IARC, 1982). When administrated orally in the diet or by
stomach tube, DDT induced hepatomas in mice and rats and lymphomas and lung
carcinomas and adenomas in mice. When administrated by subcutaneous injection, DDT
induced liver tumors in mice. The evidence for the carcinogenicity of DDT administrated
orally was negative in studies with hamsters and inconclusive in studies with dogs and
monkeys.
The results of oral administration of DDE and DDD were conclusive. In male rats, DDD
induced follicular cell carcinomas and adenomas of the thyroid. DDE induced
hepatocellular carcinomas in mice of both sexes.
Studies of DDT-exposed workers did not show increases in deaths or cancer. However,
these studies had problems or flaws so possible increases in cancer may not have been
detected. IARC has determined that DDT, DDE, and DDD are possible carcinogenic in
humans (Group 2B). The U.S. EPA considers them to be probable human carcinogens.
4.6.2 HCB
The acute toxicity of HCB to experimental animals is low (1 000 to 10 000 mg/kg body
weight). In animal studies, HCB is not a skin or eye irritant and does not sensitize the
guinea-pig (EHC, 1997).
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The available data on the systemic toxicity of HCB indicate that the pathway for the
biosynthesis of heme is a major target of HCB toxicity. Elevated levels of porphyrins and/or
porphyrin precursors have been found in the liver, other tissues and excreta of several
species of laboratory mammals exposed to HCB. Porphyria has been reported in a number
of studies in rats with subchronic or chronic oral exposure. Repeated exposure to HCB has
also been shown to affect a wide range of organ systems (including the liver, lungs, kidneys,
thyroid, skin, and nervous and immune systems), although these have been reported less
than porphyria. In experimental animals such as rats, mice and hamsters fed with diets
containing HCB, there were increases in the incidence of liver, bile duct, kidney, thymus,
spleen and lymph node tumors (EHC, 1997).
HCB has little capacity to induce directly gene mutation, chromosomal damage and
DNA repair. It exhibited weak mutagenic activity in a small number of the available studies
on bacteria and yeast, although it should be noted that each of these studies has limitations.
There is also some evidence of low-level binding to DNA in vitro and in vivo, but at levels
well below those expected for genotoxic carcinogens.
In studies of reproduction, maternal exposure to HCB was found to be hepatoxic and/or
affected the survival or growth of nursing springs, birth weight, neurobehavioural
development, and others.
The results of a number of studies have indicated that HCB affects the immune system.
Exposed rats and monkeys had histopathological alternations in the thymus, spleen, lymph
nodes, and/or lymphoid tissues of the lung. Humoral immunity and, to a lesser extent, cellmediated immunity were enhanced by several weeks exposure to HCB in the diet of the
rats, while macrophage function was unalterned. In a number of studies on various strains of
rats, short-term or subchronic exposure to HCB affected thyroid function, as indicated by
decreased serum levels of total and free thyroxin (T4) and often, to a lesser extent,
triiodothyronine (T3).
Most data on the effects of HCB on humans originate from accidental poisonings that
took place in Turkey in 1955-1959, in which more than 600 cases of porphyria cutanea
tarda (PCT) were identified. In this incident, disturbances in porphyria metabolism,
dermatological lesions, hyperpigmetation, hypertrichosis, enlarged liver, enlargement of
thyroid gland and lymph nodes, and osteoporosis or arthritis were observed, primarily in
children. Breast-fed infants of mothers exposed to HCB developed a disorder called "pembe
yara" (pink sore) and most died within a year. There is also limited evidence that PCT
occurs in humans with relatively high exposure to HCB in the workplace or in the general
environment (EHC, 1997).
The few available epidemiological studies of cancer are limited by small size, poorly
characterized exposures to HCB and exposure to numerous other agents, and are
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insufficient to assess the carcinogenity of HCB to humans. However, as there are sufficient
evidences for the carcinogenity of HCB in experimental animals IARC and US EPA have
classified HCB as possibly carcinogenic to humans (Group 2B) (IARC, 1987; US DHHS,
1994b).
The following health-based guidance values for the total daily intake (TDI) of HCB in
humans have been suggested: for non-cancer effects, 0.17 µg.kg-1 body weight.day-1
neoplastic effects, 0.16 µg.kg-1 body weight.day-1
(**)
(*)
; for
(EHC, 1997).
(*)
Based on the lowest reported NOEL (0.05 HCB/kg body weight per day), for primarily hepatic effects
observed at higher doses in studies on pigs and rats exposed by the oral route, and incorporating an
uncertainty factor of 300 (x 10 for interspecies variation, x 10 for intraspecies variation, and x 3 for
severity of effects), TDI of 0.17 mg/kg body weight per day has been derived.
(**)
The approach for neoplastic effects is based on the tumorigenic dose TD5, i.e., the intake associated
with a 5 % excess incidence of tumors in experimental studies in animals. Based on the results of the twogeneration carcinogenity bioassay in rats and using the multistage model, the TD5 value is 0.81 mg/kg
body weight per day for neoplastic nodules of the liver in females. Based on consideration of the
insufficient mechanistic data, an uncertainity factor of 5 000 was used to develop a health-based guidance
of 0.16 mg/kg body weight per day.
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4.7 Other chlorinated pesticides with PBT characteristics
The main constituents in technical CHLs are trans-chlordane (gamma-chlordane), cischlordane (alpha-chlordane), heptachlor, trans-nonachlor, cis-nonachlor. Heptachlor is one
of the most active components of technical chlordane, while technical heptachlor is used as
a pesticide. Some constituents of technical chlordane, as well as metabolites (oxychlordane
and heptachlorepoxide) are compounds very persistent under environmental conditions they
are bioaccumulated in animals and humans and are chiral (Falandysz et al., 1998).
Chlordane is not produced in Europe and Japan. This insecticide was used world-wide
and mostly in USA, south-eastern Asia and Australia. Technical chlordane was used for a
short time and small quantities in the past in Poland, and also in the Scandinavian countries
up to 1960s. Technical heptachlor also was used for a short time and in small quantities in
the past in Poland and also in Finland was used (at rate up to 60 tons annually). Dieldrin and
aldrin were imported in small quantities (< 100 tons) and used for in Poland between 1985
and 1971. Melipax (Toxaphene) is an example of the board action insecticide registered and
used extensively in Poland in the place of DDT, and no other cyclodienes (endrin, isodrin,
endosulphane 1 and 2, mirex) were registered in Poland.
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4.8 References
Bratanová Z., Kovačičová J., Gopina G. (1998): A review of existing data on the
occurrence of pesticides in water of the River Danube and its tributaries. Fresenius Envir.
Bull. 7, 495-501.
Dabrowski J., Silowiecki A., Heinisch E., Wenzel-Klein S. (1994): Anwendung
chloroorganischer Pestizide und hieraus entstehende okologische-chemische und
okotoxikologische Folgen. In: E. Heinisch, A. Kettrup, S. Wenzel-Klein (eds.)
Schaddstoffatlas Osteuropa. Okologisch-chemische und okotoxikologische Fallstudien uber
organische Spurenstoffe und Schwermetalle in Ost-Mitteleuropa. Ecomed, landsberg/Lech.,
19-24.
EHC (1997): Hexachlorobenzene. Environmental Health Criteria No. 195. World Health
Organization, Geneva, 160 pp. (ISBN 92 4 157195 0).
Falandysz J., Strandberg B., Strandberg L., Berqvist P.-A., Rappe C. (1998):
Concentrations and spatial distribution of chlordanes and some other cyclodiene pesticides
in Baltic plankton. Sci. Total Environ. 215, 253-258.
Geyer H., Scheunert I., Korte F. (1986): Bioconcentration potential of organic
environmental chemicals in humans. Regulat. Toxicol. Pharmacol. 6, 313-347.
Heinisch E, Wenzel-Klein S. (1994): Produktion und Anwendung von Chlorkohlenwasserstoff Pestiziden in der ehemaligen DDR. In: E. Heinisch, A. Kettrup, S. WenzelKlein (eds.) Schaddstoffatlas Osteuropa. Okologisch-chemische undokotoxikologische
Fallstudien uber organische Spurenstoffe und Schwermetalle in Ost-Mitteleuropa. Ecomed,
landsberg/Lech., 4-7.
Heinisch E., Kettrup A., Holoubek I., Matoušek J., Podlešáková E., Hecht H., Wenzel
S. (1997a): Persistente organische Verbindugen in Nahrugsketten 7 von Bayern und
Tschechien. Teil 1: Terrestrische Systeme. GSF-Berichte 10/97, Munich, FRG, 371 p.
Heinisch E., Kettrup A., Holoubek I., Langstädtler M., Podlešáková E., Svobodová Z.,
Wenzel S. (1997b): Persistente organische Verbindugen in Nahrugsketten 7 von Bayern
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und Tschechien. Teil 2. Aquatische Systeme. GSF-Berichte 11/97, Munich, FRG, 318 p.
Heinisch E., Kettrup A., Holoubek I., Wenzel S. (1997c): Persistente organische
Verbindugen in Nahrugsketten 7 von Bayern und Tschechien. Teil 3: Persistente organische
Verbindugen in Unteren Teil der Troposphäre in Bayern und Tschechien - Zusammenhänge
von Emission und Kontamination. GSF-Berichte 12/97, Munich, FRG, 189 p.
Holoubek I., Tříska J., Cudlín P., Čáslavský J., Schramm K.-W., Kettrup A.,
Kohoutek J., Čupr P., Schneiderová E. (1996): Project TOCOEN (Toxic Organic
COmpounds in the ENvironment). Part XXXI. The occurrence of POPs in high-mountains
ecosystems of the Czech Republic. Toxicol. Environ. Chem. 66, 17-25.
IARC (1982): Monographs on the Evaluation of the Carcinogenic Risk of Chemicals to
Humans (Supplement 4). International Agency for Research on Cancer, Lyon.
IARC (1987): Overall Evaluation of Carcinogenity: An Updating of IARC Monographs
Volumes 1 to 42 (Supplement 7). IARC Monographs on the Evaluation of Carcinogenic
Risks to Humans, Lyon.
Koci K. (1998): The trend of POP pollution in the Albanian Adriatic Coast. Case study
PCBs (1992-1996). In: UNEP/IFCS, 101-106.
PHARE (ZZ911/0106) (1997): Environmental Programme for the Danube River Basin:
Danube Regional Pesticide Study. Final Report. April 1997, 40 pp.
Roots O. (1996): Toxic chloroorganic compounds in the ecosystem of the Baltic Sea.
Estonian Environment Information Centre (EEIC). Tallinn, Estonia, 144 pp.
Schlosserova J. (1993): Evaluation of hexachlorocyclohexane residues in different
localities of the Slovak Republic. In: International HCH and halogenated pesticides Forum,
122-129.
Stobiecki S. (1998): The problem of unwanted pesticides in Poland. In: UNEP/IFCS, 283284.
Tasheva M. (1998): Persistent organic pesticides in Bulgaria. In: UNEP/IFCS, 279-282.
Toader C., Chitimiea S. (1998): The fate of some persistent organic pesticides in a
particular Romanian aquatic ecosystem. In: UNEP/IFCS, 309-314.
US DHHS (1994a): Toxicological Profile for 4,4,'-DDT, 4,4,'-DDE, 4,4,'-DDD (Update). U.
S. Department of Public and Health Service, Agency for Toxic Substances and Disease
Registry (Prepared by Clement International Corporation for US DHHS), TP-93/05,
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Atlanta, GA, 166 pp.
US DHHS (1994b): Toxicological Profile for Hexachlorobenzene (Draft). U.S. Department
of Public and Health Service, Agency for Toxic Substances and Disease Registry (Prepared
by Research Triangle Institute for US DHHS), Atlanta, GA, 198 pp.
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5.2 Sources
HCB was widely used as a pesticide, mainly as a seed dressing to prevent fungal disease
on grain and field crops. In industry, HCB has been used directly in the manufacture of
pentachlorophenol, in the production of pyrotechnic compositions for military purposes,
tracer bullets, as a peptizing agent in the production of nitroso and styrene rubber for tires in
the synthetic rubber manufacture, as a fluxing agent in primary aluminium production, as a
wood preservative, a porosity-control agent in the manufacture of graphite anodes, as a
chemical intermediate in dye manufacturing and as a plasticiser for polyvinylchloride).
It is generated as a by-product in the manufacture of chlorinated solvents
(tetrachloroethylene, trichloroethylene, carbon tetrachloride), some pesticides
(pentachloronitrobenzene - PNCB, tetrachloroisophthalonitrile - chlorothalonil,
pentachlorophenol - PeCP etc.), and other chlorinated compounds (vinyl chloride?), which
are used in metal smelting and electrolyses. An important source of HCB is represented by
high-temperature processes (incineration of waste, plastics, PCBs, combustion of fuel
containing chlorine, coal and steel producers and other metallurgical processes, including
metal recycling, internal-combustion engine operation, fires). HCB has been detected in
emissions from number of other industries, including paint manufactures, textile mills, soap
producers, probably reflecting the use products with HCB.
Currently, the principal sources of HCB in the environment are estimated to the
manufacture of chlorinated solvents, the manufacture and application of HCB-contained
pesticides, and inadequate incineration of chlorine-containing wastes. HCB is a contaminant
of a number of chlorinated pesticides. Since most current applications for these products are
dispersive, most HCB from this source will be released to the environment.
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5.3 Sources and production in CEE countries
Hexachlorobenzene (HCB) was used world-wide as a fungicide for agricultural
purposes from 1915. That compound was also registered in Poland and sold as a fungicide
under the trade name "Śnieciotox". Around 1980 hexachlorobenzene become unpopular and
finally was withdrawn from the agriculture in Poland (Falandysz et al., 2000).
Pentachlorobenzene (PeCBz) is a substrate used for the synthesis of the fungicide
pentachloronitrobenzene (PeCNBz), and apart from this application it has not found any
other special application. Pentachlorobenzene like HCB is a technical impurity in some
chemical formulations (up to 0.06 % in technical formulation of HCB, and also was found
in technical formulation of PCNBz). Another source of environmental pollution with HCB
and PCBzs are high temperature processes such as municipal solid waste incineration. All
theoretically possible congeners of chlorobenzene were identified in flue gas and fly ash
from the municipal solid waste incinerators, and contribution from PCBzs and HCB was up
to ~50 % and ~13 %, respectively. Hexachlorobenzene is highly persistent under
environmental conditions. Nevertheless, depending on the environmental matrix, HCB
slowly undergoes abiotic (photochemical) and biotic (mainly metabolised by bacteria and
lower fungi in soil and sediments as well as by man and animals) degradation.
Pentachlorobenzene is an intermediate product in metabolism of HCB and of the insecticide
Lindane (gamma-HCH).
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5.4 Environmental fate
HCB is distributed throughout the environment because it is mobile and resistant to
degradation. Volatilisation from water to air and sedimentation following adsorption to
suspended particles are the major removal processes from the water. Once in the sediments,
HCB will tend to accumulate and become trapped by overlying sediments. Although HCB
is not readily leached from soils and sediments, some desorption may occur and may be a
continuous source of HCH to the environment, even if inputs to the system cease.
Biological degradation is not considered to be important for the removal of HCB from water
or sediments. In the troposhere, HCB is transported overlong distances by virtue of its
persistence, but does undergo slow photolytic degradation or is removed from the air via
atmospheric deposition to the water and soil. In soil, volatilisation is the major removal
process the surface, while slow aerobic and anaerobic biodegradation are the major removal
process at lower depths.
The bioaccumulative properties of HCB result from the combination of its
physicochemical properties (high Kow) and its slow elimination due to limited metabolism
related to its high chemical stability. Organisms generally accumulate HCB from water and
food, although benthic organisms may also accumulate HCB directly from sediment.
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5.5 Exposure pathways and metabolism
This chapter will be published during 2000.
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5.6 Toxicological effects
This chapter will be published during 2000.
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5.7 References
Falandysz J., Strandberg L., Strandberg B., Bergqvist P.A., Rappe C. (2000):
Pentachlorobenzene and hexachlorobenzene in fish in the Gulf of Gdańsk. Pol. J. Environm.
Stud. 9, in press.
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6.2 Sources
Polychlorinated biphenyls (PCBs) are industrial products or by-products formed at
industrial processes (Holoubek et a., 1994; Kočan et al., 1994a, 1996). Owing to appropriate
physical-chemical properties (inert, insulting and lipophilic), PCBs were widely applied in
industry, either in industry, either in closed systems (coolants and lubricants in
transformers, dielectric fluids in capacitors, hydraulic fluids and heat-transfer media), or in
open systems (plastificators, additives into carbonless copy paper, lubricants, inks,
impregnating and paint agents, glue, wax, cement and plaster additives, lubrication of cast
blocks, materials for dust separators, sealing liquids, flame retardants, immersion oils and
pesticides. The excellent properties of PCBs for industrial use also make it hazardous to the
environment.
Unlike pesticides, such as DDT, PCBs has not been deliberately spread in the
environment (Bremle, 1997). Large volume of PCBs have been emitted by the open burning
or incomplete incineration of waste, and by leakage from landfill sites and in the vicinity of
factories. Another source is diffuse emission from such PCBs-containing materials as
paints, coatings and plastics. The cities are sources of PCBs on regional scale (Halsall et al.,
1995), due in particular to the out-gassing of PCBs from buildings. There has also been
release of it due to accidents, such as in souls of transformer oil. The ban on PCBs in many
countries did not lead to any immediate decrease of it in the environment. Rather, PCBcontaining materials that were replaced often ended up on municipal landfills.
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6.3 Sources and production in CEE countries
In the former Czechoslovakia, PCBs were manufactured from 1959 to 1984 in a
chemical plant in eastern Slovakia under the commercial name Delor. From the total
21 482 t produced (+ about 1 600 t PCB wastes), 46 % was exported and the remainder was
appointed for the home market of former Czechoslovakia. Within both countries (Czech
Republic and Slovakia), PCB formulations may be currently used only in the closed systems
and they are gradually replaced. Currently, waste landfillings is considered to be the most
relevant source of environmental pollution by PCBs in these countries. Estimated
contribution of applied paint to total PCB pollution within Slovakia is about 5 % and that of
industrial and municipal waste incinerators is 9 %.
It was recently rather unknown that Poland had its two own technical PCB
formulations - Chlorofen, which is similar in appearance and composition to Aroclor 1262,
and Tarnol, which is similar to Aroclor 1254 (Falandysz, 1998).
Tarnol, which was also called "Chlorowany bifenyl", was a low chlorinated technical
PCB formulation manufactured between the years 1971 and 1976 by the company Zakłady
Azotowe in Mościce near the city of Tarnów in southern-east Poland (Falandysz et al., 1993;
Falandysz, 2000). The mixture is in its physical appearance and properties similar to well
known foreign technical PCB mixtures such as Aroclor 1248, Clophen A 40, Phenoclor DP4, Fenchlor 42 or Kanechlor 400. Tarnol was a product of the "anti import philosophy",
which was on the agenda of the government in the 1970s. The total quantity of
manufactured Tarnol in 679 tonnes. Tarnol was a colour-less clear liquid of density 1.451.47 g.ml-1 in 20 °C. Chlorobiphenyl isomer and congener composition of Tarnol is
unknown in detail. According to the manufacturer of Tarnol this mixture was composed
mainly of trichlorobiphenyls with di-, tetra- and pentachlorobiphenyls as a minor
constituents. Nevertheless, the composition of Tarnol was not confirmed using the capillary
gas chromatography and low/high resolution mass spectrometry (HRGC-LR/HRMS) for
analysis. No official data on the kinds of use of the Tarnol were released - it seems that it
was used exclusively as an dielectric fluid mainly for the transformers but use as dielectric
in capacitors could be also possible.
Chlorofen was a highly chlorinated (63.6 % Cl) PCBs formulation manufactured in the
town of Zšbkowice Ślšskie in southern Poland. The mixture was a light to dark-brown
sticky and viscous resin mainly composed of PCB congeners with 5 to 9 chlorine atoms that
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comprised 99.55 % of total PCBs. The average number of Cl per biphenyl molecule in
Chlorofen is 7.3 and the average molecular weight is 405.4. Chlorofen contains at least 59
PCB congeners with the major components such as PCBs Nos. 153 of hexa-, 176, 180 and
187 of hepta-, 194, 195, 198, 201/196 of octa- and 206 of nonachlorobiphenyls.
Industrialised countries such as USA and Western European countries have some
legislative measures for controlling the flux of PCBs in the environment. One important
aspect is control of PCBs sources such as transformers, capacitors, electric motors etc. The
materials containing more then 50 µg.g-1 are subject to some regulations. These regulations
are adopted in CEE countries. Since 1993, in Poland the waste oils containing PCBs were
included on the list of hazardous substances, but to the present days the flux of these
pollutants was not a subject of any regulation (Lulek, 1996). Recently available data
(Gurgacz, 1994) have indicated that in national power plant installations about 1 400 tons of
transformers and capacitors oils are used. However, unknown is even estimated amount of
the waste industrial oils (transformers, capacitors, motors etc.) occurred in the trade. An
assessed percentage of PCB contaminated equipment is following: transformers (0.38 %),
capacitors (35-50 %), other electromagnetic equipment (25-50 %). An assessed amount of
PCB contaminated oil/capacitors/other electromagnetic equipment is up to 10 000 tonnes
(Falandysz, 2000). Determination the levels of PCBs in the random samples of waste motor
and transformer oils collected from different regions of Poland showed that these
concentrations in the most of samples did not exceed the limit value of 50 µg.g-1 (Lulek,
1996).
There has been no PCBs production in the other countries of the region. PCBs can still
be found in many closed systems, dumps and environmental matrixes in all the countries in
the region. For example, in Croatia in 1997, more than 2 000 tonnes of PCBs oils from
various countries were imported (Sinovčevič, 1998).
Part of PCBs amounts from various countries of the region was exported to the France
for destruction. Part of PCBs amount used in the region, was liquidated legally, and part
probably illegally during the period of main economic changes in these countries in the
early 1990s. Unknown part of total used amount of PCBs is still in the various
environmental compartments.
The recent inventory of PCBs in Slovakia (Kočan et al., 1999) gave the following actual
PCBs equation in this country:
PCBs (Wastes from production - 1 606 t) + PCBs (Products - 4 071 t) = PCBs (Still used 960 t) + PCBs (Liquidated - 368 t) + PCBs (Disposed - 1 605 t) + PCBs (Rest - 2 744 t)
In Croatia, there are 405 users of 22 532 PCBs capacitors and 293 users of PCBs
transformers (Sinovčevič, 1998).
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The use of PCBs in Slovenia increased after 1960, when an ISKRA condenser factory
was built in Semič, Bela Krajina (about 80 km south-east from Capitol Ljubljana) (Polič and
Leskovšek, 1996). PCBs were introduced into the production process in 1962 (until 1970
Clophen A-50 and A-30 supplied by Bayer, FRG and between 1970 and 1985 Pyralen 1500
supplied by Prodelec, France). The consumption of PCBs by ISKRA in period 1962-1985
totalled about 3 700 tons with a PCBs waste rate of 8-9 % in the form of waste impregnates,
condensers, etc. By 1974, 130 tons of waste containing around 70 tons of pure PCBs were
dumped at various waste sites within five km round the factory. After 1975 waste
impregnates were collected and sent to France for treatment (170 t), whereas smaller waste
condensers were still disposed of at local waste site. Measurements in 1982 showed very
high concentration of PCBs in the environmental compartments (air, water, sediments), as
well as in food and in animal and human tissues (Polič and Kontič, 1987).
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6.4 Environmental fate
PCBs evaporate very slowly and they are not very soluble in water. Nevertheless, they
have dispersed widely through both atmospheric processes and watercourses and trace
amounts are found in soils, surface waters, sediments and air throughout the world. Whereas
their stability was a welcome feature for industrial use, their resistance to degradation
means that they have accumulated in the environment and their presence will persist long
after their use has been phased out. PCBs are soluble in fat and they have been assimilated
through the food chain into the body fats of animals. Elevated levels of PCBs have been
reported in many aquatic and terrestrial species. Because of this tendency of PCBs to
accumulate in animal tissues and concern over possible adverse effects on wild life, they
have been classified as "eco-toxic".
Although the use of PCBs is banned in most countries today, its persistence and its
widespread use lead to its remaining in the ecosystem and being spread further, to rural and
pristine areas of the globe (Wania and Mackay, 1993; Bremle, 1997). According to the global
fractionation theory, chemicals emitted in warmer climates volatilize and are transported by
air currents to colder areas where they are deposited onto soil and water. The globe has been
said to function as a distillation apparatus or as a GC-column separating compounds of
differing volatility.
For example, PCB congeners having one chlorine can move world-wide without being
deposited, whereas congeners with 8-9 chlorines tend to be deposited closer to the source.
The concentration of volatile compounds is thus low in tropical areas and higher in
temperate or polar regions (Wania and Mackay, 1996).
In addition to the long-range transport of PCBs globally, there is also a circulation of
PCBs from soil and point sources which influences its concentration in the air on a more
regional scale. The temperate industrialized nations, where on through the 1960s-1970s
PCBs was manufactured and used extensively, are regarded as the source areas of PCBs on
global scale (Harrad et al., 1994). Contaminated aquatic environments can also act as sources
of persistent pollutants in the atmosphere since such compounds are readily volatilized from
water, as shown in the Great Lakes in North America (Achman et al., 1994; Hornbuckle et al.,
1993) and Lake Baikal in Russia (Iwata et al., 1995). If the fugacity, or escaping tendency, of
one compartment exceeds that another, PCBs will diffuse from the former to the latter,
volatilizing from contaminated soil or water bodies to the air, for example, or being
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deposited from contaminated air to cleaner soil or to water (Bremle, 1997).
A mass balance of PCBs in UK and other countries (Harrad et al., 1994) showed that soil
retained a larger amount of PCBs than other compartments did (air, freshwater, sediment, or
biota) and is today the greatest source (90 %) of it for the atmosphere through re-circulation.
The PCBs deposited from the atmosphere to the soil in the 1960s and 1970s are revolatilizing to the air now as a result of equilibrium partitioning (Harner et al., 1995). The outgassing of the more chlorinated congeners from the soil has been delayed due to their lower
volatility. The volatilization of PCBs from the soil is dependent on the ambient temperature
and on the vapour pressure and lipophilicity of these compounds. The successive line of
properties of different PCB congeners ranging from being low to high in chlorination,
follows the sequence from smaller to larger molecules, from lower to higher lipophilicity
and from higher to lower vapour pressure. The less chlorinated PCB congeners are thus
more readily partitioned to the air. The more highly chlorinated congeners, in turn, tend to
be associated with particles or with and organic carbon.
The major input of PCBs to freshwater ecosystems is by of the atmosphere (Bremle,
1997). Aerial fluxes of PCBs to the ground occur through (1) rain and snow´s scavening
vapours and particles, i.e. by wet deposition, (2) dry particle deposition, and (3) vapour
exchange across different interfaces, such as air/water, air/soil or air/plant surfaces
(Bidleman, 1988). Apart from air to water, as rain on the water surface, the PCBs deposited
on soil and vegetation can also reach the water body as a result of wash-out by precipitation
from the catchment area. The types of soils and land use in catchment areas also influence
the amount of leakage to freshwater.
In water, PCBs can exist either truly dissolved or adsorbed to suspended particles
(Eisenreich, 1987; Bremle, 1997). Although the water solubility of PCBs is low, the amount of
PCBs dissolved in water is so large. Due to the presence of suspended particles with
adsorbed PCBs, the amount of PCBs in water can sometimes exceed what would be
expected from the PCB´s water solubility. The water solubility of PCBs can also be
enhanced by humic material or dissolved organic carbon being present in water. The
transport of PCBs in rivers occurs partly as PCBs that is truly dissolved, partly through its
being associated with particles, and partly through the so-called bed load of sediment
movements. In rivers containing only small amounts of particles, the major transport of
PCBs occurs in the dissolved phase. PCBs loss from the water mass occurs through
partitioning or through sedimentation to the sediment (Eisenreich, 1987). The sediment can
also act as a source of it through desorption and through resuspension. Volatilization to air
also removes PCBs from the water phase.
The uptake of PCBs in aquatic and benthic biota is mainly governed by the lipophilicity
of the compound in question, which can be expressed by its octanol/water partitioning
coefficient. Besides the direct partitioning of PCBs between water and the fat pool via gills
of fish and other organisms, food is a source of contaminants for aquatic biota. In addition,
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physiological control of uptake, steric hinderance of large molecules, distribution of
chemicals within organims, biotransformation and biodegradation all affect the level of
pollutants (Barron, 1990; Larson et al., 1996). Species-specific factors such as fat-content, agedistribution, growth-rate, and prey selection likewise affect PCB concentrations.
For terrestrial organisms, the passive process of exchange between the organism and the
surroundings in the uptake and loss of organic pollutants, as is the case for aquatic biota,
does not generally occur (Bremle, 1997). The partitioning between air and the lung of an
organism is more limited, due to the respiration volume being low compared with that of
gill-breathing aquatic organisms. The partitioning between an organism and water is also
more thermodynamically favoured than between an organisms in the soil, such as
earthworms that can gain or lose chemicals via the soil water, the main route for the uptake
of pollutants by terrestrial organisms is by ingestion. Aquatic mammalian predators seem to
have higher concentrations of pollutants than terrestrial ones. Animals higher up in a food
chain often have higher levels of PCBs and other PBT compounds (biomagnification). Top
predators, especially in the terrestrial food chain, have a characteristic PCB pattern in which
only few of congeners dominate (Bremle, 1997; Bremle et al., 1997). The elimination of PCBs
from terrestrial organisms is mainly in terms of metabolization (Walker, 1990).
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6.5 Exposure pathways and metabolism
PCBs can enter the human body by inhalation, ingestion or, by direct contact, through
the skin. The trace quantities present in most people are the result of ingestion through the
food chain. PCBs accumulate in fatty tissues and can be transmitted in breast milk and
across the placenta.
The pathways of human exposure to PCBs and their relative contribution to the daily
intake are identical to those of PCDDs and PCDFs as these pollutants are present in the
same environmental compartments and food commodities.
Metabolism of a PCB congener usually begins with oxidation under the influence of an
enzyme of the cytochrome P450 type. The immediate result is what is known as an arene
oxide, but here the oxygen atom is incorporated in such an unstable group that this first
metabolic step is very short-lived. The arene oxide is quickly broken up and usually
replaced by a hydroxy group. The hydroxy group makes the molecule relatively soluble in
water, which normally enables it to be rapidly excreted from the body.
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6.6 Toxicological effects
Toxic effects are difficult to predict because of the complex nature of PCBs and the
common mixture of other chemicals as impurities. A significant part of the toxicity
associated with commercial PCB mixtures is related to the presence of the small number of
planar congeners. These compounds induce several similar toxic effects in mammals and
birds, such as hepatoticity, immunotoxicity, and reproductive toxicity (Eisler and Belisle,
1996). PCBs have a low acute toxicity and adverse effects have been more commonly
associated with chronic exposure to PCBs. No documented incidents of human cancer have
been associated with PCB exposure although experiments on animals have shown
carcinogenic effects.
No information is available on the acute (short-term) effects of PCBs to humans.
Animal studies reported effects on the liver, kidney, and CNS from oral exposure to PCBs.
Acute animal tests, such as the LD50 test in rats, have shown PCBs to have moderate acute
toxicity from oral exposure.
Chronic (long-term) exposure to PCBs by inhalation in humans has been reported to
result in respiratory tract symptoms, such as cough and tightness of the chest,
gastrointestinal effects, including anorexia, weight loss, nausea, vomiting, and abdominal
pain, mild liver effects, and effects on the skin and eyes, such as chloracne, skin rashes, and
eye irritation. Oral exposure to PCBs in humans has been associated with cardiovascular
effects, including hypertension, mild liver effects, and effects on the skin such as
pigmentation and acne (US DHHS, 1993).
PCBs can reach a developing fetus (across the placenta) or be transferred to a newborn
(via mother´s milk) which is a circumstance of great concern. An epidemiological study
reported that babies born to women occupationally exposed to high levels of PCBs had
lower birth weights and shortened gastetional age, as compared with babies born to women
exposed to low concentrations of PCBs. Two human studies that investigated exposure to
PCBs through the consumption of contaminated fish suggest that exposure to PCBs may
cause developmental effects in humans. Both studies reported neurodevelopmental effects,
such as motor deficits at birth, impaired psychomotor index, impaired visual recognition,
and deficits in short-term memory in infants of mothers exposed to PCBs. Human studies
are not conclusive on the reproductive effects of PCBs. One study of men who were
occupationally exposed to PCBs showed no fertility abnormalities, while another study of
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men with low sperm counts found elevated levels of PCBs in the blood and an association
between certain PCB compounds in semen and decreased sperm motility. Animal studies
have reported the developmental effects, such as learning deficits, impaired immune
functions, focal liver necrosis, and cellular alterations of the thyroid, in the offspring of
animals exposed orally to PCBs. Reproductive effects, such as decreased fertility, decreased
conception, and prolonged menstruation, have also been noted in oral animal studies (US
DHHS, 1993).
Human studies provide inconclusive, yet suggestive evidence of an association between
PCBs´ exposure and liver cancer. Several studies have reported an increase in liver cancer
among persons occupationally exposed to some PCB formulations. However, the studies are
inconclusive due to confounding exposures and lack of exposure quantification. Oral
exposure studies in animals show an increase in liver tumors in rats and mice exposed to
several commercial mixtures of PCBs and to several specific congeners. No animal
inhalation studies are available on PCBs. EPA has classified all PCBs as Group B2,
probable human carcinogens (US DHHS, 1993). Equally, IARC concluded that PCBs are
probable carcinogenic to humans (Group 2A) (IARC, 1987).
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6.7 References
Achman D. R., Hornbuckle K. C., Eisenreich S. J. (1993): Volatilization of
polychlorinated biphenyls from Green Bay, Lake Michigan. Environ. Sci. Technol. 27, 7587.
Bidleman T. (1988): Atmospheric processes. Wet and dry deposition of organic
compounds are controlled by their vapour-article partitioning. Environ. Sci. Technol. 22,
361-367.
Bremle G. (1997): Polychlorinated biphenyls (PCBs) in a river ecosystem. PhD Thesis.
Dept. Ecol., Chem. Ecol. and Ecotoxicol., Lund University, Lund, Sweden.
Bremle G., Larsson P., Heldin J. O. (1997): Polychlorinated biphenyls in a terrestrial
predator, the pine marten (Martes martes, L.). Environ. Toxicol. Chem.
Eisenreich S. J. (1988): The chemical limnology of nonpolar organic contaminants: PCBs
in Lake Superior. In: Source and fates of Aquatic Pollutants. (Eds. Hites RA, and Eisenreich
SJ.), pp. 393-469. Washington, D.C., ACS Advanes in Chemistry Series # 216, ACS.
Eisler R., Belisle A. A. (1996): Planar PCB hazards to fish, wildlife, and invertebrates: a
synoptic review. National Biological Service Biologial Report 31, 75 pp.
Falandysz J., Yamashita N., Tanabe S., Tatsukawa R. (1993): Composition of PCB
isomers and congeners in technical Chlorofen formulation produced in Poland, 305-312,
Environmental Analytical Chemistry of PCBS. J. Albaigés (red.). Current topics in
environmental and toxicological chemistry, vol. sixteen, Gordon and Breach Science
Publishers, 1993, Singapore.
Falandysz J. (1998): Polychlorinated naphthalenes: an environmental update. Environ.
Pollut. 101, 77-90.
Falandysz J. (2000): Manufacture, use, inventory and disposal of polychlorinated
biphenyls (PCBs) in Poland. Organohalogen Compd. (to be submitted; Dioxin ´2000,
Monterey, USA).
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Gurgacz W. (1994): Waste oils and dioxins. 1st Symposium Dioxin-Human-Environment,
Krakow, Poland, 14-26.
Hallsall C. J., Lee R. G. M., Coleman P.J., Burnett V., Harding-Jones P., Jones K. C.
(1995): PCBs in UK urban air. Environ. Sci. Technol. 29, 2368-2376.
Harner T., Mackay D., Jones K. C. (1995): Model of the long-term exchange of PCBs
between soil and the atmosphere in the southern UK. Environ. Sci. Technol. 29, 1200-1209.
Harrad S. J., Stewart A. P., Alcock R., Boumphrey R., Burnett V., Duarte-Davidson
R., Halsall C., Sanders G., Waterhouse K., Wild S. R., Jones K. C. (1994):
Polychlorinated biphenyls (PCBs) in the British environment: sinks, sources, and temporal
trends. Environ. Pollut. 85, 131-146.
Hornbuckle K. C., Achman D. R., Eisenreich S. J. (1993): Over-water and over-land
polychlorinated biphenyls in Green Bay, Lake Michigan. Environ. Sci. Technol. 27, 87-98.
IARC (1987): Overall Evaluation of Carcinogenity: An Updating of IARC Monographs
Volumes 1 to 42 (Supplement 7). IARC Monographs on the Evaluation of Carcinogenic
Risks to Humans, Lyon.
Iwata H., Tanabe S., Ueda K., Tatsukawa R. (1995): Persistent organochlorine residues
in air, water, sediments, and soil from Lake Baikal, region Russia. Environ. Sci. Technol.
29, 792-801.
Larsson P., Backe C., Bremle G., Eklow A., Okla L. (1996): Persistent pollutants in a
salmon population (Salmo salar of the southern Baltic Sea. Can. J. Fish. Aquat. Sci. 53, 6269.
Lulek J. (1996): Determination of polychlorinated biphenyls in waste motor and
transformer oils. Organohalogen Compounds, 28, 267-270.
Polič S., Kontič B. (1987): Report on PCBs remediation in Bela Krajina. World
Conference on Hazardous Waste, Budapest, Hungary, 925-929.
Polič S., Leskovšek H. (1996): Fate and transport of polychlorinated biphenyls (PCBs)
between water and atmosphere of the polluted Krupa River in Slovenia. Organohalogen
Compounds 28, 35-38.
Sinovčevič R. (1998): POPs management in the Republic of Croatia. In: UNEP/IFCS, 213230.
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US DHHS (1993): Toxicological Profile for Selected PCBs. U.S. Department of Public and
Health Service, Agency for Toxic Substances and Disease Registry (Prepared by Clement
International Corporation for US DHHS), TP-92/16, Atlanta, GA, 209 pp.
Walker C. H. (1990): Kinetic models to predict bioaccumulation of pollutants. Functional
Ecology 4, 295-301.
Wania F., Mackay D. (1993): Global fractionation and cold condensation of low volatility
organochlorine compounds in polar regions. Ambio 22, 10-18.
Wania F., Mackay D. (1996): Tracking the distribution of persistent organic pollutants control strategies for these contaminants will require a better understanding of how they
move around the globe. Environ. Sci. Technol. 30, 390A-396A.
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7.2 Sources
Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/Fs) are environmental
ubiqitous because detectable in almost all compartments of the global ecosystem in trace
amounts. Because PCDDs/Fs have never been produced intentionally and have never served
any useful purpose unlike other PBTs such as PCBs or DDT. PCDDs/Fs are formed as
unwanted by-products in many industrial and combustion processes. Among their natural
sources are forest fires and volcanoes.
Due to their chemical, physical and biological stability, PCDDs/Fs are able to remain in
the environment for long time. As a consequence dioxins from so-called "primary
sources" (once formed in industrial or combustion processes) can be transferred to other
matrices and enter the environment. Such secondary sources are sewage sludge/biosludge,
compost, or contaminated areas (Fiedler, 1999).
Primary sources of environmental contamination with PCDDs/Fs in the past were due to
production and use of chloroorganic chemicals, including the pulp and paper industry.
PCDFs were/are formed as inadvertent by-products in the production and use of
polychlorinated biphenyls (PCBs) and, in combination with PCDDs, in the production of
chlorophenols and have been detected as contaminants in these products. PCDFs also are
found in residual waste from the production of vinyl chloride and the chloralkali process for
chlorine production. In wet-chemical processes the propensity to generate PCDDs/Fs during
synthesis of chemical compounds decreases in the following order:
Chlorophenols > chlorobenzenes > aliphatic chlorinated compounds > inorganic chlorinated
compounds.
Factors favorable for the formation of PCDDs/Fs are high temperatures, alkaline media,
presence of UV/light, and presence of radicals in the reaction mixture/chemical process
(Hutzinger and Fiedler, 1991, 1993; Fiedler, 1999).
Changes in the industrial processes have resulted in reduction of PCDDs/Fs
concentrations in the products. Emissions of PCDDs/Fs into the environment via water and
to soils from kraft pulp and paper mills. PCDDs/Fs were detected in the final product (pulp,
paper) as well as in the pulp and paper sludges. With advanced bleaching technology, their
contamination in effluents, products, and sludges was reduced.
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As a consequence, products containing any of the above mentioned chemicals are
contaminated with PCDDs/Fs as well. Amongst these, wood treated with pentachlorophenol
(PeCP) or other chlorinated preservatives as well as PCB-based electric fluids are amongst
those with the highest contaminations. Other PeCP-treated materials include textiles, leather
goods, and cork products (Fiedler, 1999).
Whereas in the past, the chemical industry and to a lesser extent the pulp and paper
industry were considered to be the main source of PCDDs/Fs and also the cause of today´s
contaminated sites in many industrialized countries, today´s dioxin input is mainly due to
thermal processes. There is still a considerable focus on waste incineration but based on the
requirements for dioxin reduction in stack gases set by several national authorities, the
importance of this category has declined during the last years. Examples can be seen
especially in the European emission inventories (Fiedler, 1999).
The process by which PCDDs/Fs are formed during incineration are not completely
understood nor agreed upon. Three possibilities have been proposed to explain the presence
of PCDDs/Fs in incinerator emissions (NATO/CCMS 1988b):
●
PCDDs/Fs are already present in the incoming waste and are incompletely destroyed
or transformed during combustion; not relevant for modern MSWIs.
●
PCDDs/Fs are produced from related chlorinated precursors (pre-dioxins) such as
PCBs, PCPs, or PCBzs.
●
PCDDs/Fs are formed via de novo synthesis - they are formed from the pyrolysis of
chemically unrelated compounds such as polyvinylchloride (PVC) or other
chlorocarbons, and/or the burning of non-chlorinated organic matter such as
polystyrene, cellulose, lignin, coal, and particulate carbon in the presence of chlorinedonors.
From the knowledge gained from MSWIs it can be concluded that PCDDs/Fs can be
formed in other thermal processes in which chlorine-containing substances are burnt
together with carbon and a suitable catalyst (preferably copper) at temperatures above 300 °
C in the presence of excess air or oxygen (Fiedler, 1999). Preferentially dioxin formation
takes place in the zone when combustion gases cool down from about 450 °C to 250 °C (de
novo synthesis) and not in the combustion chamber. Possible sources of the chlorine input
are PVC residues as well as chloroparaffins in waste oils and inorganic chlorine.
An overview on combustion sources known to generate and to emit PCDDs/Fs
(Fiedler, 1999):
Stationary sources:
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Waste incineration:Municipal solid waste, clinical, hazardous waste, sewage sludge
Steel industry:
Steel mills, sintering plants, hot-strip mills
Recycling plants: Non-ferrous metals (melting, foundry; Al, Cu, Pb, Zn, Sn)
Energy production:Fossil fuel power plants, wood combustion, landfill gas
Diffuse sources:
Traffic:
Home heating:
Accidents:
Automobiles
Coal, oil, gas, wood
PCB fires, fires in building, forest fires, volcanic eruptions
It should be mentioned that PCDDs/Fs are not only found in the stack gases but also in
the solid residues from any combustion process, e.g. bottom ashes, slags, and fly ash. With
advanced technology and better burn-out of the ashes and slags (characterized by a low
content on organic carbon), the PCDDs/Fs concentrations declined (Fiedler, 1996b, 1999).
Secondary sources of PCDDs/Fs, their reservoirs are those matrices where they are
already present, either in the environment or as products. The PCDDs/Fs found in these
reservoirs are not newly generated but concentrated from other sources. A characteristic of
the reservoir sources is that they have the potential to allow re-entrainment of PCDDs/Fs
into the environment. Product reservoirs include PCP-treated wood, PCB-containing
transformers and sewage sludge, compost, and liquid manure, which can be used as
fertilizers in agriculture and gardens. Reservoirs in the environment are for example
landfills and waste dumps, contaminated soils (mainly from former chemical production or
handling sites), and contaminated sediments (especially in harbours and rivers with
industries discharging directly to the waterways).
Other reservoirs include the former use of PCDDs/Fs-contaminated products such as
2,4,5-trichlorophenoxyacetic acid (2,4,5-T), PCBs, and pentachlorophenol or their sodium
salt (PeCP/PeCP-Na). Although there are estimates of the total amount of these compounds
produced for various purposes, it seems impossible to deduce from these numbers a
quantitative impact of PCDDs/Fs to the environment or humans (Fiedler, 1995, 1999).
Although these reservoirs may be highly contaminated with PCDDs/Fs, the chemicalphysical properties of these compounds imply that dioxins and furans will stay absorbed to
organic carbon of soils or other particles. On the other hand, mobilization can occur in the
presence of lipophilic solvents (leaching into deeper layers of soils and/or groundwater) or
in cases of erosion or run-off by rain from topsoil (translocation into the neighberhood).
Experience has shown that PCDDs/Fs transport due to soil erosion and run-off does not play
a major for environmental contamination and human exposure (Fiedler 1995, 1999).
Enzymatic reactions can dimerize chlorophenols to PCDDs/Fs. However, compared to
chemical-industrial and combustion sources, biological formation seems to be negligible.
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PCDDs and PCDFs are ubiquitous in soil, sediments and air. Excluding occupational or
accidental exposures, most human exposure to PCDDs and PCDFs occurs as a result of
eating meat, milk, eggs, fish and related products, as both PCDDs and PCDFs are persistent
in the environment and accumulate in animal fat. Occupational exposures to both PCDDs
and PCDFs at higher levels have occurred since the 1940s as a result of production and use
of chlorophenols and chlorophenoxy herbicides and to PCDFs in metal production and
recycling. Even higher exposures to PCDDs have occurred sporadically in relation to
accidents in these industries. High exposures to PCDFs have occurred in relation to
accidents such as the Yusho (Japan) and Yu-cheng (Taiwan) incidents involving
contamination of rice oil and accidents involving electrical equipment containing PCBs.
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7.3 Sources and production in CEE countries
Main sources of PCDDs/Fs in the region are typical for industrial countries - they are
formed as by-products, mainly in chemical industry - production of chlorophenols and their
derivatives (former Czechoslovakia, USSR, GDR, Poland, probably Romania), processes in
which chlorinated catalysts and solvents are used; pulp and paper production - bleaching
based on chlorine treatment, metallurgical production - if metal chlorides are used,
magnesium production, metal scrap recycling; municipal, hospital, hazardous and industrial
waste incineration; solid fossil fuel combustion (coal, wood, peat), internal-combustion
engine operation - leaded petrol use with the addition of chlorinated compounds; dry
distillation (dry cleaning of clothes); fires (forest, agriculture..).
Despite of two decades of world-wide interest and intensive studies on PCDDs/Fs,
practically till now there are no data available in these compounds in environmental
matrices in CEE countries. Limited information exist in Czech Republic, Slovakia, Poland,
Slovenia, the lack of information exist in others.
The knowledge on sources of environmental pollution and emission rates of PCDDs/Fs
in Poland is also described as extremely limited (Falandysz et al., 1997). In the past some
technical products potentially contaminated with dioxins were used. For example a popular
wood preservative of the Xylamit series contained technical pentachlorophenol (similar
products were also in former Czechoslovakia), and Masc grzybobójcza (fungicidal
ointment) contained the waste products of the distillation of technical chlorophenols and
was used for technical purposes. A technical pentachlorophenol (e.g. Antox), and herbicides
such as 2,4-D; 2,4-DP; MCPA, MCPP and Dicamba were also used in the past in Poland.
Some efforts have been undertaken to elucidate the status of PCDDs/Fs in some of those
formulations, nevertheless, a detailed composition and concentrations of contaminating
dioxin residues remain unknown.
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7.4 Environmental fate
Because of their persistent nature and lipophilicity, once PCDDs/Fs enter the
environment and living organisms, they will be present there for a very long time like other
halogenated aromatic compounds. Since value of environmental chemical parameters such
as Kow or Koc are very high for all these compounds, they will intensively adsorb onto air,
soil and sediment particles containing organic carbon and accumulate in fat-containing
tissues. The strong adsorption of PCDDs/Fs and related compounds to soil and sediment
particles causes their mobility in these environmental compartments to be negligable. Their
mobility may be increased by the simultaneous presence of organic solvents such as mineral
oil. The air compartment is probably the most significant compartment for the
environmental distribution and fate of PBTs compounds.
A part of PCDDs/Fs emissions into air will be bound to particles, while the other part
will be in gaseous phase, which can be subject to long-range transport (up to thousands of
km). In the gaseous phase, removal processes include chemical and photochemical
degradation. In the particulate phase, these processes are of minor importance and the
transport range of the particulate phase will primarily depend on the particle size. PCDDs/
Fs are extremely resistant towards chemical oxidation and hydrolysis, hence, these
processes are not expected to be significant in the aquatic environment. Photodegradation
and microbial transformation are probably the most important degradation routes in surface
water and sediment.
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7.5 Exposure pathways and metabolism
Generally, organohalogen persistent pollutants such as dioxins and related compounds
enter the human body by ingestion, inhalation, and skin penetration. The inhalation and skin
penetration are of less importance except occupational exposure. Eating, in particular, fatcontaining food such as fish, meat, milk, eggs represents more than 90 % of daily intake of
these chemicals for the human general population. Especially, foodstuffs of animal origin
are responsible for the daily intake of approximately 2 pg TEQ.kg-1 bw.d-1 (Fiedler, 1999).
All other foodstuffs, especially the "non-fatty" ones, are of minor importance in terms of
PCDDs/Fs intake. They are either of plant origin or do not have a high potential for
bioaccumulation of lipophilic compounds. Due to many measures to reduce emissions of
PCDDs/Fs into the environment, reduction of PCDDs/Fs contamination in food was
observed. As a consequence, the daily intake via food decreased. Although no adverse
health effects could be causally linked so far with background exposures of PCDDs/Fs in
human milk, for reasons of preventive health care, the relatively high exposure of breast-fed
infants must still be considered a matter of concern.
In May 1998, WHO evaluated the risks which dioxins may cause to health. During a
previous meeting in Bilthoven 1990, WHO experts established a tolerable daily intake of
10 pg TCDD.kg-1 bw.d-1. Since then, new epidemiological data has emerged, especially on
neurotoxicological development and the endocrine system. Finally, WHO agreed on a new
tolerable daily intake (TDI) of 1 to 4 pg.kg-1 bw.d-1. The expert however, recognized that
subtle effects occur in the general population in developed countries at background levels of
2 to 6 pg.kg-1 bw.d-1. They therefore recommended that every effort should be made to
reduce exposure to the lowest possible level. In addition, the range established for 2,3,7,8TCDD should be applied to a TEQ including the seventeen 2,3,7,8-substituted PCDDs/Fs as
well as the coplanar and mono-ortho substituted PCBs (WHO, 1998; van Leeuwen and Younes,
1998; Fiedler, 1999).
PCDDs and PCDFs are slowly eliminated from animal and human organisms as monoand dihydroxylated metabolites. Oxidation (through the P540 cytochrome) leading to the
formation of hydroxylated derivatives occurs preferably on the 2, 3, 7 or 8 positions. If all
the 2, 3, 7 and 8-positions are substituted with chlorine atoms, metabolic conversion of the
molecule is strongly hindered. Therefore in human and animal samples congeners
substituted at 2, 3, 7 and 8-positions have been detected only.
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7.6 Toxicological effects
Perhaps the most widely noted property of dioxins and dioxin-like compounds (not
DDT, HCB or multiortho-substituted PCB congeners) is their remarkably high acute
toxicity. In certain species, such as the guinea pig, even very small doses can result in death.
Poisoning by these substances is a fairly protracted process: death is preceded by gradual
emaciation and normally does not occur until several weeks after exposure, even when the
dose is well above the lowest lethal level. Scientists are still not able to identify the real
cause of death in dioxin poisoning, nor they can pinpoint the organ in the body, which is the
weakest link. What is more, there is only a vague idea of why some species, breeds and
strains are far less sensitive than others to the acute effects of dioxin-like substances.
Some of the symptoms of dioxin-like toxicity appear even after doses far lower than the
acute lethal dose. One of these symptoms recurs in all the species studied, namely a marked
reduction in the size of the thymus and a decrease in the number of T lymphocytes. Another
sublethal characteristic symptom caused by exposure of human beings, monkeys, rabbit and
white mouse to dioxins and some other organochlorine substances is chloracne, a severe
skin disease. Toxicological tests on experimental animals and human poisonings caused by
occupational exposure and by the ingestion of food contaminated with PCBs have shown
that persistent organochlorines cause reproductive disorders, disturbing vitamin A
metabolism and disrupting liver functions (e.g., porphyria).
The root cause of many of the damaging effects of dioxins on living organisms is that
they bind effectively to a specific receptor, a protein in the cytoplasm of the cell which is
referred to as the Ah receptor. The binding of a dioxin to this receptor triggers a chain of
reactions, the end result of which is that the receptor binds to a DNA sequence after
entering the cell nucleus. This causes a powerful induction (increased production or release)
of an enzyme of the cytochrome P450 type and thus results in some pathological changes.
PCDDs/Fs produce a spectrum of toxic effects in animals; however, most information is
available on 2,3,7,8-TCDD only. Most toxicity data on TCDD result from high dose oral
exposures to animals. There is a wide range of difference in sensitivity to PCDD lethality in
animals. The signs and symptoms of poisoning with chemicals contaminated with TCDD in
humans are similar to those observed in animals. Dioxin exposures to humans are associated
with an increased risk of severe skin lesions (chloracne and hyperpigmentation), alterd liver
function and lipid metabolism, general weakness associated with drastic weight loss,
changes in activity of various liver enzymes, depression of the immune system, and
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endocrinne and nervous system abnormalities. 2,3,7,8-TCDD is a potent teratogenic and
fetotoxic chemical in animals and a potent promotor in rat liver carcinogenesis. TCDD also
cancers of the liver and other organs in animals.
In human tissues, current mean background levels of 2,3,7,8-tetrachlorodibenzo-pdioxin (2,3,7,8-TCDD, or "dioxin", the PCDD that has caused most concern) are in the
range of 2-3 ng/kg fat and the sum of the penta- and hexa-chlorinated PCDF congeners
commonly found in human tissues is generally in the range 10-100 ng/kg fat. Accidental
exposures to high levels of PCDDs or PCDFs have led to increases in tissue concentrations
above these background levels of up to four orders of magnitude for TCDD and one or more
orders of magnitude for PCDFs. Because of the long half-lives of many of these substances
in humans (e.g., ca. 7 years for TCDD), a single, acute exposure from the environment
results in the exposure of potential target tissues for a period of years.
Human carcinogenicity data
PCDDs. The most important epidemiological studies for the evaluation of 2,3,7,8TCDD are four cohort studies of herbicide producers (one each in the United States and the
Netherlands, two in Germany). These studies involve the highest exposures to 2,3,7,8TCDD. The cohort of residents in a contaminated area from Seveso, Italy is well known, but
the exposures at Seveso were lower and the follow-up shorter than those in the industrial
settings. Most of the four industrial cohorts include analyses of sub-cohorts considered to
have the highest exposure and/or longest latency. Additional studies of herbicide
applicators, both cohort and case-control studies, and military personnel in Viet Nam who
have considerably lower exposures to 2,3,7,8-TCDD, were not considered to be critical for
the evaluation.
Overall, the strongest evidence for the carcinogenicity of 2,3,7,8-TCDD is for all
cancers combined, rather than for any specific site. An increased risk of lung cancer, with
about the same relative risk, is also present in the most informative studies. There are few
examples of agents, which cause an increase in cancers at many sites; an important example
is tobacco smoking (for which, however, there are clearly elevated risks for certain specific
cancer sites). This lack of precedent for a multi-site carcinogen without particular sites
predominating means that the epidemiological findings must be treated with caution. On the
basis of various studies, the International Agency for Research on Cancer (IARC)
concluded that there is limited evidence in humans for the carcinogenicity of 2,3,7,8-TCDD.
There was inadequate evidence in humans for the carcinogenicity of PCDDs other than
2,3,7,8-TCDD.
Two incidents, each involving about 2000 cases, occurred in which people were
exposed to sufficient PCBs and PCDFs to produce symptoms. Fatal liver disease is 2-3
times more frequent than national rates in both cohorts. In Japan, at 22 years of follow-up,
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there is a three-fold excess of liver cancer mortality in men, which was already detectable
and even higher at 15 years of follow-up. In Taiwan (Yucheng cohort), after 12 years of
follow-up, there is no excess of liver cancer mortality. Based upon these data, IARC
concluded that there is inadequate evidence in humans for the carcinogenicity of PCDFs.
PCDDs. In a number of experiments with rats and mice in which 2,3,7,8-TCDD was
administered, increases in the incidence of liver tumours was consistently found in both
males and females. In addition, tumours were increased at several other sites in rats, mice
and Syrian hamsters, but these effects were dependent upon the species, sex and route of
administration of 2,3,7,8-TCDD. Although the doses resulting in increased tumour
incidence in rodents are extremely low, they are very close to doses that are toxic in the
same species. These data led to the conclusion that there is sufficient evidence in
experimental animals for the carcinogenicity of 2,3,7,8-TCDD.
Evaluation of much smaller databases led to the conclusion that there is limited
evidence in experimental animals for the carcinogenicity of a mixture of 1,2,3,6,7,8- and
1,2,3,7,8,9-HxCDD and that there was inadequate evidence for the carcinogenicity in
experimental animals of 2,7-dichloroDD, 1,2,3,7,8-pentachloroDD and 1,2,3,4,6,7,8heptachloroDD.
PCDFs. There are no long-term carcinogenicity studies on PCDFs, but some tumour
promotion studies were evaluated in which rats and mice were exposed to some of the
congeners following short duration exposure to known carcinogens. It was concluded that
there is inadequate evidence in experimental animals for the carcinogenicity of 2,3,7,8TCDF, but there is limited evidence in experimental animals for the carcinogenicity of
2,3,4,7,8-pentaCDF and 1,2,3,4,7,8-hexaCDF.
Other evidence
The toxicity of 2,3,7,8-TCDD segregates with the cytosolic aryl (aromatic) hydrocarbon
receptor (AhR), and the relative toxicities of other PCDD congeners is associated with their
ability to bind to the receptor, which occurs in all rodent and human tissues. The AhR
binding affinities of 2,3,7,8-TCDF, 1,2,3,7,8- and 2,3,4,7,8-pentaCDFs are in the same
order of magnitude as that observed for 2,3,7,8-TCDD. PCDDs with at least three lateral
chlorine atoms bind with some affinity to the AhR. Current evidence is that most, if not all,
biological effects of 2,3,7,8-TCDD and other PCDDs arise from an initial high affinity
interaction with the AhR and it appears that the biochemical and toxicological consequences
of PCDF exposure are the result of a similar mode of action. The limited carcinogenicity
data available for congeners other than 2,3,7,8-TCDD indicate that carcinogenic potency is
also proportional to AhR affinity. Based on this evidence, all PCDDs and PCDFs are
concluded to act through a similar mechanism and require an initial binding to the AhR.
Binding of 2,3,7,8-TCDD to the AhR results in transcriptional activation of a battery of
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2,3,7,8-TCDD-responsive genes, but currently no responsive gene has been proven to have
a definitive role in its mechanism of carcinogenesis.
Overall evaluation
Taking all of the evidence into consideration, the following evaluations were made by
IARC (IARC, 1997; Fiedler, 1999):
●
2,3,7,8-Tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) is carcinogenic to humans
(Group 1).
Supporting evidence:
i. 2,3,7,8-TCDD is a multi-site carcinogen in experimental animals mechanism
involving the;
ii. Ah receptor highly conserved in an evolutionary sense and functions the same
way in humans as in experimental animals;
iii. tissues concentrations are similar both in heavily exposed human populations
in which an increased overall cancer risk was observed and in rats exposed to
carcinogenic dosage regimens in bioassays.
●
Other polychlorinated dibenzo-p-dioxins are not classifiable as to their
carcinogenicity to humans (Group 3).
●
Dibenzo-p-dioxin is not classifiable as to its carcinogenicity to humans (Group 3).
●
Polychlorinated dibenzofurans are not classifiable as to their carcinogenicity to
humans (Group 3).
Toxic Equivalency Factors (TEF)
Many regulator agencies have developed so-called Toxicity Equivalency Factors (TEF)
for risk assessment of complex mixtures of PCDDs/Fs (Kutz et al., 1990; Fiedler, 1999). The
TEF are based on acute toxicity values from in vitro studies. This approach is based on the
evidence that there is a common, receptor-mediated mechanism of action for these
compounds. However, the TEF approach has its limitations due to a number of
simplifications. Although the scientific basis cannot be considered as solid, the TEF
approach has been developed as an administrative tool and allows to convert quantitative
analytical data for individual PCDDs/Fs congeners into a single Toxic Equivalent (TEQ).
TEF particularly aid in expressing cumulative toxicities of complex PCDDs/Fs mixtures as
one single TEQ value. Today, almost all literature data are reported in I-TEQ.
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It should be noted that TEF are interim values and administrative tools (Fiedler, 1999).
They are based on present state of knowledge and should be revised as new data gets
available. Today´s most commonly applied TEFs were established by a NATO/CCMS
Working Group on Dioxins and Related Compounds as International Toxicity Equivalency
Factors (I-TEF) (NATO/CCMS 1988a). However, in 1997, a WHO/IPCS working group reevaluated the I-TEFs and established a new scheme. The re-evaluation concluded to include
non-ortho and mono-ortho-substituted polychlorinated biphenyls into the TEF scheme for
dioxin-like toxicity as well (see Table 7-1).
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7.7 References
Falandysz J., Florek A., Stranddberg L., Strandberg B., Berqvist P.-A., Rappe C.
(1997): PCDDs and PCDFs in Biota from the Southern part of the Baltic Sea.
Organohalogen Compounds 32, 167-171.
Fiedler H. (1995): EPA DIOXIN-reassessment: Implications for germany. Organohal.
Comp. 22, 209-228.
Fiedler H. (1996a): Dioxine in Prrodukten un Abfallen. In: Dioxine-Vorkommen,
Minderungsmassnahmen, Messtechnik. VDI Band 1298, VDI-Verlag, Dusseldorf, 231-247.
Fiedler H. (1996b): Sources of PCDD/PCDF and impact on the environment.
Chemosphere 32, 55-64.
Fiedler H. (1998): Thermal formation of PCDD/PCDF - a survey. Environ. Eng. Sci. 15-1,
49-58.
Fiedler H. (1999): Dioxin and furan inventories. National and regional emissions of PCDD/
PCDF. UNEP Chemicals. Geneva, Switzerland 1999, 100 pp.
Hutzinger O., Fiedler H. (1993): From source to exposure: some open questions.
Chemosphere 27, 121-129.
IARC (1997): Polychlorinated Dibenzo-p-Dioxins and Polychlorinated Dibenzofurans.
Summary of Data Reported and Evaluation. IARC Monographs Vol. 69, IARC Press, Lyon
1997, 666 pp.
Kutz F. W., Barnes D. G., Bretthauer E. W., Bottimore D. P., Greim H. (1990): The
international toxicity equivalence factor (I-TEF) method for estimating risks associated with
exposures to complex mixtures of dioxins and related compounds. Toxicol. Environ. Chem.
26, 99-110.
NATO/CCMS (1988a): International toxicity equivalence factor (I-TEF) method of risk
assessment for complex mixtures of dioxins and related compounds. Report Number 176,
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August 1988, NATO, Committee on Chalanges of Modern Society.
NATO/CCMS (1988b): Hutzinger O, Fiedler H.: Emissions of dioxins and related
compounds from combustion and incineration sources. Pilot Study on International
Information Exchange on Dioxins and Related Compounds, NATO/CCMS Report No. 172.
Van den Berg M., Birnbaum L., Bosveld A. T. C., Brunstrom B., Cook P., Feeley M.,
Giesy J. P., Hanberg A., Hasegawa R., Kennedy S. W., Kubiak T., Larsen J. C., van
Leeuwen F. X. R., Liem A. K. D., Nolt C., Petersen R. E., Poellinger L., Safe S.,
Schrenk D., Tillit D., Tysklind M., Younes M., Waern F., Zacharewski T. (1998): Toxic
equivalency factors (TEFs) for PCBs, PCDDs, PCDFs for humans and wildlife. Environ.
Hlth. Perspect. 106, 775-792.
Van Leeuwen F. X. R., Younes M. (1988): WHO Revises the Tolerable Daily Intake
(TDI) for Dioxins. Organohal. Compds. 38, 295-298.
WHO (1998): WHO Experts Re-evaluate Health Risks from Dioxins. Press Release
WHO/45, 3 June 1998.
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8.2 Sources
Technical PCN formulations have found numerous industrial applications such as:
dielectrics for flame-proofing and insulating in the energy, electric and automobile
industries, preservatives with some fungicidal and insecticidal activities for the wood, paper
and textile industries, impregnate in paper inlays in gas-masks, additives in engines,
lubricants for graphic electrodes, separators in batteries, in grinding wheel lubricants, high
boiling capacity solvents, heat exchange fluids, dye carriers and in dye production, additives
in rubber industry, flame retardant, moisture-proof sealant for chemically resistant gauge
fluids and instrumental seals, casting materials for alloys, refractive index testing materials,
masking compounds in electroplating, temporary binders in the manufacture of ceramic
components (Falandysz, 1998).
They are three known main sources of PCNs in the environment: the technical PCN
formulations, technical PCB formulations, and thermal (e.g. combustion, roasting, metal
reclamation) and other processes (e.g. chloro-alkali industry) in the presence of chlorine.
Knowledge on the amounts, composition and sources of PCNs due to thermal and other
processes in presence of chlorine is very limited. The patterns of tetra- to hexa-CNs formed
in combustion products such as fly ash, flue gas and circulating water of the solid waste
incinerator, seem to be similar, and only recently have basic differences in the tetra- to hexaCNs pattern in fly asn between the Stoker and fluidised bed type incinerators been found
(Imagawa and Takeuchi, 1995). There are only a few records giving patterns of PCNs in
emissions due to combustion that include mono-, di- and tri-CNs (Takasuga et al., 1994; Abad
et al., 1997). Nevertheless, until now no detailed quantitative and congener-specific data
have been available on PCNs formed during combustion processes.
Incineration, copper ore roasting and aluminium reclamation are sources of
environmental pollution with PCNs (Falandysz, 1998).
Various chloronaphthalene congeners were recently quantified in graphite sludge at a
chloro-alkali plant in Sweden (Jarnberg et al., 1997) and also in the environmental matrices
at a superfund site, near a chloro-alkali plant in Georgia, USA (Kannan, personal
communication). The highly chlorinated pattern of PCNs in graphite sludge can be related
to highly chlorinated technical PCB formulation used in the chloro-alkali process, such as
Aroclor 1268 (Kannan et al., 1997) or possible use of technical PCN formulation (Halowax
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1051) as a lubricant for the graphite electrodes, and less to formation due to reactions of
released chlorine. Nevertheless, in the absence of a technical PCN mixture used as a
lubricant, the technical PCB mixtures contaminated with PCNs can be used for the same
purpose, and including the reactions of chlorine itself will lead to a multiple source of
PCNs. A magnesium refinery can be a source of environmental pollution by PCNs
(Schlabach et al., 1995).
The roughly estimation of the total production of PCNs due to combustion and other
processes involving chlorine to be 1-10 metric tons. The open question now is how much of
the most persistent and highly toxic congeners of chloronaphthalene are released due to
thermal processes.
Another known sources of environmental pollution with PCNs are technical PCB
formulations. PCNs are usually common impurities found in technical PCB mixtures. The
conditions for the production of PCBs on a technical scale are largely the same as for PCNs.
Hence, the chlorination profiles of PCNs formed as by-products on the technical synthesis
of PCBs has to follow the chlorination profile of the chlorobiphenyl mixture, while the
compositional structure patterns can be found in original PCN formulations.
The PCB mixtures of Aroclor or Clophen series can contain up to 0.087 % of PCNs, and
the available median value is 0.0067 % (Haglund et al., 1995; Jarnberg et al., 1997). The PCN
content of the PCB mixtures of series other than Aroclor or Clophen in unknown. By
multiplying the median PCN concentration for those two series of technical PCBs by the
volume of the total worldwide production of PCBs (ca 1 500 000 metric tons), a value of
100 metric tons is derived. Nevertheless, since the development of safe technologies of
disposal or recycling of used technical PCB formulations as well as wastes with high
concentrations of PCBs, the amount of PCNs potentially escaping into the environment can
be lower than could be predicted from their residual concentrations in technical
chlorobiphenyl mixtures.
The technical mixtures of PCNs are known under trade names such as Halowaxes,
Nibren waxes, Seekay Waxes, Clonacire waxes, N-Oil, N-Wax and Cerifal Materials. The
production of PCNs decreased in the late 1970s. Until 1989 technical PCNs were used as
casting materials in Germany (Popp et al., 1993), in a factory in the former Jugoslavia (Jan et
al., 1994), and were also found in old type but still in service electronic equipment (cables)
in Sweden (Weistrand et al., 1992). The original data on the quantum of technical PCN
mixtures produced world-wide are not available. However, based on 1.5 million metric tons
of the technical PCBs produced, PCNs are roughly assessed to be 0.0067 % of the PCBs
produced, i.e. 100.5 metric tons. The amount of PCNs environmentally available from that
source, as in the case of produced PCB mixture (the formulations retained in technical
equipment or safely disposed) can be lower than 100 tones.
It is an open question as to how much of the synthesised PCNs escaped into the
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environment and how much was still retained in the technical products. The roughly
estimated volume of PCNs produced due to human activities, however, seems to indicate
that the technical PCN formulations are a dominating source of these chemicals in the
environment (Falandysz, 1998).
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8.3 Sources and production in CEE countries
Virtually nothing in known on the type and quantity of PCNs potentially manufactured
in CEE countries. The former Czechoslovakia and USSR produced PCB formulations,
based on approaches, which were mentioned above, we can roughly assess 0.0067 %
content of PCNs in PCB mixtures. In the case of former Czechoslovakia, we can suppose
the potential input onto the environment round 1.6 metric tons of PCNs during period of
production (1959-1984) and some secondary inputs after year of banning (from disposals,
combustion, incinerators, contaminated soils and sediments).
1-chloronaphthalene was utilised in Xylamits, a popular wood (and other purpose)
preservative widely applied in the past in Poland and also containing technical
pentachlorophenol together with the waste products of chlorophenols distillation and other
substances (Falandysz et al., 1996).
At least 2-chloronaphthalene was produced and used as a solvent in Poland (Falandysz et
al., 1998). Is possible that in the chemical plant in Tarnów-Mościce in southern Poland
(manufacturer of the technical PCB formulation Tarnol) some higher chlorinated
naphthalenes were produced at small scale in the past (1930-1950 ?).
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8.4 Environmental fate
PCNs are ubiquitous global pollutants and only recently data on congeners that
accumulated in wildlife and abiotic environmental matrices become available (Falandysz,
1998 and references there).
Based on the similarity in concentrations, profile and patterns of tetra- to hexa-CNs
determined in subsurface plankton and some other samples from the southern Baltic proper,
it was suggested that the atmosphere can be a dominating long-range transportation and
spread route for these substances on a global scale. Indeed, the contamination of the
ambient air with PCNs was confirmed recently in Europe, North America and the Arctic
(Dörr et al., 1996; Harner and Bidleman, 1997; Harner et al., 1997).
The more volatile mono-, di- and tri-CNs show a much higher abundance than the more
chlorinated and less volatile tetra- to octa-CN homologous in air at the manufacturing sites
and in the gas phase emissions from the MSWI. In the atmosphere in gas phase, tri- and
tetra-CNs show much higher abundance than penta- to octa-CNs, while on the particles
there is a stepwise increase from tri- to octa-CNs (Harner and Bidleman, 1997). On average,
98 % of PCNs in ambient air was in the gas phase and 2 % on the particles (Dörr et al., 1996).
Due to different physicochemical properties and sources there can be a large seasonal
variations in both the concentration and composition of PCN homologue groups in ambient
air. Apparently, in the nothern hemisphere PCNs can occur at five-times higher
concentrations in ambient air in summertime than in the winter or spring, and tri- to pentaCNs are more abundant constituents when the temperature of the lower troposphere is
getting warmer, while hexa- to octa-CNs increase when it gets colder (Dörr et al., 1996).
Apart from the atmosphere, some data have recently become available on the
composition of PCNs in abiotic matrices such as surface and ground water, sediments or
biota (Falandysz, 1998).
A relatively higher abundance of tetra- and penta-CNs (and probably also of tri- and diCNs) in abiotic samples such as ambient air, fresh water and surface sediments, and also in
some biological matrices (plankton, blue mussels), indicate their resistance to
biodegradation by abiological means. Nevertheless, the environmental chemistry of PCNs is
little known. Physico-chemical properties such as vapour pressure and water solubility
(Crookes and Howe, 1993) will favour higher environmental mobility (atmospheric diffusion
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and water leaching from soil surface horizon) of di- to penta-CNs when compared to hexa-,
hepta- or octa-PCNs. The physico-chemical properties of low chlorinated PCNs seem to
determine their relative abundance in background abiotic environmental compartments. The
relative significance of a particular source of PCNs (technical PCNs, technical PCBs,
combustion), and also of particular PCN homologue groups, to long-range atmospheric
transport is unknown.
The technical PCN formulations exhibit a wide range of patterns from nearly mono- and
di-CNs (Halowax 1031 and 1000) to nearly octa- and hepta-CNs (Halowax 1051), and the
same seems to apply to PCNs contained in technical PCB products. The congener of PCNs
such as 1,3,6,7-TCN (no. 44), which is formed exclusively during the combustion process,
was only recently quantified in wildlife (Falandysz, 1998 and his other papers). Hence, apart
from in very well-defined local situations, it can be very difficult or impossible to relate the
pattern of PCNs found in an abiotic or biological matrix to any particular source of
environmental pollution to those substances.
The patterns of CN congeners of technical Halowax mixtures have been published
(Falandysz et al., 2000). Normalised pattern (DB-5 capillary column) of polychlorinated
naphthalenes (PCNs; CNs) for all seven technical Halowax formulations and mass percent
contribution (CN %) for an equivalent mixture of Halowax 1031, 1000, 1001, 1099, 1013,
1014 and 1051 (Equi-Halowax) is presented. 2,3-DiCN (PCN No. 10), 1,6,7-and 2,3,6TrCNs (PCNs Nos. 25 and 26) and probably also 1,3,5-TrCN (PCN No. 19), 1,3,6,7-,
1,2,3,6- and 1,2,3,8-TeCN (PCNs Nos. 44, 29 and 31), and 1,2,3,6,7,8-HxCN (PCN No. 70)
were absent in commercial PCNs formulations. The congeners such as 1,2,3-TrCN (PCN
No. 13), 1,3,8-TrCN (PCN No. 22) and 1,2,3,6,7-PeCN (PCN No. 54) were present in the
mixtures at very low concentrations. The congeners most abundant in Halowax mixtures are
usually chlorinated at alpha-positions (1, 4, 5, 8 - positions) of the naphthalene nuclei.
Because of some unresolved peaks observed on the chromatograms due to insufficient
separation power of DB-5, and also of many other liquid phases used in capillary gas
chromatographic separation of PCNs even when mass spectrometric detection was used, a
perfect isomer and congener composition of PCN mixtures still has to be elucidated.
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8.5 Exposure pathways and metabolism
Biological membranes are permeable even for higher molecular weight CN congeners
such as hepta-CNs (Falandysz and Rappe, 1996). Bioaccumulation studies of PCNs in biota
from feed or water indicate that many congeners are metabolised and/or eleminated by
higher trophic animals in the food web. PCN congeners, which do not have vicinal
(adjacent) carbon atoms, on one or both rings, unsubstituted with chlorine (NVC-Cl PCNs)
have bioaccumulation factor values higher than 1 in animals of different trophic levels
(together 15 congeners) (Falandysz, 1997).
PCN congeners, which have two vicinal carbon atoms unsubstituted with chlorine
(DVC-Cl PCNs) seem to be relatively resistant to metabolism by animals, while those with
more than two vicinal carbon atoms unsubstituted are more easily metabolised or
eliminated.
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8.6 Toxicological effects
All congeners of chloronaphthalene are planar and lipophilic compounds, structurally
similar to highly toxic 2,3,7,8-tetrachlorodibenzo-p-dioxin, and can contribute to an aryl
hydrocarbon (Ah) receptor-mediated mechanism of toxicity, including a combination of
toxic responses such as mortality, embryotoxicity, hepatotoxicity, immunotoxicity, dermal
lesions, teratogenicity and carcinogenicity. Apart from a limited knowledge on the toxicity
of the individual, parent compounds there are no data on the properties of metabolites of
PCNs, e.g. on the less or more persistent hydroxy- and methylsulfone-derivatives.
A few available data indicate that several PCNs are as potent inducers of H4IIE-EROD,
AHH and H4IIE-luc as some of the highly toxic planar PCBs (Hanberg et al., 1990; Engwall et
al., 1994; Blankenship et al., 1999 and 2000; Villeneuve et al., 2000). Structure-activity
relationships were observed both in terms of the degree of chlorination and the positions of
chlorine substitution. Toxic equivalence factors are known only for a several PCNs (Table 81). Amongst of the chloronaphthalene congeners tested the most potent EROD, AHH and
Luciferase inducers are hexachloronaphthalenes and pentachloronaphthalenes are also
rather potent, while tetra-, tri-, di- and monochloronaphthalenes were less active.
Hydroxylated or methyl sulphone metabolites of PCNs are possible, nothing is known
on accumulation features, half-life or receptor binding (endocrine-ER or dioxin-Ah)
affinities of both types of metabolites of PCNs.
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Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
8.7 References
Abad E., Caixach J., Rivera J. (1997): Dioxin like compounds from MWI emissions:
assessment of polychlorinated naphthalenes presence. Organohalogen compounds 32, 403406.
Blankenship A., Kannan K., Villalobos S., Villeneuve D., Falandysz J., Imagawa T.,
Jakobsson E., Giesy J. P. (1999): Relative potencies of Halowax mixtures and individual
polychlorinated naphthalenes (PCNs) to induce Ah receptor-mediated responses in the rat
hepatoma H4IIE-luc cell bioassay. Organohalogen Compounds, 42, 217-220.
Blankenship A., Kannan K., Villalobos S., Villeneuve D., Falandysz J., Imagawa T.,
Jakobsson E., Giesy J. P. (2000): Relative potencies of Halowax mixtures and individual
polychlorinated naphthalenes (PCNs) to induce Ah receptor-mediated responses in the rat
hepatoma H4IIE-Luc cell bioassay. Environ. Sci. Technol. Submitted.
Crookes M. J., Howe P. D. (1993): Environmental hazard assessment: halogenated
naphthalenes. Toxic Substance Division. Directorate for Air, Climate and Toxic Substances,
Department of the Environment, TSD/12.
Dörr G., Hippelein M., Hutzinger O. (1996): Baseline contamination assessment for a
new resource recovery facility in Germany. Part V: Analysis and seasonal/regional
variability of ambient air concentrations of PCN. Chemosphere 33, 1563-1568.
Engwall M., Brundstrom B., Jakobsson E. (1994): Ethoxyresorufin O-deethylase
(EROD) and arylhydrocarbon hydroxylase (AHH) - inducing potency and lethality of
chlorinated naphthalenes in chicken (Gallus domesticus) and eider duck (Somateria
mollissima) embryos. Arch. Toxicol. 68, 37-42.
Falandysz J. (1997): Bioaccumulation and biomagnification features of polychlorinated
naphthalenes. Organohal. Compds. 32, 374-379.
Falandysz J. (1998): Polychlorinated naphthalenes: an environmental update. Environ.
Pollut. 101, 77-90.
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Falandysz J., Rappe C. (1996): Spatial distribution in plankton and bioaccumulation
features of PCNs in a pelagic food chain in the southern part of the Baltic proper. Environ.
Sci. Technol. 30, 3362-3370.
Falandysz J., Strandberg L., Berqvist P.-A., Kulp S. E., Strandberg B., Rappe C.
(1996): Polychlorinated naphthalenes in sediment and biota from the Gdaňsk Basin. Baltic
Sea. Environ. Sci. Technol. 30, 3266-3274.
Falandysz J., Kawano M., Ueda M., Matsuda M., Kannan K., Giesy J. P., Wakimoto
T. (2000): Composition of chloronaphthalene congeners in technical chloronaphthalene
formulations of the Halowax series. J. Environ. Sci. Health., 35A, in press.
Hanberg A., Waern F., Asplund L., Haglund E., Safe S. (1990): Swedish dioxin survey:
determination of 2,3,7,8-TCDD toxic equivalent factors for some polychlorinated biphenyls
and naphthalenes using biological tests. Chemosphere 20, 1161-1164.
Hanberg A., Stahlberg M., Georgellis A., de Vit C., Ahlborg U. G. (1991): Swedish
dioxin survey: evaluation of the H-4-II E bioassay for screening environmental samples for
dioxin-like enzyme induction. Pharmacol Toxicol 69, 442-449.
Haglund P., Jakobsson E., Masuda Y. (1995): Isomer-specific analysis of polychlorinated
naphthalenes in kanechlor KC 400, Yusho rice oil, and adipose tissue of Yusho victim.
Organohal. Compds. 26, 405-410.
Harner T., Bidleman T. F. (1997): Polychlorinated naphthalenes in urban air. Atmos.
Environ. 31/32, 4009-4016.
Harner T., Bidleman T. F., Kylin H., Strachan W., Halsall C. (1997): Polychlorinated
naphthalenes in urban and Arctic air. Organohal. Compds., 33, 134-139.
Imagawa T., Takeuchi M. (1995): Relation between isomer compositions of
polychlorinated naphthalenes and congener compositions of PCDDs/Fs from incinerators.
Organohal. Compnds. 23, 487-490.
Imagawa T., Yamashita N. (1994): Isomer specific analysis of polychlorinated
naphthalenes in Halowax and fly ash. Organohal. Compnds. 19, 215-218.
Jan J., Zupancic-Kralj L., Kralj B., Marsel J. (1994): The influence of exposure time
and transportation routes on the pattern of organochlorine in plants from polluted region.
Chemosphere 29, 1603-1610.
Järnberg U., Asplund L., de Wit C., Egeback, A.-I., Widequist U., Jakobsson E.
(1997): Distribution of polychlorinated naphthalene congeners in environmental and sourcehttp://www.recetox.muni.cz/old/index-old.php?language=en&id=4349 (2 of 3) [26.1.2007 8:24:32]
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related samples. Arch. Environ. Contam. Toxicol. 32, 232-245.
Kover F. D. (1993): Environmental hazard assessment report: chlorinated naphthalenes. US
EPA, EPA-560/8-75-001. NTIS Publ. PB 248-834.
Popp W., Hamm S., Vahrenholz C., Balfanz E., Kraus R., Theisen J., Schell C.,
Norporth A. (1993): Increased liver enzyme values in workers exposed to polychlorinated
naphthalenes. Organohal. Compnds. 13, 225-228.
Takasuga T., Inoue T., Ohi E., Ireland P. (1994): Development of an all congener
specific, HRGC/HRMS analytical method for polychlorinated naphthalenes in
environmental samples. Organohal. Compnds. 19, 177-182.
Villeneuve D. L., Khim J. S., Kannan K., Falandysz J., Blankenship A. L., Nikiforov
V., Giesy J. P. (2000): Relative potencies of individual polychlorinated naphthalenes to
induce dioxin-like response in fish and mammalian in vitro bioassays. Arch. Environ.
Contam. Toxicol. Submitted.
Weistrand C., Lunden A., Noren K. (1992): Leakage of polychlorinated biphenyls and
naphthalenes from electronic equipment in a laboratory. Chemosphere 24, 1197-1206.
Weidmann T., Ballschmiter K. (1993): Quantification of chlorinated naphthalenes with
GC-MS using the molar response of electron impact ionization. Fresenius J. Anal. Chem.
346, 800-804.
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9.2 Project TOCOEN model sites
The list of TOCOEN model sites is given in Table 9-1.
Table 9-1:
TOCOEN model sites
Number of
site
Description of sites
Period of experiments
1
Brno - town with more than 400 000
inhabitants, with high concentration of
industry
1988-1994
1a
Mokrá - the surroundings of cement
work
1992 - U
2
Dam Nové Mlýny - agricultural site
with large dam
1988-1995
3
Observatory Košetice - background site
4
Stream Fryšávka - background site
5
DEZA Valašské Meziříčí - the
surroundings of model source of PAHs
6
LIAZ Mnichovo Hradiště - the
surroundings of model source of
PCBs, PCDDs/Fs (industrial WI)
1990
7
Technoplast Chropyně - the
surroundings of model source of
PCBs, PCDDs/Fs (industrial WI)
1990
8
Ostrava - big town with very
concentration of industrial source (coal
mining, metallurgy, chemical industry)
1990
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1988
1989-1991
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9
Prague - Capitol of CR, large towm,
more than 1 millions inhabitants, with
very high concentration of industrial
sources and very high density of traffic
1990
10
Vřesová - the surroundings of coal
conversion factory, model source of
PAHs
1991 - U
11
Morava river catchment area including
model area of model industrial sources
DEZA and Technoplast (model sites
no. 5 and 7) and region Zlín - area of
regional ecological risk assessment
project IDRIS
1990 - U
12
Region Zlín - area of regional
ecological risk assessment project
IDRIS
1992 - U
U - At present time, this parts of Project continue without time limitation
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9.3 Sites with long-term programmes
9.3.1 Cement Mokrá (model site No. 1a)
This chapter will be published during 2000.
9.3.2 Regional background observatory - Košetice (model site No. 3)
The Košetice observatory (see Fig. 9-1) of the Czech Hydrometeorological Institute was
established as a regional station of the integrated background monitoring network of the UNEP
project GEMS. The observations were launched at the end of the 1970s, the building of the
observatory was completed in 1988 (Váňa et al., 1997). The monitoring area comprises the
Anenský Brook catchment and the station itself, situated outside this catchment (see Fig. 9-2).
Figure 9-1:
Area of Košetice observatory
The climatic classification of the area where is observatory located (Želivská Hills) is moderately
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warm and moderately humid upland zones. The basic characteristics for period 1961-1990 are
following:
●
mean annual temperature: 7.1 °C
●
annual precipitation total: 621 mm
●
number of snow-cover days: 60 - 100 per year
●
sunshine: 1 800 hours per year
Figure 9-2:
Scheme of monitoring area, Košetice observatory (for
map click on the scheme)
This part of project TOCOEN is focused to the determination of PAHs, Cl-PEST and PCBs
in the air samples A (once in a week), rain water samples RW (every event), surface waters
(W), sediments (SED), soils (S), terrestric biota (earthworms (E), mosses (M) and needles (N) once in a year). The sampling period started in fall of 1988 (see Fig. 9-3).
Figure 9-3:
Sampling network of Project TOCOEN, Košetice
observatory
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9.3.3 The model source of PAHs DEZA Valašské Meziříčí (model site No. 5)
The TOCOEN model source of PAHs is the Corporation DEZA Valašské Meziříčí
(Holoubek et al., 1991). Crude tar and benzene are processed by the manufacturing plant of
DEZA and a rich assortment of product results. The crude benzene processing department
produces pure benzene, pure and varnish toluene, xylenes, and solvent naphtha. The tar
distillation department also produced road tar for road surfaces and tar being used as a
binding agent in the building industry. A large number of fractions are semi-finished
products, which are transferred from the tar distillation department to another
manufacturing department, e.g. to the department producing pure anthracene. Another
manufacturing department producing technical naphthalene supplies the phthalic anhydride
manufacture with initial material. Phthalic anhydride is a parent material for dioctyl
phthalate which is used as a plasticizer. Oil furnace black represents a significant export
article of the corporation. They are produced by ISAF Black (Super Abrasion Furnace
Black) production line.
The surroundings of the Corporation were selected as TOCOEN model site No. 5 - as
model sources of PAHs. The measurement was started in 1989. This model site includes 37
sampling sites for collection of air, sediments, soils, earthworms, needles, mosses and
aquatic biota.
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9.3.4 The model source of PAHs Coal and Gas Fuel Company Vřesová (model site No. 10)
The Coal and Gas Fuel Company Vřesová is situated in the Sokolov coal basin between
the cities Karlovy Vary and Sokolov. This company carries out lignite mining in this part of
the coal basin and produces briquettes, city gas, power, heat, tar, crude benzene, phenol
concentrate, liquid ammonia and other products. The Company is an important producer of
fuels and power which enables the company to contribute to the improvements of the social
and economic life of the region. On the other hand, the Company has the negative effects,
the worst are the ecological ones resulting from the concentration of different industrial
activities in a relatively small area. The surrounding of the Company was selected as
TOCOEN model site No. 10 - as model sources of PAHs. The measurements were started in
1991. This model site includes 21 sampling sites for collection of air, sediments, soils,
earthworms, needles, mosses and aquatic biota.
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9.3.5 Morava river catchment area (model site No. 11)
This chapter will be published during 2000.
9.3.6 Region Zlín - Project IDRIS
This chapter will be published during 2000.
9.3.7 Other research areas
This chapter will be published during 2000.
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9.4 References
Dušek L. (1995): Activity of nitrifying populations in grassland soil polluted by
polychlorinated biphenyls (PCBs). Plant and Soil, 176, 273-282.
Dušek L., Tesařová M. (1996): Influence of polychlorinated biphenyls on microbial
biomass and its activity in grassland soil. Biol. Fertil. Soils, 22, 243-247.
Holoubek, I., Houšková, L., Šeda, Z., Holoubková, I., Kott, F., Kořínek, P., Boháček,
Z., Čáslavský, J. (1990): Project TOCOEN. The fate of selected organic compounds in the
environment - Part I. Introduction. Toxicol. Environ. Chem. 29, 9-17.
Holoubek I., Houšková L., Šeda Z., Holoubková I., Kořínek P., Boháček Z., Čáslavský
J. (1990): Project TOCOEN. The fate of selected organic compounds in the environment Part IV. Soil, earthworms and vegetation 1988. Toxicol. Environ. Chem. 29, 73-83.
Holoubek I., Houšková L., Šeda Z., Kaláček J., Štroufová Z., Vančura R., Holoubková
I., Kořínek P., Boháček Z., Čáslavský J., Kuběna O., Vrtělka V., Vala J. (1991): Project
TOCOEN. The fate of selected organic compounds in the environment - Part V. The model
source of PAHs. Preliminary study. Toxicol. Environ. Chem. 29, 251-260.
Holoubek I., Šeda Z., Houšková L., Kaláček J., Štroufová Z., Vančura R., Kočan A.,
Petrik J., Chovancová J., Bíliková K., Holoubková I., Zemek A., Kořínek P., Matoušek
M., Mikulíková R., Vávrová M. (1992a): Project TOCOEN. The fate of selected organic
pollutants in the environment. Part X. The PCBs, PCDDs and PCDFs in Soils from
Czechoslovakia - Preliminary Study. Toxicol. Environ. Chem. 36, 105-114.
Holoubek I., Kočan A., Petrik J., Chovancová J., Bíliková K., Kořínek P., Holoubková
I., Pekárek J., Kott F., Pacl A., Bezačinský M., Neubauerová L. (1992b): Project
TOCOEN - The Fate of Selected Organic Compounds in the Environment. Part XI. The
PAHs, PCBs, PCDDs/Fs in Ambient Air at Area of Background GEMS Station. Seasonal
Variations. Toxicol. Environ. Chem. 36, 115-123.
Holoubek I., Šeda Z., Houšková L., Kaláček J., Štroufová Z., Vančura R., Kočan A.,
Petrik J., Chovancová J., Bíliková K., Holoubková I., Zemek A., Kořínek P., Matoušek
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M., Mikulíková R., Vávrová M. (1992c): Project TOCOEN. The fate of selected organic
pollutants in the environment. Part X. The PCBs, PCDDs and PCDFs in Soils from
Czechoslovakia - Preliminary Study. Toxicol. Environ. Chem. 36, 105-114.
Holoubek I. (1993): Soil and sediment contamination by persistent organic pollutants in the
Moravian and Slovakian parts of the Danube catchment area and some Bohemian sites in
the Elbe catchment area. Land Degradation and Rehabilitation, 4, 333-337.
Holoubek I., Čáslavský J., Dušek L., Pokorný B., Leníček J., Kočan A., Oehme, M.,
Hajšlová J., Kocourek V. (1993): SYMOS - System of Monitoring of Organic Compounds
in the Ambient Air. Proposal of Monitoring System, Control and Ambient Air Assessment
of Persistent Organic Pollutants. TOCOEN Report No. 87. Masaryk University, Brno, 64
pp..
Holoubek I., Čáslavský J., Helešic J., Vančura R., Kohoutek J., Kočan A., Petrik J.,
Chovancová J. (1994): Project TOCOEN - The fate of selected organic pollutants in the
environment. Part XXI. The contents of PAHs, PCBs, PCDDs/Fs in sediments from Danube
river catchment area. Toxicol. Environ. Chem. 43, 203-215.
Holoubek I., Čáslavský J., Helešic J., Vančura R., Kohoutek J., Kočan A., Petrik J.,
Chovancová J. (1994a): Project TOCOEN. The fate of selected organic pollutants in the
environment. Part XXI. The contents of PAHs, PCBs, PCDDs/Fs in sediments from Danube
river catchment area. Toxicol. Environ. Chem. 43, 203-215.
Holoubek I., Čáslavský J., Vančura R., Dušek L., Kohoutek J., Kočan A., Petrik, J.,
Chovancová J., Dostál P. (1994b): Project TOCOEN. The fate of selected organic
pollutants in the environment. Part XXII. The contents of PAHs, PCBs, PCDDs/Fs in soil
from surroundings of Brno municipal waste incinerator. Toxicol. Environ. Chem. 43, 217228.
Holoubek I., Čáslavský J., Vančura R., Kočan A., Chovancová J., Petrik J., Drobná B.,
Cudlín P., Tříska J. (1994c): Project TOCOEN. The fate of selected organic pollutants in
the environment. Part XXIV. The content of PCBs and PCDDs/Fs in high-mountain soils.
Toxicol. Environ. Chem. 45, 189-197.
Holoubek I., Čáslavský J., Helešic J., Kočan A., Petrik J., Chovancová J., Drobná B.,
Kořínek P., Boháček Z., Holoubková I., Kaláčková L., Kaláček, J., Vančura R., Šeda
Z., Dušek L., Mátlová L., Kohoutek J., Štaffová K., Zemek A. (1994d): TOCOEN
Project. Centr. Eur. J. Publ. Hlth. 2, 122-129.
Holoubek I., Dušek L., Mátlová L., Čáslavský J., Patterson D. G., Turner, W. E.,
Pokorný B., Bencko V., Hajšlová J., Kocourek V., Schoula R., Kočan A., Chovancová
J., Petrik J., Drobná B. (1995): The fate of selected organic compounds in the
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environment Part XXVI. The contents of PCBs and PCDDs/Fs in human fat in Czech and
Slovak Republics. DIOXIN ´95. Organohalogen compounds, 26, 257 - 559.
Holoubek I., Čáslavský J., Kořínek P., Štaffová K., Kohoutek J., Hrdlička A. (1996):
Project TOCOEN. The fate of selected organic pollutants in the environment. Part XXVIII.
Levels of PAHs and some halogenated POPs in ambient air in Czech Republic. Polycyclic
Aromatic Compounds 9, 159-167.
Holoubek I. (1998): Project IDRIS - The relationships between environmental levels of
pollutants and their biological effects. Annual Meeting of Society for Risk Analysis.
Phoenix, USA, December 06-09.
Holoubek I., Tříska J., Cudlín P., Čáslavský J., Schramm K.-W., Kettrup A.,
Kohoutek J., Čupr P., Schneiderová E. (1998a): Project TOCOEN. The fate of selected
organic pollutants in the environment. Part XXXI. The occurrence of POPs in high
mountain ecosystems of the Czech Republic. Toxicol. Environ. Chem. 66, 17-25.
Holoubek I., Tříska J., Cudlín P., Schramm K.-W., Kettrup A., Jones K. C.,
Schneiderová E., Kohoutek J., Čupr P. (1998b): Project TOCOEN. The fate of selected
organic pollutants in the environment. Part XXXIII. The occurrence of PCDDs/Fs in highmountain ecosystems of the Czech Republic. Organohalogen Compounds 39, 137-144.
Holoubek, I., Dušek, L., Adamec, V., Ansorgová, A., Baldrián, P., Cudlín, P., Čupr, P.,
Doležal, L., Elfenbein, Z., Faitová, K., Gabriel, J., Gelnar, M., Helešic, J., Hofman, J.,
Hofmanová, J., Hrdlička, A., Chroust, K., Jurajda, P., Kozubík, A., Minksová, K.,
Machala, M., Maršálek, B., Moldan, B., Prokop, Z., Šmíd, R., Škoda, M., Tříska, J.,
Vondráček J. (1998c): Ecological Risk Assessment. Final Report of Project No. VaV
340/1/96. For Czech Ministry of the Environment TOCOEN Ltd. Brno. TOCOEN REPORT
No. 136. Brno, CR, November 1998, 470 pp. (in Czech).
Holoubek I., Machala M., Štaffová K., Helešic J., Ansorgová A., Schramm K.-W.,
Kettrup A., Giesy J. P., Kannan K., Mitera J. (1998d): PCDDs/Fs in sediments from
Morava river catchment area. DIOXIN 98. Organohalogen Compounds, 39, 261-266.
Škoda M., Dušek L., Holoubek I. (1998): Microbial biomass and its mineralization
activity in a compararative study of five anthropogenic grassland soils contaminated by
persistent organic pollutants. Toxicol. Environ. Chem. 66, 113-126.
Váňa M., Pacl A., Pekárek J., Smítka M., Holoubek I., Honzák J., Hruška J. (1997):
Quality of the natural environment in the Czech Republic at the regional level. Results of
the Košetice Observatory. CHMI Prague, 102 pp.
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Persistent, Bioaccumulative and Toxic Chemicals in Central
and Eastern European Countries - State-of-the-art Report
Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
10.2 Air
10.2.1 Emission inventories
During last two decades there has been a growing interest within environmental research
community to understand the fluxes, behaviour, fate, and effects of PBT compounds
(Holoubek et al., 1993). Various studies and assessments of PBTs in the environment have
been carried out by several international organisations, such as United Nations
Environmental Programme (UNEP), the United Nations Economic Commission for Europe
(UN ECE), the World Health Organisation (WHO), the Nordic Council of Ministers, the
Paris and Oslo Commissions, the Helsinki Commission, and the Great Lakes Commission,
as well as the Arctic Monitoring and Assessment Programme (AMAP). Although a large
quantity of data has been collected, particularly on the levels of PBTs in various
environmental compartments, their migration through the environment and their
environmental effects, the information on fluxes of PBTs is limited.
In 1991 the UN ECE Task Force on Emission Inventories was established to help
developed the procedures and methodologies for emission estimation and reporting for
various persistent air pollutants. An Atmospheric Emission Inventory Guidebook is
currently being prepared within this Task Force (EEA, 1999). The Guidebook is organised in
the form of chapters, each representing various categories, subcategories, or even activities
that generate emission of atmospheric pollutants. The guidebook also includes information
on main groups of PBTs (POPs).
In 1993 the Department of Foreign Affairs Canada, through the Greenplan initiatives,
funded a study to review the information on emission measurements in these countries,
which could be used to elaborate emission rates/emission factors of POPs. This study
(comprising Phase One) was co-ordinated by Axys Environmental Consulting Ltd. (Sidney,
Vancouver, Canada) and involved the joint co-operation of scientists from Czech Republic,
Slovak Republic, Norway and Canada (Holoubek et al., 1993; Parma et al., 1995). The major
output of the study was a report entitled "Compilation of Emission Factors for POPs: A
Case Study of Emission Estimates in the Czech and Slovak Republics.
A set of emission factors has been specified for the POPs studies. Although incomplete,
this set of emission factors should be regarded as an important contribution to a handbook
of emission factors for these pollutants being prepared within the Expert Panel of the
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UNECE Task Force on Emission Inventories in close co-operation with the PARCOM
programme. Emission factors compiled during the project have been used to estimate
emissions of POPs from sources in the Czech and Slovak Republics. The results of these
estimates confirmed that emission factors prepared in the study were sufficiently transparent
with respect to the source categories and therefore can be used together with the statistical
information to assess POP emissions on a preliminary basis.
A variety of technological, meteorological, physical and chemical parameters have been
examined to assess their impact on emission factors for POPs. The parameters have been
grouped so as to allow inclusion into the guidelines on emission estimation and reporting
within the UNECE region. Although neither accurate nor complete, the methodology for
estimation of POP emissions should be a significant step towards obtaining the tools needed
to provide qualitative and quantitative information on emission of POPs at the national
level. This information will be essential for identifying meaningful emission reduction
strategies.
During the course of this study, the most important sources of information related to the
use and emission of PBTs (POPs) in the Czech and Slovak Republics were reviewed. The
available data were found in some cases to be inadequate and in other cases unreliable for
making satisfactory estimates of emission factors for and emissions of PBTs in region.
Consequently, there was a range in the confidence, which the authors place in the specified
emission factors and emissions.
A summary of the level of confidence, based on an arbitrary four-level (A, B, C, D
rating system) placed in the emission factors for the POPs examined in this study
(trichloroethylene, tetrachloroethylene, PAHs, polychlorinated benzenes, phenols,
biphenyls, dibenzo-p-dioxins and dibenzofurans, DDT and its metabolites, HCHs, HCB and
atrazine) for each of the eleven UNECE-designated broad source categories.
The information provided in the report could be used generally in two ways. Experts in
countries where emission factors are known could use the report as a means of data
comparison. Experts in countries where emission factors are not known could use the
information in the report to make a first approximation of their national emissions of POPs.
No emission factors achieved the highest (A) rating except the PAH emission factor for
aluminium products. In general, the highest degree of confidence exists for emission factors
related to the combustion categories because there is a comprehensive historical data set for
both stationary and mobile combustion sources and because concentrations of POPs
associated with most combustion sources are usually relatively high and consequently easily
measured using standardised, well-established techniques. Direct measurements of emission
factors for combustion sources in the Czech and Slovak Republics, however, did not appear
to have been made. Similar situation was in all other CEE countries in the first part of 90´s.
Thus, the quality of the specified emission factors for most of PBTs related to combustion
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sources was rated B. Exceptions were emission factors for HCHs and HCB associated with
industrial combustion plants and processes with combustion because the existence of HCH
and HCB emissions from these sources were not conclusive.
There were far fewer data on emission factors from non-combustion sources because the
concentrations and emission rates tend to be lower and more difficult to quantify than those
for combustion sources. In addition, less was known about the nature of the emission
processes associated with these sources. Consequently, the rating of the reliability of
emission factors of the various significant POPs for non-combustion processes was
generally C except for PAHs which rate due to the existence data and a better understanding
of the processes involved.
The overall goal of the phase two of this project (Parma et al., 1995) was to prepare a set
of guidelines (including the guidelines for emission verification procedures) for estimating
PBT emissions from various sources. Care was taken to ensure that the results of the project
would be compatible with the above-mentioned UN ECE Guidebook on the emission
estimation.
Emission inventories are never completely accurate, because unsurveyed or
inadequately described sources are always present. Inventories are also never finished,
because society moves ever on, building new sources of emissions, controlling the
emissions of others, and ceasing the operation of still others.
As a result of phase two of this project was report "Atmospheric emission inventory
guidelines for persistent organic pollutants" (Parma et al., 1995) which presented new
information on emission factors of POPs. These emission factors were performed by direct
measurement of Czech emission sources. This guidelines was fully compatible with the
format of the UN ECE Atmospheric Emission Inventory Guidebook and was in 1995 good
tool with the aim to help developing national and regional emission inventories.
These guidelines had some subjects, which require further study in order to ensure the
accuracy, completeness, and transparency of the POP emission surveys, prepared with the
help of these guidelines. Some of these subjects included:
●
elaboration of more accurate and complete species profiles for at least major source
categories of POPs,
●
broader information on the impact of different industrial (combustion, incineration)
technologies on the amount of POPs emissions,
●
broader information on the impact of different flue gas treatment operations on the
amount of PBT emissions, and
●
application of proposed emission factors to estimate POPs emissions in selected
regions and comparison of these estimates with either measurements or independent
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calculation.
These guidelines included results of measurement of emission factors and species
profiles for various source categories. Both can be used in other CEE countries because the
technologies and their state are similar.
There were similarities in source profiles of POPs for some source categories discussed
in this study. This particularly applies to combustion of fossil fuels in large power plants
and incineration of wastes in major incinerators. Obviously, the content of chlorine in fuels
and wastes may differ significantly. The process of POP generation during combustion of
fuels and incineration of wastes, however, is similar.
Combustion of generates higher emissions of most of the studied POPs than the
combustion of oil, gas, and fuel wood. This particularly applies to the emissions of PCBs
and PCDDs/Fs during combustion of hard coal. In the emissions from the burning of fossil
fuels there is a considerable content of PCDDs/Fs in comparison with their emissions from
other sources. There is also a higher proportion of phenanthrene compared with other
PAHs. During the combustion of industrial waste, phenanthrene, fluorenthene and pyrene
are characteristically, significantly higher in the flue gas.
At present time, only Czech Republic from the CEE countries perform very broad
project concerning the measurements of emissions from typical sources of POPs (MOE CR,
1997). The comparison of former estimation (Warmenhoven et al., 1989; Holoubek et al., 1993)
and the first inventories based partly on the measurements, partly on the expert estimation
(Parma et al., 1996) with the results of this project is shown in Tables 10.2-1 - 10.2-5
(Holoubek et al., 2000a).
The present number of PBTs emission inventories is very small. UNEP published the
review of national PCDDs/Fs emission inventories (Fiedler, 1999). The situation in the
Czech Republic was discussed above, UNEP report still describes the results of emission
inventories in Hungary and Slovakia (Fiedler, 1999). In 1997, the Hungarian Institute of
Environmental Protection published a report on emissions of POPs in preparation of
international agreements. In this report, an inventory for PCDDs/Fs from sources in
Hungary was included. Based on emission factors as established in the report by TNO (UBA,
1997), PCDDs/Fs emissions were determined for various reference years 1985, 1990, 1993,
1995, and 1996. The estimated values were 214.65, 167.36, 119.57, 112.21 and 103.53 g ITEQ annually, respectively.
In 1994, the Slovak Republic undertook a first study to establish an emission inventory
of POPs (Kočan, 1994). The estimate is based on available information on emission sources,
source parameters and emission factors obtained from either own measurements or from
published literature sources (Holoubek et al., 1993). The reference year was 1993.
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The total emissions of PCDDs/Fs into the atmosphere were estimated to be 42 g I-TEQ.
a-1 for this reference year. In 1993, incineration of waste was responsible for 61 % of the
total emissions, the serious sectors of metal industry accounted for 20 % and energy
production for 17 %. The Slovak Republic is aware of potential further sources, e.g.
emissions from the chemical industry (including oil exploitation, transport and storage,
petrochemical industry, production of organohalogen compounds and paints), but could not
be quantified at this time. Emissions from landfills and waste dumps, re-entrainment of
PCDDs/Fs from contaminated soils and from water surfaces, were identified but could not
be quantified. In addition, the numbers of this preliminary estimation should be regarded as
lower estimates, actual values are expected to be higher as for some sources there are high
uncertainties in emission rates. The uncertainties in the emission estimates result from the
uncertainty in the emission factor, the activity rate (the amount of fuel processed) and the
efficiency of the pollution control device (flue gas cleaning system).
The TNO study (UBA, 1997) presents the results of an emission inventory project for
heavy metals and POPs for 1990 on the basis of submissions of emission data from the
Parties to OSPARCOM, HELCOM and the Convention on LRTAP (Fiedler, 1999). The
inventories included total of 38 European countries with exception of the three Caucasian
countries and Turkey. For the countries, sources or compounds missing in official
submissions, default emission estimates have been prepared and applied to complete the
inventory. In general terms, the PCDDs/Fs emission per source category has been estimated
for each country by multiplying the activity rate of the source (e.g. ton cement produced)
with an emission factor (e.g. mg I-TEQ emitted per ton cement produced). The default
emission factors have been applied uniformly over Europe for most categories due to lack
of detailed and reliable data rather than deliberate choice. Differences in default emission
factors between regions and countries in the validation database were based on differences
both in techniques and in abatement.
In order to determine the total emissions for the 38 European countries, Europe was split
in three groups: North-western (including Italy), Southern (excluding Italy) and Central and
Eastern countries. Aggregated emissions were summarized for the OSPARCOM (15
countries), EU members (15), HELCOM (9) and CEE countries (19) (see Table 10.2-6). For
the HELCOM and CEE countries combustion of hard coal was identified as the major
contributor to the dioxin emission inventory followed by sinter plants and the copper
industry.
Some measurements of PCDDs/Fs in industrial emissions were performed in Poland,
too (Grochowalski and Chraszcz, 1997; Chraszcz et al., 1995). Measurements of the PCDDs/Fs
present in combustion gases from Polish power stations, which were performed in 1995-96,
revealed that those gases contained small amounts of these compounds (about 0.0050.01 ng TEQ.m-3). The level in emission from Krakow power station was higher (0.010.2 ng TEQ.m-3). This power station had worse burning conditions such as oxygen
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deficiency, lower temperatures of burning, lack of after-burning and slower cooling of
combustion gases in chimneys.
Also the contents of PCDDs/Fs in eleven medical wastes incinerators in Poland installed
in Polish towns, were measured (Chraszcz et al., 1995). The level of stack gas concentration
of PCDDs/Fs in new type of incinerators installed in 1992-96 was in good accordance with
appropriate regulations concerning maximum acceptable limit in West European countries
(0.1 ng TEQ.m-3). The contents of PCDDs/Fs in new types of medical waste incinerators
(8) ranged between 0.015 and 0.32 ng.m-3 (only one was over the value 0.1), but in older
types (3) ranged between 2.1 and 23 ng TEQ.m-3. The contents of PCDDs/Fs in bottom ash
in new types were between 7.8 and 22 ng TEQ.g-1 and in older ones between 9 and
43 ng TEQ.g-1. Unfortunately, the emission factors for these sources were not published.
In Hungary at present time, about 35 % (3.105 t) of the total household waste and about
25-30 % (1.5.105 t) of the total hospital waste of country are combusted by one municipal
waste incinerator (Northeast region of Budapest) and about 100-150 hospital waste
incinerators. Present total emissions of PCDDs/Fs into the air are estimated at about 5-10 g.
a-1 from MWI and 3-15 g.a-1 from HWIs (Kisfalvi, 1995). The emissions from 25 HWIs,
were measured. The average concentrations of PCDDs/Fs in stack gases were between
0.1 - 70 ng TEQ.m-3. Only one HWI equipped by new cleaning system agreed with
Hungarian regulation (0.1 ng TEQ.m-3). The emissions from all others were higher and
ranged between 10 and 70 ng TEQ.m-3. Again unfortunately, the emission factors from
these measurements, were not published.
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Persistent, Bioaccumulative and Toxic Chemicals in Central and
Eastern European Countries - State-of-the-art Report
Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
10.2.2 Ambient air
The Ministry of the Environment of the Slovak Republic promoted the project entitled "Phare
Project EU/93/AIR/22 Local Studies of Air Quality in the Cities of Bratislava and Košice National
Needs Assessment of Air Pollution", with the financial support of the European Union (PHARE
Programme). Average life expectancy for the Slovak population is reported as one of the shortest
in Europe. From this reason the MOE SR have prepared the comprehensive study which was
focused to the improvement a national strategy for air pollution control including the risk
assessment of air pollution. The specific objectives of this study were the identification and
analysis of available data on main emission sources of volatile organic compounds (VOCs),
persistent organic pollutants (POPs) and heavy metals, quantification of emissions. It was based on
available data, implementation of sampling and analytical procedures for ambient air samples and
implementation of QA/QC procedures, in accordance with European and international guidelines
and specifications, ambient air quality measurements and assessment, comparing the results from
measurements with national or international standards and baseline risk assessment. Samples were
collected in 20 selected sampling locations throughout the Slovakia during one year in order to
evaluate seasonal variations (PHARE, 1997).
They prepared for Slovak Ministry of the Environment during period 1997-1999 very on the
European level unique study concerning the environmental and human population load in the area
contaminated with PCBs (Kočan et al., 1999).
The first information concerning to ambient air levels of PBTs compounds in former
Czechoslovakia were published as results of Project TOCOEN (Holoubek et al., 1992; Chovancová et
al., 1994).
In many cases, emissions to the atmosphere represent the main way the compounds are
released into environment. To assess the effect of the steps taken to reduce the POPs emission,
monitoring of their concentration levels is required. Aiming at the study of long range transport
and deposition, measurements of PBTs compounds atmospheric concentrations were being carried
out in Czech Republic and data obtained were related to air concentrations of other pollutants and
to meteorological parameters (Holoubek et al., 1996).
Czech Ministry of the Environment and RECETOX Brno realised in CR System of Monitoring
of Organic Compounds in the Ambient Air (SYMOS), a preliminary monitoring system of PBT
compounds in ambient air in CR. During SYMOS pilot study in 1994-1995, PAHs, PCBs,
chlorinated pesticides and PCDDs/Fs were monitored in the area of Košetice observatory
(professional observatory of Czech Hydrometeorological Institute located in south Bohemia).
Observatory Košetice was established as a regional background station of international monitoring
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(EMEP, GAW, GEMS) and national monitoring programmes (monitoring of Czech MOE, Project
TOCOEN, GEOMON) (Váňa et al., 1997).
In the pilot study of the SYMOS Project, samples were taken in area of Košetice observatory
from July to December 1995. The 24-hours samples were collected weekly, starting on
Wednesdays, 8 a.m., PCDDs/Fs were sampled in four-weeks intervals. The pollutants were
collected by using of a high volume sampler equipped with quartz filter and polyurethane foam
adsorbents.
Concentrations of observed pollutants found during the pilot study of the SYMOS Project in
Košetice observatory are shown in the following Tables 10.2-7 - 10.2-10.
A comparison of the results from Košetice with values from various rural and urban areas are
given in Table 10.2-11. The PAHs range found in ambient air in UK was estimated in London,
Manchester, Cardiff and Stevenage (Halsall et al., 1993). The sampling and analytical methods were
similar, but the sampling strategy was different because week samples, each one per 2 weeks, were
taken regularly in the period of 1990-1991. In Sweden, 24-hours samples were taken in Rorwik
field station, Swedish west coast, in rural area about 40 km south of Gothenburg in three to fourdays periods in January - February 1989, February and May 1990.
From 1996, the regular monitoring of semi-volatile PBTs was continued at the Košetice
observatory, under a co-operation scheme between Czech Hydrometeorological Institute Praha and
RECETOX - TOCOEN & Associates, Brno. The Košetice Observatory is included among regional
background stations under both international (GAW, EMEP) and national (TOCOEN)
programmes (CHMI, 1997, 1998, 1999). In present time, the TOCOEN monitoring programme of
PBTs at Košetice observatory has been carried out on a regular basis for already 12 years - a
unique achievement globally (see Chapter 9.3.2 too). The sampling procedure (one samples per
week for determination of PAHs, PCBs and OCPs) and analytical determination is based on
conclusions of EMEP co-ordinating meeting took place in Norway in November 1997 (EMEP,
1998). Pollutants mentioned above are monitored in the gaseous state as well as in atmospheric
particulates. The Tables 10.2-12 - 10.2-17 show the results of measurements from 1996 to 1999.
The Figures 10.2-1 - 10.2-8 depict profiles of observed concentrations of Sum of PAHs, Sum of
PCBs, DDT and its metabolites and HCB (Holoubek et al., 2000b).
The PAHs concentrations identified follow characteristic course prompted by the higher
occurrence of these compounds in winter when they are produced by various combustion
processes. The high New Year 1997 value was probably the result of episodic input from local
heating systems. PCBs and OCPs concentrations display a totally different profile in which no
such "seasonality" has been identified. These compounds are present in the atmosphere today due
to their volatilization from soil and sediments, i.e. as secondary inputs from old deposits, and also
due to a long-range atmospheric transport from regions in which they are still used. These results
reflect the global trends. PCBs occurrence remains at the level of the European background.
Predominance of degradation metabolites of DDT (DDE and DDD) was observed (the same trend
exists in all environmental samples from this observatory - see Chapter 9.3.2). This predominance
reflected old loads - input from old usage and environmental accumulation of DDT rather than
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long-range transport from regions where the compound is still in use.
Several study activities upon request of the Ministry of the Environment or Ministry of the
Health SR have been conducted in the Slovak Republic in the recent years, aimed at characterising
the ambient air situation within the national territory. Analysis of emissions of air pollutants in
selected areas has been conducted, based mainly on a specific, while only partially updated,
database on emissions and direct emission balance of selected toxic and carcinogenic organic and
inorganic compounds in ambient air in selected locations of the Slovak Republic.
In fact, only limited information on ambient air concentrations of hazardous air pollutants,
such as heavy metals, was available in Slovakia. Almost nothing was known about benzene,
toluene, ethylbenzene, xylenes (collectively known as BTEX), 1,3-butadiene, and very limited
information on persistent organic pollutants (POPs) such as polycyclic aromatic hydrocarbons
(PAHs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/Fs) and pesticides. From
the point of view of health risk, the ambient air particulate matter (PM 10) concentrations were
also not known.
The first study of PCB contamination of ambient air in Capitol of Slovakia Bratislava, were
performed in the centre of town, suburban regions of Bratislava and in the selected background
area (Chovancová et al. 1994). The observed values of PCBs in suburban part and in the selected
background area were similar to levels ranged from 0.05 to 1.4 ng.m-3 (0.69 ng.m-3 average) that it
was determined in a Czech rural area (background observatory Košetice, South Bohemia)
(Holoubek et al. 1992, 1995, 1996, 1997, 1998). This data were also comparable with background
PCB concentrations in ambient air in other parts of the world.
Higher PCB levels (4.7 and 4.2 ng.m-3) were found in the centre of Bratislava with dense
automobile traffic. There has been considerable similarity between PCB homologous group
concentrations of all the samples.
The MOE SR recognised that without a deeper examination of hazardous air pollutants in
ambient air, they would not be able to assess the risk of air pollution to humans with a
consequential stalling of further developments in air protection policy. It was therefore decided
that the first PHARE project in the field of air pollution (PHARE Project EU/93/AIR/22) should
have been aimed at assessing hazardous air pollutants.
The overall aim of the project was to strengthen the capacity of the MOE SR to improve the
national strategy for air pollution control, which is based on sound data/information on the
pollutants of interest, including a sound scientific basis for the evaluation of the health risks caused
by toxic and carcinogenic substances in ambient air.
This project had a pilot study (Kočan et al., 1998) and data from this study introduced the initial
information for the PHARE Project (EU/93/AIR/22) "Local Studies of Air Quality in the Cities of
Bratislava and Košice. National Needs Assessment of Air Pollution". This project was solved in
1996-7 and aimed at improving air quality in Slovakia (PHARE, 1997). During the pilot study,
ambient air samples were collected at 17 sampling locations. Two sampling sites can be
considered as agricultural areas, one as a background and the remaining sampling sites were
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situated in polluted (non-attainment areas).
The highest levels of both total PAHs and carcinogenic PAHs were found not surprisingly in
sample Košice (Šaca) collected several km far from the biggest Slovak metallurgical plant
releasing large quantities of PAHs into the atmosphere. The concentration would be even higher,
however, wind was blowing from the sampling site towards the plant. Approximately 10- to 20times lower total PAHs levels were found in an air sample from the background location of Starina
if compared with Bratislava and Košice. Influence of traffic can be seen from difference of PAH
levels in samples from Bratislava (capitol of Slovakia with about half million inhabitants. A
calculated PAH concentration in one site (Patronka, a crossroads with heavy traffic in the north
part of town) by day, i.e. at higher automobile burden, was 750 ng.m-3 while concentration by
night was only 270 ng.m-3.
As expected, the highest PCB concentration was found in sample collected in Strážské, i.e. in a
town where PCB formulations were produced in the period 1959-1984 (11.31 ng.m-3). Increased
PCB levels were also found in the Michalovce (town which is located 15 km from Strážské, only 1.72 ng.m-3), in Bratislava, Patronka (as we noted earlier - busy crossroads) showing that
automobile traffic could be a source of those pollutants (4.36 ng.m-3) and in the Žiar nad Hronom
(it can be caused by emissions from an aluminium works - 4.17 ng.m-3).
The highest HCB concentrations were observed in the sample from the agricultural areas
(Levice - 4.74 ng.m-3, Topolníky - 4.45 ng.m-3), a busy crossroads (Bratislava, Patronka - 3.62 ng.
m-3) and in the vicinity of the waste incinerators (Bratislava - 3.6 and 3.57 ng.m-3 resp.). This can
be caused by using HCB as a fungicide (already banned), and by its formation during combustion
processes. In spite of high p,p´-DDE levels in the Slovak human population, air concentrations of
this pollutant were about 10-times lower than HCB concentrations. They ranged from 0.032 to
0.87 ng.m-3. The lowest levels of almost all the monitored PBTs were determined in the samples
collected in the background forest area of Starina (northeast part of Slovakia, near to the Ukraine
border).
The main part of Project PHARE was performed during period of 1996-7. Monitoring
programme envisaged sampling activities, so that both seasonal variability and emission patterns
were taken into account. Target regions throughout Slovakia were selected for sampling, including
eight industrial non-attainment areas (Bratislava, Košice, Krompachy-Rudňany, Žiar nad Hronom,
Vranov-Strážské-Humenné, Žilina, Prievidza, Ružomberok), agricultural sites (Levice-Mochovce,
Topolniky, Hurbanovo) and a background area (Starina). "Non-attainment areas" were defined as
areas where air quality does not meet national ambient air quality standards.
The sampling schedule involved making eight measurements at twenty sites within the target
regions over a year, i.e. 160 samplings. This means that there could be a maximum of 160 results
for each compound of interest. However, not all of them were sampled on each occasion. In fact
the number of results for each group of analytes was 160 for VOCs, PCBs, PAHs, heavy metals
and vapour mercury, 112 for PCDDs/Fs and 48 for PM10 and determination of morphology and
mutagenicity.
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In addition there were 160 measurements of total particulate matter obtained from the PCB and
PAH samples. Since most of the analysed groups involved the measurement of several individual
analytes, from 8 heavy metals to 42 VOCs, the total number of individual analytical results was
more than 15 000.
Analyses for the selected compounds of interest were based on standard method and
procedures, as defined by international organisations. The method were largely determined by the
choice of sampling equipment and the availability of a comprehensive set of procedures which are
widely accepted and used. The validity of the analytical methods was established by the use of
spikes and surrogates. The validity of sampling and analysis was established by the measurement
of duplicates. Extremely good performance of the selected methods and procedures was found,
indicating that the results should be reliable. Meteorological data was also recorded during
sampling. It was also used to determine which of the major sources of emissions might contribute
to the measured levels for each individual campaign.
The comparative risk screening analysis evaluates air pollution problems of selected sites in
Slovakia. The analysis was focused on adverse human health effects that vary widely in type and
severity. The risks were characterised in quantitative terms wherever data and methods were
available. However, due to the preliminary nature of the screening analysis and the large degree of
uncertainty inherent in any risk assessment, the quantitative estimates were primarily used for
comparing relative risks and not as measures of actual individual risk or the incidence of adverse
health effects in the exposed population. Because this screening analysis does not address every
possible environmental problems and effects, the results do not provide a complete basis for risk
management decisions. But this analysis identifies clearly risk problems that require immediate
attention, as well as further research and analysis needed to make risk decisions for other
environmental problems in Slovakia.
Some sampling locations, mainly in city centres showed a definite seasonal variation for
particulate matter, with higher levels in winter, but other locations, particularly rural ones, did not
show any significant seasonal variation.
Analysis of the relative amounts of each PAHs showed an essentially constant pattern. Based
on this pattern, their origin was confirmed as being from combustion processes. Additionally there
was usually also a strong correlation between PAH and particulate levels, which again was
expected from the likely source and the physical properties of the PAHs. This indicates that
reduction of particulate levels should also reduce PAH levels independent of any specific
measures to reduce PAHs.
As regards PAHs originating from specific industrial processes, such as the production of
carbon anodes at the aluminium plant at Žiar and the coke plant at a major steel plant at Velká Ida
near Košice, the evidence was mixed. At Žiar, there was no evidence for any significant
contribution from a specific source. The seasonal pattern was similar to other sites where the major
contribution was assumed to derive largely from heating and power generation and general
combustion. At Velká Ida, the levels found in the different campaigns did not show such an
obvious seasonal variation and were more readily explained as deriving from a process in
operation at roughly the same level throughout the year, i.e. an industrial process. Additionally, the
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levels were much higher than would be expected from the combustion requirements of the local
population. However it might equally be associated with the significant power generation activities
at the steel plant.
Almost all the PCDDs/Fs congener patterns observed were very similar and typical of the
pattern observed from general combustion sources, with the exception of the highest level sample
from Bratislava - Starohájská, the source of which was not clear, but probably resulted from the
combustion of specific chemical material. The range of results was comparable with published
data from various part of the world.
The PCB congener patterns observed for all samples were similar, although there were
differences in relative amounts depending largely on temperature. This was expected since there
should be relatively little fresh PCB input into the environment. Most of the PCBs in the
atmosphere is believed to be due to re-evaporation from the soil and very little from current
industrial activity, even combustion. Consideration of the individual results at each location did
show a slight trend to higher overall levels in summer as compared with winter. While the mean
level at Strážské was indeed slightly higher than most other locations, as expected since this was
the former source of production of commercial PCB mixtures in former Czechoslovakia, it was not
markedly so and did not indicate a major problem in relation to the ambient air. The Slovakian
results are significantly lower than for example results from UK.
These activities of Kočan group continue and they prepared for Slovak Ministry of the
Environment during period 1997-1999 very on the European level unique study concerning the
environmental and human population load in the area contaminated with PCBs (Kočan et al.,
1999a). The results will be published latter, now we will publish on some the first summary
information.
The goal of this study was to study of actual level of contamination with PCBs in Slovakia.
The first part of product prepared actual inventory of PCBs in Slovakia (summary of this you can
see in Chapter 6.3), the second part was focused on the collection of environmental, food and
human samples and analysis of PCBs and selected organochlorine pesticides (DDT, HCB and
HCH). Samples of air, surface, drinking and ground water, sediments, soils, wildlife, food and
human blood were collected in the vicinity of Chemko Strážské (former producer of PCBs),
District Michalovce, Eastern Slovakia and for comparison, the same samples were collected in
rural region - District Stropkov.
Summary of results from measurement of ambient air is described in the Table 10.2-18.
Twenty times higher level of PCBs were observed in the vicinity of the former producer and its
waste dumps.
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Table 10.2-18: Summary of concentrations of PCBs and OCCs in ambient
air [pg.m-3]
Study of environmental and human exposure load in the
area contaminated with PCBs (Kočan et al., 1999a)
Pollutants
District Michalovce (n=6)
District Stropkov (n=6)
100 - 1 700
64 - 200
HCB
21 - 37
53 - 100
DDT + DDE
33 - 260
23 - 1 100
Sum of PCBs
Figure 10.2-9: PCBs concentrations in pg.m-3 in ambient air samples
collected around Michalovce and Stropkov districts (Kočan
et al., 1999b).
We can compare these data with actual levels from Košetice regional background area in
Czech Republic.
The measurements of PBTs compounds in ambient air of the Capitol of CR, Prague, were few
years organized by Czech Ministry of the Environment. From 1994 to 1996, four sampling
campaigns were performed. Unfortunately, these obtained data never been published. Ranges of
measured values from these measurements, are shown in Table 10.2-19 (AXYS, unpublished data).
DDTs, HCHs, CHLs, HCB and PCBs concentrations were determined on monthly intervals in
ambient air samples collected in city of Gdańsk in 1991-92. These are the first data on persistent
organochlorines in ambient air in Poland. The pesticides such as technical DDT, gamma-HCH
(Lindane), technical HCB and Melipax were intensively used in Poland from around 1950 to
around 1980. HCB, alpha-HCH, gamma-HCH, p,p´-DDT, o,p´-DDT, p,p´-DDE, o,p´-DDE, p,p´DDD, o,p´-DDD and PCBs were detected in all air samples collected in city of Gdańsk in 199091, while the constituents of technical chlordane were absent above detection limit of the method.
The concentrations of HCB and PCBs were dependent on the air temperature, hence their main
source can be related to a process of degassing from the soil (Table 10.2-20).
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Some measurements of PCDDs/Fs in ambient air were also done in Poland, in city of Krakow
(Grochowalski et al., 1995, 1997). Krakow, the second largest city in Poland (round 950 000
inhabitants) is one of high population density. In the surroundings of town are located heavy
industrial complexes, black coal mines, iron smelters. Town has very high density of traffic, power
generation and household heating facilities are based on black coal burning. Krakow has very
serious air pollution, which has increased with the growth of industry and traffic. As a result, it
was revealed that the basic source of the PCDDs/Fs emission into the air over Krakow, were
uncontrolled processes of waste burning. In 1996, the measurements of PCDDs/Fs in air
suspended particulate matter (the dimensions less than 10 µm), was performed. The results showed
that the level of dioxin content in ambient air in Krakow is much higher, with comparison to, their
contents in air in other big cities in Western Europe. In general, the ambient air concentration in
Western cities is described about 0.3 pg TEQ.m-3. In Krakow, during winter months, the level of
PCDDs/Fs was over 5 pg TEQ.m-3 (maximum ranged from 2.58 to 5.74). The average content in
air during period January-March 1996 was about 2 pg TEQ.m-3 (four sampling sites, samples were
collected twice per months during period January-March and June 1996, together 32 samples). The
level of PCDDs/Fs in samples collected in June was much lower in the range 0.06-0.12 pg TEQ.m3. The maximal content of PCDDs/Fs to mass unit of suspended particulate matter in the air was
observed during winter months (23.5 ng TEQ.g-1). During summer months (June), the level in s.p.
m. was of one order lower - about 2 ng TEQ.g-1.
The Baltic Sea is vulnerable to pollution due to its semi-closed character and hydrology. The
long residence time of water has led to the accumulation of nutrients as well as PBT compounds.
Although trends in levels of PBTs in some Baltic biota are well documented, little is known about
the origin of these pollutants and the flow between different compartments in the ecosystem (Agrell
et al., 1999). It is unclear, whether the atmosphere, the rivers or the sediments constitute the
dominant source of pollutants to the biota of the system. Furthermore, many of the fundamental
processes, which these compounds undergo, need to be better understood if we are to quantify and
predict their environmental fate and transport in the Baltic ecosystem. These processes include
deposition from the atmosphere, transfer across the surface microlayer, partitioning between
different compartments in the water-phase, interaction with biota, incorporation into the sediment,
redistribution from sediment to water and volatilization across the water-air interface.
The ambient air levels of OCCs were studied in the Gulf of Riga (Roots, 1996). These
compounds are carried to the Gulf of Riga by two ways: either they are carried there from the
Central Europe by the means of long-range transport or with air-transport from the Kola peninsula
(Oehme et al., 1994), or from the local waste-centre near the gulf. PCBs and OCPs were measured
by the Lund University on the samples taken in three Baltic air research stations (two in Estonia
and one in Latvia) (Larsson and Okla, 1989). The results have shown, that the air and rainwater
samples taken in Estonia stations were relatively clean compared to the samples taken in Latvia.
This refers either to the long-range transport to the local waste-centre situated near the Gulf of
Riga. Based on these preliminary results, the project "Organic pollutants, load and critical
processes", were prepared (Agrell et al., 1999). The industrial mixtures of PCBs, OCPs such as
HCHs (alpha and gamma), DDTs (DDE, DDT) have been used as model compounds to evaluate
the contamination situation.
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The use of DDT were restricted or banned in all countries surrounding the Baltic Sea during 7and 80ies. In some countries adjacent to the Baltic Sea, e.g. Denmark, Poland, Germany and
Norway, lindane is still in use for controlling crop and forest pests and fumigating storage rooms.
In Norway there is no restrictions against usage of this product but it is banned in Poland,
Denmark and Germany. In Sweden (1988), Estonia, Latvia and Lithuania, a total ban against usage
of both technical HCH and lindane exists. Finland has banned usage of lindane, but technical
mixture of HCH is unregistered.
Ambient air and precipitation samples were collected at 16 sampling stations across the
Bothnian Bay and Baltic Proper from October 1990 to February 1993. In these samples, 51 PCB
congeners, DDTs and HCHs were determined. Sampling was carried out continuously during one
year for most of the stations, and up to two years for some stations. PBTs in the rivers Wistula and
Odra in Poland during 1991-1993, in order to calculate the river input from densely populated and
industrialized catchment areas. During the autumn of 1993, PCBs, DDTs and lindane were also
measured in two smaller Swedish rivers, the southern river Morrum and the northern river Ume.
During the study a total of 299 air samples, 192 samples of precipitation and 775 river water
samples were collected around the Baltic Sea.
The median concentration in the air samples for all stations were 57 pg.m-3 for PCBs, 1.6 pg.m3 for DDTs (sum of p,p´-DDT and p,p´-DDE) and 25 pg.m-3 for HCHs (sum of alpha and gamma).
The ration between maximum and minimum median concentration between stations was 2.5 for
PCBs at 15 of the stations. The concentrations ranged from 32 to 80 pg.m-3. Due to this
homogeneity, this PCBs concentration interval could be considered as background levels for the
Baltic Sea. The ratio between maximum and minimum in median concentration between stations
was larger for DDTs, and especially for HCHs, 13 and 26 times respectively. One explanation of
this discrepancy between the pesticides and PCBs may be that the diffuse sources of PCBs are
more evenly distributed over the Baltic Sea area, whereas the source-areas of DDT and HCHs are
found mainly in the agricultural, southern parts. Also, the variation in concentration of pollutants
within the station was greater for the pesticides than for PCBs. This could be explained by that,
HCHs and DDTs as pesticides are used seasonally, which is not the case for the industrial
chemical PCBs. The finding that concentrations in the atmosphere within a station generally show
greater variation for pesticides than for PCBs, agrees with a similar study on deposition of POPs to
Skagerack area, west Sweden (Brorstrőm-Lundén, 1995).
The station in Latvia (Salaspils) consistently showed the highest values of PCBs and DDTs in
air, with a median of 454 pg.m-3 of PCBs and 12 pg.m-3 of DDTs. These levels, which are about
eight and six times higher than the median concentrations of all stations, are most likely the result
of local sources. This sampling station was situated only 10 km from Riga, an industrial city with
one million inhabitants. On the other hand, the levels of HCHs in Salaspils were similar to other
stations in the vicinity (median of 39 pg.m-3), indicating that Riga does not act as a point source
for HCHs. Instead, the highest median concentrations of HCHs were found in Swibno (103 pg.m3) and Dziwnow (72 pg.m-3), the two Polish stations which also had high median concentrations of
DDTs (6 and 9 pg.m-3). Both stations are situated in agricultural areas and it is possible that the
insecticides have either been used recently, as Poland does not have restrictions against usage of
lindane, or previously (HCHs and DDTs) in such large amounts that revolatilization from the
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ground.
The study of the pathway of benzo(a)pyrene (BaP) migration from bulk deposition to soil and
vegetation, with special emphasis on the forest ecosystem, was performed in Lithunia (Milukaite,
1998). The flux of BaP in Lithuania varied from year to year, exposing ecosystem to various loads
of carcinogen. The monthly flux of BaP at the background station (Preila) ranged from 0.3 to
3.8 µg.m-2mo-1 over the past six years. The flux of BaP was higher at suburban site in the eastern
part of Lithuania, where it varied from 0.6 to 4.8 µg.m-2mo-1. The average annual flux generally
increased from year to year, except for 1993. Across all of Lithuania, the total annual flux of BaP
ranged from 624 kg in 1993 to 2574 kg in 1995. BaP uptake from the soil by vegetation was
studied (see Chapter 10.8).
Rain could washout BaP from the atmosphere was studied in Lithunia, too. The comparison of
monthly average meteorological parameters and flux of BaP from the atmosphere from the
atmosphere to the ground during three studied years showed that the amount of precipitation had
no obvious influence on BaP flux intensity, except during heavy snowfalls (Milukaite and
Mikelinskiene, 1998). Ambient temperatures higher than 25 °C can have an effect on the BaP
partition between the vapour and aerosol phases. The vapour phase may increase by up to 28 %
during the hot midday, and the high temperatures can effect the reliability of BaP photochemical
transformation.
The construction of a mobile plant for thermal destruction of waste, primarily industrial
(´PUTO´), located at Jakuševec, a village south of Zagreb, initiated an investigation of levels of
PCDDs/Fs, in the ambient air of Zagreb (Krauthacker et al., 1998). The new mobile incineration
plant ´PUTO´ for industrial waste equipped with modern emission control devices was constructed
in 1997 at the landfill site of Zagreb. A total of twenty ambient air samples was collected at five
locations. These sites were different in the expected levels and possible PCDDs/Fs sources. These
sites were followed: location at ´PUTO´, Jakuševec - village located south of ´PUTO´, Dordičeva
street - location of intensive traffic in the city center, Žitnjak - the main industrial zone of Zagreb
city and Imi - location in the north of the city with the lowest air contamination levels.
In general the results of the spring measurements are lower than in winter. There are no
limitations for the PCDDs/Fs level in the ambient air. In the spring all results are significantly
bellow the "guide value" of 150 fg I-TEQ.m-3 (used as recommended level in Germany) whereas it
was occasionally exceeded over winter. Obviously the sampling point Imi, which is located at the
north edge of Zagreb, indicates the background level of the region with about 10 fg I-TEQ.m-3 in
the spring and up to 70 fg I-TEQ.m-3 in winter. The calculated I-TEQ values were between 9 and
47 fg.m-3 for samples collected in May/June 1997 and between 17 and 308 fg.m-3 for samples
collected from January to April 1998. The samples collected in 1997 showed the highest levels at
the location of ´PUTO´ plant and in the Jakuševec village. The highest levels in the samples from
1998 were found at the location of Žitnjak, while the lowest I-TEQ values were determined at the
Imi location. The sampling points PUTO and Jakuševec seem to be influenced by the same sources
(waste disposal, industry), because the results at each location in both sampling periods showed
comparable results as well as similar profile of the isomer distribution. The elevated
concentrations in winter months are probably due to the meteorological conditions with more
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inversion situations resulting in a worse transportation of the pollutants and due to the private
heating systems. As the emissions of PCDDs/Fs reduced mainly due to the installation of modern
filter systems at incineration plants and plants with other thermal processes such as metal
reclamaition or steel production, the reduction of private coal heating systems and the ban of
halogenated scavangers in the (leaded) gasoline, the level of PCDD/PCDF has been decreasing
over the recent years.
Table 10.2-21: Ranges of PCDD/PCDF-concentrations in the ambient air in
Germany and other European countries
Region or country
Period of investigation
PCDD/PCDF
[fg I-TEQ.m-3]
Minimum
Maximum
1990 to 1992
40
150
July 1991 to April 1992
22
270
April 1992 to March 1993
15
125
The Netherlands
April 1991 to October 1991
5
80
Belgium
April 1992 to October 1992
18
379
July 1993 to May 1994
15
114
probably 1996
10
950
May 1997 to June 1997
9
47
January 1998 to April 1998
17
306
Germany
Hessen
Erlangen region
Baden-Wurtternberg
Luxembourg
Spain
Croatia, Zagreb
Levels of organochlorinated pesticides and polychlorinated biphenyls were determined in
ambient air samples in Zagreb (Romanic and Krauthacker, 1998). Sampling was done in October,
November and December 1997 at two locations: Ksaverska cesta, which is at the north edge of the
city and Jakuševec, a village at the south edge of Zagreb. All compounds were found in all
analysed samples. The levels of organochlorine pesticides were in the range 3 - 88 pg.m-3, and of
PCB congeners in the range of 4 - 94 pg.m-3. In the group of organochlorine pesticides, gammaHCH was present at the highest concentration in samples from both locations (medians: 47 pg.m-3
(Ksaverska c.) and 74 pg.m-3 (Jakuševec)). Within the PCB group, PCB-28 showed highest
concentration levels (medians: 30 pg.m-3 (Ksaverska c.) and 37 pg.m-3 (Jakuševec)). All
compounds except of p,p´- DDD and p,p´-DDT were found at higher levels in samples collected at
Jakuševec than in those collected in Ksaverska cesta. This may be explained by the influence of
emissions from the municipal waste dump about 100 meters distant from the sampling point.
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Table 10.2-22: Concentrations in the ambient air [pg.m-3]
Compound
Ksaverska cesta (N=14)
Jakuševec (N=10)
Range
Median
Range
Median
0.5 - 46
27
14 - 58
29
alpha-HCH
2 - 57
27
15 - 67
31
beta-HCH
3 - 21
8
5 - 34
15
gamma-HCH
3 - 77
47
35 - 88
74
p,p´- DDE
2 - 26
10
8 - 29
19
p,p´- DDD
2 - 57
10
3 - 15
6
p,p´- DDT
4 - 30
13
4 - 38
9
PCB 28
17 - 58
30
15 - 94
37
PCB 52
8 - 34
18
9 - 41
20
PCB 101
4 - 27
10
5 - 35
13
PCB 138
2 - 21
8
4 - 24
10
PCB 153
3 - 15
7
9 - 19
12
PCB 180
1 - 12
5
9 - 48
12
38 - 152
80
69 - 219
107
HCB
Sum of PCB
To the top | last update: 22. 01. 2007
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Persistent, Bioaccumulative and Toxic Chemicals in Central
and Eastern European Countries - State-of-the-art Report
Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
10.2.3 References
Agrell C., Larsson P., Okla L., Bremle G., Johansson N., Klavins M., Roots O.,
Zelechowska A. (1999): Atmospheric and river input of PCBs, DDTs and HCHs to the
Baltic Sea. In: A system analysis of the changing Baltic Sea. Eds. Wulff F., Larsson P. and
Rahm L. Submitted to press.
Brorstrőm-Lundén E. (1995): Measurements of semivolatile orgaganic compounds in air
and deposition. Ph.D. Thesis. Dept. Anal. Mar. Chem., Chalmers University of Technology,
Gőteborg, Sweden.
CHMI (1997): Air Pollution in Czech Republic in 1996. Czech Hydrometeorological
Institute, Praha, Czech Republic, 148 pp.
CHMI (1998): Air Pollution in Czech Republic in 1997. Czech Hydrometeorological
Institute, Praha, Czech Republic, 192 pp.
CHMI (1999): Air Pollution in Czech Republic in 1998. Czech Hydrometeorological
Institute, Praha, Czech Republic, in press.
Chovancová J., Petrik J., Kočan A., Holoubek I. (1994): Project TOCOEN. The fate of
selected organic pollutants in the environment. Part XXIII. Sampling and analysis of PCBs,
PCDDs and PCDFs in ambient air in Bratislava. Toxicol. Environ. Chem. 44, 73-80.
Chraszcz R., Grochowalski A., Pielichowski J. (1995): PCDD/F mass concentration in
residues from incineration of medical wastes in Poland. Organohalogen Compounds, 27, 4245.
EMEP (1998): EMEP Expert Meeting on Measurements of Persistent Organic Pollutants
(POPs) in Air and Precipitation. Lillehamer, Norway, 11-14 November 1997. Proceedings
ed. By A. Lukewille, NILU, EMEP/CCC-Report 8/98.
Falandysz J., Brudnowska B., Iwata H., Tanabe S. (1998): Seasonal concentrations of
PCBs and organochlorine pesticides (OCs) in the ambient air in the city of Gdańsk, Poland.
Organohalogen Compounds, 39, 219-222.
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Falandysz J., Brudnowska B., Iwata H., Tanabe S. (1999): Organochlorine pesticides
and polychlorinated biphenyls in ambient air in city of Gdańsk (in Polish). Roczn. Panstw.
Zakl. Hig., 50, 39-47.
Fiedler H. (1999): Dioxin and furan inventories. National and regional emissions of PCDD/
PCDF. UNEP Chemicals. Geneva, Switzerland 1999, 100 pp.
Grochowalski A., Wybraniec S., Chraszcz R. (1995): Determination of PCDDDs/PCDFs
in ambient air from Cracow city, Poland. Organohalogen Compounds 24, 153-156.
Grochowalski A., Chraszcz R. (1997): PCDD/F levels in suspended particulate matter in
ambient air from the Krakow city, Poland. Organohalogen Compounds 32, 76-80.
Halsall C., Burnett V., Davis P., Jones P., Pettit C., Jones K. C. (1993): Chemosphere
1993: 26: 2185.
Holoubek I., Kočan A., Petrik J., Chovancová J., Bíliková K., Kořínek P., Holoubková
I., Pekárek J., Kott F., Pacl A., Bezačinský M., Neubauerová L. (1992): Toxicol.
Environ. Chem. 1992: 36: 115.
Holoubek I., Čáslavský J., Dušek L., Pokorný B., Leníček J., Kočan A., Oehme, M.,
Hajšlová J., Kocourek V. (1993): SYMOS - System of Monitoring of Organic Compounds
in the Ambient Air. Proposal of Monitoring System, Control and Ambient Air Assessment
of Persistent Organic Pollutants. TOCOEN Report No. 87. Masaryk University, Brno, 64
pp.
Holoubek I., Čáslavský J., Kořínek P., Štaffová K., Kohoutek J., Hrdlička A. (1996):
Project TOCOEN. The fate of selected organic pollutants in the environment. Part XXVIII.
Levels of PAHs and some halogenated POPs in ambient air in Czech Republic. Polycyclic
Aromatic Compounds 9, 159-167.
Holoubek I., Kohoutek J., Mitera J., Fara M. (2000a): The emission inventory of POPs
(PAHs, PCBs, PCDDs/Fs, HCB) in the Czech Republic. Organohalogen Compd. (to be
submitted; Dioxin ´2000, Monterey).
Holoubek I., Ansorgová A., Kohoutek J., Holoubková I. (2000b): The regional
background monitoring of POPs (PAHs, PCBs, OCPs) in the Czech Republic.
Organohalogen Compd. (to be submitted; Dioxin ´2000, Monterey).
Kisfalvi A. (1995): Dioxin sources in Hungary. Organohalogen Compounds 24, 87-89.
Kočan A. (1994): Air pollution by emissions of persistent organic pollutants in the Slovak
Republic - Summary. Institute of Preventive and Clinical Medicine, Bratislava, Slovak
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Republic, November 1994.
Kočan A., Uhrínová H., Petrik J., Chovancová J., Drobná B. (1998): The occurrence of
semivolatile persistent organic pollutants in ambient air in selected areas of Slovakia.
Kočan A., Petrik J., Drobná B., Chovancová J., Jursa S., Pavúk M., Kovrižnych J.,
Langer P., Bohov P., Tajtaková M., Suchánek P. (1999a): The environmental and human
load in the area contaminated with polychlorinated biphenyls. Prepared by Institute of
Preventive and Clinical Medicine, Bratislava, Slovakia for Ministry of the Environment,
Slovakia, February 1999. 240 pp.
Kočan A., Petrik J., Chovancová J., Jursa S., Drobná B. (1999b): Environmental
contamination following PCB manufacture in Eastern Slovakia. Organohalogen
Compounds 43, 105-109.
Krauthacker B., Wilken M., Milanovic Z., Herceg S. (1998): Ambient air measurements
for determination of PCDD and PCDF in Zagreb. Gospodarstvo i okolis 35/98.
Larsson P., Okla L. (1989): Atmospheric transport of chlorinated hydrocarbons to Sweden
in 1985 compared to 1973. Atmos. Environ. 23, 1699-1711.
Milukaite A. (1998): Flux of Benzo(a)pyrene to the ground surface and its distribution in
the ecosystem. Water, Air and Soil Pollut. 105, 471-480.
Milukaite A., Mikelinskiene A. (1998): The influence of meteorological and physicochemical factors on benzo(a)pyrene washout from the atmosphere. Proceedings of
EUROTRAC Symposium ´98.
Ministry of the Environment CR (1999): Emission inventory of persistent organic
pollutants. Research project, Prague, Czech Republic, 1997-1999.
Oehme M., Haugen J., Schlabach M. (1994): Ambient air levels of persistent
organochlorines in spring 1992 at Spitzbergen and the Norwegian Mainland. Comparison
with 1984. Results and Quality control measures. Sci. Total Environ.
Parma Z., Vošta J., Hořejš J., Pacyna J. M., Thomas D. (1996): Atmospheric emission
inventory guidelines for persistent organic pollutants. Report for External Affairs Canada.
AXYS Ltd, Sidney, Canada/Prague, CR.
Phare (1997): Project EU/93/AIR/22 Local Studies of Air Quality in the Cities of
Bratislava and Košice National Needs Assessment of Air Pollution.
Romanic H., Krauthacker B. (1999): Distribution of organochlorine pesticides and
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polychlorinated biphenyls (PCBs) in ambient air collected in Zagreb. Zaštita Zraka.
Roots O. (1996): Toxic chloroorganic compounds in the ecosystem of the Baltic Sea.
Ministry of the Environment of Estonia. Environment Information Centre (EEIC). Tallinn,
Estonia, 144 pp.
UBA (1997): The European Atmospheric Emission Inventory of Heavy Metals and
Persistent Organic Pollutants for 1990. TNO Institute of Environmental Sciences, Energy
and Process Innovation. Forschungsbericht 104 02 671/03 im Auftrag des
Umweltbundesamtes Berlin.
Váňa M., Pacl A., Pekárek J., Smítka M., Holoubek I., Honzák J., Hruška J. (1997):
Quality of the natural environment in the Czech Republic at the regional level. Results of
the Košetice Observatory. CHI Prague, 102 pp.
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Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
10.3 Water and sediments
10.3.1 Introduction
Three important European rivers have the main part of their basins in CEE countries Danube, Elbe and Odra. In all three basins, the long-term research projects are carried out Project Elbe, Project Odra, Danube River Projects (Project TOCOEN / Chemical Time
Bombs and activities in this region), Danube Pesticide Regional Study. Very broad
measurements concerning the water and sediment quality are done in Baltic and Adriatic
region.
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Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
10.3.2 The Adriatic Sea
Two sea regions in CEE countries are studied from the PBTs contamination, fate and
effects point of view - the Adriatic and Baltic Seas.
The Adriatic Sea, part of Mediterranean Sea, as semienclosed body of water, is of
special interest for an evaluation of the entry, extent and fate of the pollution. Group of Dr.
Picer from Centre for Marine Research, Ruder Boškovič Institute, Zagreb, Croatia works in
this field long time and studies the existing levels and fate of mainly chlorinated compounds
(PCBs, chlorinated pesticides) in various components of coastal and sea ecosystem.
Part of this research, were made in the Rijeka Bay (Picer and Picer, 1992). Water from
three regions (Opatia, Rijeka and the northwest part of Island of Krk) flows into Rijeka Bay.
The coastal area is under the influence of human activities: residential, industrial and
recreational. Since the sea currents of the Rijeka Bay are very small, its aquatic system
behaves as a virtually closed system with a slow exchange of water masses. Therefore,
Rijeka Bay is seriously jeopardized by various human activities. Moreover, valuable tourist
and recreational resources, such as the Opatia Riviera, Cres and the Krk coast, should have
a pristine natural aquatic environment.
During 1976-1981, an intensive ecological investigation of the Rijeka Bay aquatic
ecosystem was performed (Jeftič, 1981; Picer et al., 1981). A significant portion of the
investigation concentrated on determining the extent of pollution from persistent chlorinated
hydrocarbons, particularly on the distribution of DDT and its DDE and TDE analogous, as
well as dieldrin and PCBs in various parts of the Rijeka Bay ecosystem. It must be stressed
that the investigated pollutants belong to the global group of POPs which are introduced
into the Rijeka Bay from the atmosphere and through various local sources of pollution,
urban and industrial wastewaters, maritime activities, insecticides used on trees in tourism
areas, etc.
Ten years after the intensive investigation of the distribution of OCCs in the Rijeka Bay
ecosystem, the same team investigated the levels of these pollutants there again. The levels
of OCCs in rainwater, wastewater, surface microlayer and water column in the Rijeka Bay,
were determined. Samples were collected between 1976 and 1987 at several stations located
in the Bay.
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Summary of these results is described in Table 10.3-1.
Table 10.3-1: Concentrations of PCBs and OCCs in samples from
Rijeka Bay area, Adriatic See, Croatia, 1976-1987
(mean, SD, range) [ng.l-1 (water samples); ng.g-1
(sediment samples)]
Type of samples
Rainwater
Sum of PCBs Sum of DDTs
Dieldrin
1.3 - 12.2
0.69 - 2.43
< 0.02 - 0.12
< 0.3 - 9 115.5
< 0.2 - 657.2
< 0.1 - 179.3
Coastal seawater (1m)
0.2 - 17.0
0.07 - 104.9
< 0.01 - 3.4
Coastal seawater (surface
microlayer)
28.0 - 597
3.0 - 25.3
< 0.1 - 1.8
Open seawater (1m)
0.2 - 1.7
0.05 - 0.57
Open seawater (surface
microlayer)
1.0 - 52
0.75 - 4.2
Wastewater
It is possible to conclude that concentrations of DDT in rainwater collected in the city of
Rijeka were comparable with published data from Brest and Menton, France, but PCBs
levels were twice as low in comparison with Brest and four times higher in comparison with
Menton. Relatively good negative linear correlation existed among DDT concentrations
with precipitation intensity.
Levels of chlorinated hydrocarbons in wastewater samples from Rijeka were among the
lowest values in comparison with other data from around the world. A tendency of
decreasing DDT concentrations in wastewater samples from 1979-1981 to 1986 was evident
but not for PCBs. A trend of decreasing chlorinated hydrocarbons concentrations in
seawater samples was also observed. About 50 % of the DDT and 80 % of the PCBs were
concentrated in the suspended matter of the water samples, PCBs were more concentrated in
the surface microlayer than were DDTs and dieldrin. Although PCBs and DDT were sorbed
preferentially to suspended matter and concentrated in surface microlayers, it seems that
PCB distribution in the coastal zone of the Rijeka Bay was slightly more influenced by
sedimentation and evaporation from surface films than were DDTs (Picer and Picer, 1992).
DDT and PCBs levels and study of long-term trends in sediments collected from 1976
to 1992 at over sixty stations located in the eastern Croatian coastal and open waters of the
middle and northern Adriatic Sea were subject of other study of Picer and Picer (Picer and
Picer, 1997). OCPs and PCBs mass fractions in the surface sediment samples ranged from
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< 0.1 to 96.7 for DDTs and from < 0.5 to 294.109 for PCBs dw. The results of the statistical
calculations for all the data were presented.
Linear regression analysis of the mass fractions of total DDT and PCBs with organic
matter in the sediments of northern Adriatic (samples collected only during 1990) showed
significant correlation for total DDT, but not for PCBs. Linear regression analysis of the
mass fraction of total DDT with PCBs in all the sediment samples showed high correlation.
It was evident that the levels of DDT and PCBs were higher in samples obtained from
the west stations (especially for PCBs) in comparison with levels obtained from the east
stations of the open waters of the nothern and middle Adriatic. Higher PCBs levels were
observed in sediment samples from Rovinj area and significantly higher levels were in
samples from the Pula and Dubrovnik (important harbours).
Authors also compared their data (as arithmetic means) on the OCPs and PCBs levels in
sediment samples collected from the Adriatic waters during the 1976-1992 period on a dry
weight basis with Mediterranean Sea. The levels of PCBs from the Mediterranean sediment
samples, were significantly higher in areas of south coast of France, west coast of Italy and
east coast of Greece in comparison with samples from the Adriatic Sea. In the case of DDT
higher levels were observed in west coast of Greece and south-east Mediterranean than in
Adriatic Sea.
As a part of Project MEDPOL Phase II from the beginning of the year 1993, PCBs have
been systematically analysed in sediments and biota of the Albanian Adriatic Coast (Koci,
1998). Comparing the available data, in the year 1993 the level of total PCBs in this part
was the lowest of whole Adriatic Sea, ranging from around 1 to 5 ppb in sediments and
from around 10 to 20 ppb for mussels (fresh weight). The pattern of the PCBs confirmed
their mostly airborne origin (predominance of most volatile PCB congeners, like
Aroclor 1242 or 1254. In the coming years a distinct increase of the PCB concentrations in
sediments and biota, were found. The pattern of PCB congeners has changed as well, in
favour of the less volatile technical mixtures (like Aroclor 1250), speaking for land-based
source contamination. This increasing was due to the importation of transformer oils
contaminated with PCBs and the malfunctioning of the transformer units as well. Another
source of pollution was probably the used oil spilled everywhere from old cars imported in
Albania during last period (the number of cars has increased from about 2 000 in 1990 to
more than 150 000 in 1998, most of them are used cars).
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10.3.3 The Baltic Sea
The content of chloroorganic compounds in the Baltic Sea water has been determined
by a great number of authors, but besides the toxicant content, data on the water salinity,
temperature, suspended matter etc. were missing. It was the greatest obstacle in the way of
comparising the results and making proper conclusion (Roots and Peikre, 1984; Roots, 1996).
The study of the distribution of toxic organochlorines in the Baltic Sea waters was
performed by Estonian scientists during period 1976-1987 and in 90ies (Roots, 1996). Aim
of this project was to determine how do toxic chloroorganics react in water, to study the
temporal and spatial changes of PCBs and OCPs in the Baltic Sea.
Concentrations of organochlorines in the Baltic Sea water were characterized by the
close mean concentrations in the Gulf of Finland and the Open Baltic. PCBs and DDTs
concentrations were rather stable over a longer period of observation during the years 19791987. In the Baltic sea water there was some seasonal variability of the PCBs and DDTs
concentrations, probably caused by the influence of meteorological, hydrological,
hydrochemical, hydrobiological and other factors of the sea environment. In shallow sea
areas one was observed the so-called secondary pollution, where under certain conditions
PCBs and DDTs accumulated from bottom sediments into water and even re-enter the
atmosphere (Roots, 1996). In the Baltic Sea water, DDT and its metabolites DDE and DDD
have become less important as environmental hazards and PCBs came more pronounced.
The contents of chloroorganic compounds in the sea water only reflected the actual situation
and they could not be a basis for long-term conclusions about the distribution of toxicants in
the Baltic Sea.
On the other hand, the sediments can be regarded as a kind of a specimen bank. When
the rate of sedimentation is stable and the effects of certain disturbances (currents,
bioturbation) are small, the sediment layers reflect the situation in the water mass at the time
of deposition. On the Estonian shelf, one can distinguish three zones of sedimentation: the
zone with stable a abrasion, the transit zone with temporary accumulation and the zone with
stable accumulation of sedimentary material. At present time, the scientists have good
knowledge concerning the geological structure of the Estonian shelf, actual state and
accumulation rates. At present the modern sediments are characterized by a non-uniform
distribution of the sedimentary matter and wide residual sediments. The estimation of the
accumulation rates varied between the values 0.1 - 1 mm.y-1.
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The Baltic suspended matter could be described as mixtures of mean terrigenous and
marine biological matter. It has been observing the possible connection between the degree
of marine eutrophication and the more or less temporary fixation of PBT compounds in the
sediments; there are strong indications that the levels of DDTs, PCBs and other PBTs are
kept down in heavily eutrophicated marine environment.
The levels of PBT compounds in bottom sediments were published in many papers. At
present it is very difficult to evaluate the total amount of PCBs and DDTs in bottom
sediments of the Baltic Sea, because even if the bottom sediment samples have taken by the
neighbouring stations, the toxicant contents in these samples fluctuate to a great extent (1030 times). In general, the highest levels were found in the vicinity of major population
areas, but also in cities with shipyards and shipping (Roots, 1996).
The group of Prof. Falandysz studies long time coastal and sea parts of Baltic Sea. The
main topics of their interest are all types of chlorinated compounds including PCNs and
metabolites of OCCs in waters, sediments and various types of biota.
The determination of PCNs in surface sediment and biota from the Gdaňsk Basin, Baltic
Sea collected in 1992, were done. A surface sediment sample was taken from the nearshore
sedimentation area of the Visla River in Kiezmark under Gdaňsk. PCNs were detected in
the Wisla River surface sediment and in all biological samples. Sediment contented total
6.7 ng.g-1 of PCNs, 37 congeners were identified and quantified. The profile of PCN
congener groups shows very high contribution from tetra-CNs (82.1 %). Tetra-CNs are
more volatile than higher chlorinated PCNs. The differences in volatility of different PCN
homologue groups can prefer the higher environmental mobility of lower chlorinated
congeners. A specific composition of PCN homologue groups in the sediments as well as in
the biological matrices like plankton and mussel, with higher proportion of tetra- and pentathan hexa- and hepta-CNs, seems to support such a hypothesis. This finding can suggests
the atmosphere as a main route of transportation, deposition, and source of PCNs to the
Gdaňsk Basin (Falandysz et al., 1996).
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10.3.4 The Black Sea
Aliphatic and aromatic hydrocarbons have been determined in 28 samples of suspended
particulate matter (SPM) collected at subsurface seawater and 11 dissolved samples
(subsurficial + deep) in the north-western part of Black Sea (Maldonado et al., 1999). In
addition, three vertical profiles of seawater particles were collected in a transect from the
continental shelf, slope and deep basin of the western Black Sea were sampled, to evaluate
the processes along the water column. In the Black Sea, petroleum inputs are significant as
a consequence of river discharges, accidental crude oil spills, ballast operations, sewage
disposal, offshore production, and transport. The north-western part of the Black see is the
most severely affected region, the known sources of oil contamination include offshore oil
production, pipeline transport, and shipping.
The highest concentrations of hydrocarbons were detected in the Danube, Dnieper, and
Dniester River Estuaries and other point sources of pollution located offshore Romania and
Bulgaria where oil production and refining is carried out (i.e. Constantza, Varna). The
concentrations of PAHs in the SPM of the Danube, Dnieper and Dniester Estuaries (ca.
1 600 pg.l-1) are higher than in other estuaries of the western Mediterranean (ca. 560 pg.l-1).
Concentrations of hydrocarbons decreased with increasing distance from the coast, but
relatively high concentrations were found at the open stations where the particulate organic
carbon (POC) is higher. The western Black Sea can be considered as a medium PAH
contaminated area (compare Table 10.3-2). The spatial distribution of fossil PAHs in the
SPM is controlled by salinity, POC and PON (particulate organic nitrogen). The highest
PAHs concentrations in dissolved phase (DP) were found at the continental slope, followed
by offshore Constantza (Table 10.3-3). The UCM concentrations of aliphatic hydrocarbons
in the SPM maximised at the stations collected in river estuaries (Table 10.3-4) and point
sources of oil pollution. In the DP, the concentration of the UCM in the slope was higher
than in the river estuaries.
PAHs distribution characteristic of fossil fuel or uncombusted fossil fuel residues is
predominant in the coastal stations. In the western Black Sea SPM, the higher contribution
of the alkylated species denotes higher fossil inputs, but far from riverine inputs, pyrolytic
PAHs predominate. The unresolved complex mixture (UCM) of aliphatic hydrocarbons is
predominantly of a fossil common origin according to the hopane and stearane distribution.
The vertical profiles of PAHs and UCMs show maximum in surficial waters and two
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submaxima at the biomass and redox cline where the composition of PAHs is modified
attributable to bacterial processes, there is an enrichment referred to POC. The large portion
of anoxic conditions in the water column leads to a better preservation of hydrocarbons
through the water column than in well-oxygenated seas allowing a large portion of PAHs to
reach the sediments.
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10.3.5 Danube River Projects and Studies
Project Chemical Time Bombs / Project TOCOEN
The accumulation of PBT compounds in soils and sediments is a potential risk for the future,
potential "Chemical Time Bombs". In many regions, freshwater sediments were found to be a
major continental reservoir of PBT compounds. Consequently, information on the amount of
pollutants in sediments is important in assessing the distribution, accumulation, fate, effects of
pollutants in aquatic ecosystems and risks connected with this contamination.
Sediments and their contamination is also very important and long-term part of Project
TOCOEN activities. Sediment samples were collected in the surroundings of industrial sources
(DEZA Valašské Meziříčí) and in the area of background observatory Košetice. The first broader
sampling network in Morava river catchment area was realised in 1992 as a part of European
project Chemical Time Bombs. River Morava is one from the most important tributaries of river
Danube. This river and some other tributaries in Moravia and Slovakia were included to the first
phase of this project (see map) (Holoubek et al., 1994a). The description of sediment sampling sites
in the Moravian and Slovakian part of Danube river catchment area is shown in Table 10.3-5.
Table 10.3-5: Project TOCOEN - Chemical Time Bombs sampling sites,
1989-1991
Number of site
Description of sites
DU-01
The surroundings of chemical factory DEZA Valašské Meziříčí (8
sediment sampling sites)
DU-02
River Morava, town Tovačov, behind town Přerov (chemical
industry)
DU-03
River Bečva, town Tovačov, near the confluence of Bečva and
Morava rivers
DU-04
River Morava, town Napajedla, under agglomeration Zlín (chemical,
rubber and plastic industry)
DU-05
River Morava, village Kostolany na Morave
DU-06
River Morava, village Rohatec, in front of town Hodonín (coal-fired
power station, enginnering industry)
DU-07
River Morava, village Budské, behind town Hodonín
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DU-08
River Danube, channel Patince
DU-09
River Hron, village Kamenice nad Hronom
DU-10
River Ipel´, village Patovice
DU-11
River Nitra, town Nové zámky
DU-12,13
River Váh, town Kolárovo
DU-14,15
River Little Danube, town Kolárovo
DU-16,17
Bílý potok, small stream, TOCOEN model site No. 4
The results published in 1994 described the first part of co-operation between Project
TOCOEN and European programme Chemical Time Bombs focused on persistent organic
chemicals in river Danube sediments. Sampling sites were selected especially in the places of
important industrial and urban sources of pollution and near the confluence of river Danube and its
most important tributaries. The most polluted sites were found below the confluence of rivers
Morava and Bečva below the large chemical industry centre Přerov and some other sources.
The contamination of Danube river sediments were lower than the contamination of sediments
from river Elbe in Bohemia. Nondek and Frolíková (1991) described the state of contamination of the
15 sites on river Elbe and 10 on river Jizera (one of the main tributaries of the river Elbe). The
concentrations of low chlorinated PCBs (Czech Technical mixture Delor 103) ranged from < 20 to
1 800 ng.g-1 and high chlorinated PCBs (Delor 106) ranged from 50 to 1 900 ng.g-1 in the case of
river Elbe. In the case of river Jizera the content of PCBs in sediments ranged from 15 to 450 ng.g1. In sediments from river Danube and its tributaries the contents of PCBs in sediments were
between 4.9 and 232 ng.g-1.
The highest contents of PAHs in sediments from these sampling sites were observed in small
villages (DU-01, 16, 17). The reason is probably high contribution by local heating systems.
The highest contents of PCBs in small stream Bílý potok in Czech-moravian highlands is a
result of PCB spill in factory for preparing of pre-coated gravel. The sampling site is located 5 km
from spill site and the sample was collected 7 years after spill (site 16). This is excellent example
of long-term risk of PBTs in the environment, typical Chemical Time Bombs - PCB storage in
small stream and gradual input to the environment.
All data from TOCOEN sediment measurements will be published during 2000.
The measurements of PCBs and OCCs contents in samples of surface, drinking and
groundwater and sediments were also part of very unique study concerning the environmental and
human population load in the area contaminated with PCBs (Kočan et al., 1999), (see also to
Chapter 10.1).
Summary of results from measurements of water and sediments samples is described in the
Tables 10.3-6 - 10.3-8 and Figure 10.3-1. Twenty times higher level of PCBs were observed in the
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vicinity of the former producer and its waste dumps.
Figure 10.3-1: PCB levels in sediment samples from some waters in
Michalovce and Stropkov districts
The contamination of sediments from Laborec River (river where leads the channel from
producer) and Zemplínská Šírava (dam where leads Laborec River) is 100 - 2 000 times higher (µg.
g-1) than in sediments from the Ondava River and Domaša Dam (district Stropkov). The highest
levels of PCBs were found in the channel which connected the former producer area with river
Laborec (1.9-4.1 mg.g-1). Authors of study (Kočan et al., 1999) estimated that the amounts of PCBs
in sediments from this channel is in ten´s metric tons.
The use of PCBs in Slovenia increased after 1960, when an ISKRA condenser factory was
built in Semič, Bela Krajina (about 80 km south-east from Capitol Ljubljana) (Polič and Leskovšek,
1996). Measurements in 1982 showed very high concentration of PCBs in the environmental
compartments (air, water, sediments), as well as in food and in animal and human tissues (Polič and
Kontič, 1987). PCBs levels were particularly high in the nearly 3 km long Krupa river. The source
of Krupa river with mean flow of 4 m3.s-1 is located in a typical Karstic terrain about 2 km from
the factory. In view of the high pollution level found in the environment of the ISKRA factory and
the Krupa River, the Slovene Authorities and research institutes started in 1984 a PCBs
remediation programme - waste disposal project, environmental monitoring programme and health
research. In early 1985 the factory had to stop its production of PCB condensers. The analysis of
soils in waste sites showed very high level of contamination up to 50 mg PCBs.g-1 of dry weight.
It was established that some 6 000 m3 of contaminated subsoil should be decontamined. Also an
environmental monitoring programme containing an extensive sample analysis in potentially
threatened environmental compartments (soil, sediments, water, air), in food and living organisms
(milk, eggs, meat, fruit, vegetables, fish) was initiated. Some typical values of PCB concentrations
in the polluted area are shown in Table 10.3-9.
A comparison of PCBs concentrations in samples before and after decontamination in a 10http://www.recetox.muni.cz/old/index-old.php?language=en&id=4365 (3 of 5) [26.1.2007 8:25:17]
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years period (1984-1994) showed a slow decrease in these concentrations in air, soil and food,
confirming the effectiveness of the remediation measures, namely the elimination of gross PCBs
emissions in the environment. But still the highest concentrations of PCBs have been confirmed by
measurements made in the region around the Krupa River recently. Also the measurements have
shown an increase of PCB concentrations in soil in the NE Krupa area which is the most common
direction of the wind blowing (intensive deposition). Sediment samples were taken in 1995 the
deepest section of the river source where disturbances of the water column are minimal. Results of
PCB concentrations in sediment showed the level of PCBs in the sediment layer 30-34 cm lower
than 0.1 µg.g-1, about 1 µg.g-1 between 6-8 cm and over 160 µg.g-1 between 0-1 cm.
The contamination of water in Danube River and its tributaries were measured in many
countries of this region. As a consequence of a serious contamination with PCBs of a relatively
narrow karst area in Slovenia (Brumen et al., 1984) the presence of those pollutants was established
also in the water, suspended particles, sediments and fish from Kupa River in Croatia. The PCB
levels in unfiltered river water samples collected during 1985 near the town Sisak, 200 km
downstream from the primary contaminated area, ranged from 1 to 52 ng.l-1 (Šmit et al., 1987).
Sisak is the centre of an industrialised region in continental Croatia, in which the water for public
network comes from the Kupa River after purification. The purity of the Sisak drinking water
depends on the pollution of the Kupa River and on efficacy of the purification procedures. The
monitoring study on the levels of PCBs and OCPs in the Kupa River water and drinking water
from the nearby town of Sisak, was performed during period 1988/9 (Fingler et al., 1992). The
levels of PCBs and OCPs in the Sisak drinking water were compared with those determined in
drinking water samples from two other urban areas in Croatia - the capitol and major industrial
centre Zagreb and Labin, small town on the Istrian peninsula in Northern Adriatic. These towns
have the different sources of drinking water - Zagreb the ground waters and Labin the karst water.
The PCBs concentrations (as Aroclor 1254 and 1260) found in the Kupa River were two orders
of magnitude lower than those found in the heavily contaminated river waters like those of the
Hudson and the Niagara River (1-8 ng.l-1). But in most analysed samples the PCBs concentration
exceeded the maximum limit of 1 ng.l-1 permitted by relevant Croatian regulation in freshwaters
of the I and II categories, used as drinking water or drinking water supplies after an appropriate
treatment (Fingler et al., 1992).
Lindan was the only organochlorine pesticides present in all samples from Kupa River water
and also with the highest measured concentrations. Lindan was in this time still widely used for
public health care.
The same situation was in the case of analysed drinking water. PCBs and lindan were
positively detected in all samples. The highest levels of PCBs were found in the Kupa River,
probably as a consequence of drinking water preparation from the contaminated river water. The
observed values of pesticides and PCBs were below the maximum admissible concentration
established by EU or maximum contaminant level of US EPA.
The similar studies as in Croatia concerning to drinking water quality is performed long time
by Hygienic Survey, laboratory in Brno (Kořínek, 1999). Town of Brno has two important sources
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of drinking water - ground water from Březová and purification of surface water from Svratka
River. The following results describe study from the period 1988 - 1995 and this study was
focused on the quality of water in Svratka River from the upstream to the water treatment plant in
Brno-Pisárky. Analysis were made by the Czech norm for quality of drinking water and content
the chemical analysis including organic pollutants such as PAHs, PCBs, OCCs, VOCs,
microbiological and toxicological determination. From the group of OCCs were determined HCB,
gamma-HCH, p,p´-DDT, heptachlor a methoxychlor.
The source of Svratka River is located in the middle part of Bohemian-Moravian Highlands.
The collection of samples, were made the every second Monday in month on the six sites.
(Dalečín, Vír - WTP - raw water, Vír - WTP - treated water, Tišnov, Brno-Pisárky - raw water,
Brno-Pisárky - treated water. The results are in the following Tables 10.3-11 - 10.3-13 (three
examples - the first from upstream part, the second in front of Brno WTP and the third beside
WTP as a drinking water for town of Brno.
The levels of OCCs determined in the surface water from Svratka River are bellow limit values
and they are not a problem for water treatment plant and quality of drinking water for town of
Brno.
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TOCOEN REPORT
Persistent, Bioaccumulative and Toxic Chemicals in Central
and Eastern European Countries - State-of-the-art Report
Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
10.3.6 Danube Pesticide Regional Study
The river Danube is one from the most important European rivers. Its riparian area
covers 987 300 km2. The Danube basin is an important agricultural area for the riparian
countries. In all of them, the agricultural production strongly relies on the use of pesticides.
During the period of 1995-1997, the "Danube Pesticide Regional Study", a project
supported by PHARE, was completed (Bratanova et al., 1998). The main objective of the
project was to evaluate the risks of pesticide application to humans and the aquatic life in
the region and to recommend the adequate legal, management and policy measures to the
respective governments. One of the tasks of the project was gathering all available
information on the occurrence of pesticide residues in the water of the Danube ant its
tributaries. The data on the occurrence of pesticides in the water were collected from 10 of
the Danube riparian countries: Germany, Austria, Slovakia, Hungary, Slovenia, Croatia,
Bulgaria, Romania, Moldova and Ukraine. The data from period of 1990-1995 were
included in the study.
The cumulative number of the analysed pesticides was 77. Residues of 39 of them have
been found in the waters. The most positive findings of pesticides (i.e. those over the
detection limits of the respective methods) in the Danube water relate to organochlorine
pesticides (HCHs, HCB and DDT) and atrazine and its degradation product
desethylatrazine. Remarkably high levels and high proportion of positive samples have been
found for some chlorophenols.
DDT and lindane data from Romania exceeded by one to two orders of magnitude those
from the other countries. Some findings can be episodically high, for example mean
concentration of DDT in Danube water from Slovakia was 0.047 µg.l-1, but findings up to
0.26 µg.l-1 were reported (Veningerová et al., 1996). It is also interest that lindane and other
HCH isomers were detected in two of the nine examined Danube tributaries, both of them
on the Romanian teritory (lindane - river Olt, 0.15 µg.l-1 and river Arges 0.25 µg.l-1) (Bujis
et al., 1992). This would indicate occasional unauthorized uses of organochlorine pesticides
in some parts of the region and also suggests Romania as one of the hottest spots for
environmental contamination with chlorinated pesticides in the Danube river basin. In other
Danube basin countries, the levels of DDT and lindane in the Danube and tributaries were at
the order of 10-2 µg.l-1.
The residues of HCB were detected quite frequently in the Danube River (35 % positive
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samples). Most of the positive findings come from the Slovakian and Bulgarian part of the
Danube. As for the changes in the levels of contamination with chlorinated pesticides
observed in the last decades, no comprehensive data are available on the whole of the
Danube. However, some idea can be obtained on the basis of the results from Bulgaria and
Slovakia. The data indicate that the levels of DDT in Bulgarian section of the Danube
dropped considerably between the seventies and the nineties i.e. from 0.098 µg.l-1 in the
seventies to below 0.001 µg.l-1 in the nineties. The levels of lindane in the Bulgarian part
did not show any pronounced decreasing trends. The data from the Slovakian part of the
Danube indicate a drop off in DDT, gamma- and beta-HCH concentrations by about 50 %
between early seventies and late eighties.
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TOCOEN REPORT
Persistent, Bioaccumulative and Toxic Chemicals in Central and
Eastern European Countries - State-of-the-art Report
Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
10.3.7 Project Elbe
One from the first papers, which summarized the determination of PCBs and organochlorine pesticides
in water and sediments in former Czechoslovakia, was published by Nondek and Frolíková (1991). During
1987-90, water and sediment samples taken from more than 200 localities (streams and reservoirs), were
analysed. The purpose of this activity was not only to localize point sources, but also estimate the
"athropogenic" background. Three different localities have been examined in detail: Labe (Elbe) River,
Jizera River and three lakes in remote part of Sumava Mountains. From the results was evident that the
Labe River flows through several heavily polluted regions receiving industrial and municipal waste waters
which were mostly untreated in this time. Several chemical factories at Pardubice, Kolín, Neratovice, Štětí,
Lovosice and Ústí discharged their waste waters containing besides chlorinated solvents, benzene and
alkylbenzene, chlorobenzenes and many other organic compounds, into the river. The contamination of
bottom sediments with PCBs was therefore not surprising. From this time, the determination of water and
sediment quality is determined as a part of an international programme "Project Elbe". The Jizera River is
one of the main tributaries of the Labe River. The main sources of PCBs were Škoda car factory at Mladá
Boleslav and an industrial dump site upstream of Mladá Boleslav. The contamination of Sumava Lakes
was described as a result of atmospheric transport to non-industrialised areas. They are located in SouthWest Bohemia, long distance from industrial sources, in natural park at an altitude of 1 028 - 1 096 m a.s.l.
The concentrations of PCBs were described as Delor 103 and Delor 106 and their are summerized
together with HCB, lindan and DDE for all three sampling sites in the Table 10.3-14.
Table 10.314:
Concentrations of PCBs and other OCCs in bottom sediments
from rivers Labe and Jizera and from Sumava Lakes, 1989 [ng.g-1]
Sampling
site
(numbers
of site)
HCB
gama-HCH
DDE
PCBs (low as
Delor 103)
PCBs (high as
Delor 106)
Elbe
River
(15), 1989
< 1 - 440
ND
< 5 - 205
< 20 - 1 800
50 - 1 900
Jizera
River
(10), 1990
Šumava
Lakes
(3), 1986
15 - 450
0.8 - 2.0
0.5 - 1.8
1.0 - 1.6
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Hincovo
Pleso
(High
Tatras,
Slovakia)
0.9
2.4
1.2
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15
TOCOEN REPORT
Persistent, Bioaccumulative and Toxic Chemicals in Central
and Eastern European Countries - State-of-the-art Report
Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
10.3.8 Project Odra
The Odra is a one of the biggest rivers flowing to the Baltic Sea with the river basin of
118 861 km2 (Protasowicki et al., 1999). Being the border river, it contains the contamination
from Poland, Czech, and Germany e.g. the municipal and industrial wastes from 20 Polish
and German cities may be found there. Because the river basin covers also a lot of the
agricultural area, the subterranean waters feed it with noticeable amounts of organic matter,
harmful and toxic substances. Therefore the Odra waters on the length of 741.9 km are
below the 3rd class of purity, according to Polish standards, due to the amount of chemical,
physical, and biological contamination.
The sediments in the lower Odra are of various structures. In the port basins of Szczecin
as well as in some sections of the river and in the central part of the Szczecin Lagoon
typical muddy sediments with rich organic mater exist which amounts to 15-20 % or more
in dry matter. However, in the other parts of the Szczecin Laggon and in the port approach
in Swinoujscie some muddy-sandy and sandy sediments exist with a very low amount of
organic matter (up to 5 %).
In the studies carried out so far, on the basis of the analysis of the core of the sediments
it has been stated that the contamination with heavy metals in the mouth of the Odra River
was of antropogenic character (Protasowicki et al., 1999). The amount of the contaminants
increases together with the youngest sediments level. It must be noted that along the
waterway of the Odra River from Szczecin to Swinoujscie the amount of contaminants in
bottom sediments decreases. It proves high effciency of the process of self-cleaning of the
Roztoka Odrzanska and of the Szczecin Lagoon. The same differences in the level of
pollution in the mouth region of the Odra River were stressed in the results of the
hydrobiota research and particularly plankton in which the levels of contaminants lowered
as we get closer to the Baltic Sea and further away from Szczecin. Some differences were
observed by examining fish tissues. It has been stressed that in comparison with the
sediments of the mouth of the Elbe River and the Weser River the contamination is lower.
The Odra River is the main sink of waste waters from zones of provinces adjacent to the
Odra bed and also from provinces of the Odra River catchment area (Wolska et al., 1999).
The following main factors may have effect on the quality of water along Odra River:
●
point sources of pollution, wastewater from industry and from urbanised areas (not
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sufficiently cleaned municipal and industrial wastewater);
●
industrial wastes deposited in landfills located along the Odra River and its basin
area - composition of pollutants depends on production profile;
●
municipal wastes with different chemical and biological composition;
●
diffuse sources related to farming and agricultural use of wastewater;
●
wastes from rural areas discharged directly to groundwater, amount and composition
of these wastes are difficult to estimate.
Majority of provinces located on catchment area of the upper and middle Odra is
characterised by relatively high urbanisation and industrialisation. Specifics of this region
are that industry is concentrated in urban centres. Such localisation of industry makes
wastewater management easier, and from analytical point of view, simplifies identification
of pollutant sources narrowing the spectrum of compounds which could be looked for in the
studied samples.
Food industry is prevailing in these regions due to agricultural character of that territory.
It significantly contributes to environmental pollution, though it is difficult to overestimate
the environmental impact of other industries placed in these provinces. Pollution of the
environment by farming cannot be neglected. Farming in these provinces is characterised by
high productivity and efficiency which implies that fertilisers and pesticides are widely
used.
No systematic investigations of sediments and waters on the pollution level by regulated
organic compounds, i.e., polycyclic aromatic hydrocarbons (PAHs), polychlorinated
biphenyls (PCBs), pesticides, volatile organic compounds (VOCs), have been conducted in
that region. However, the data concerning the content of these compounds in the Baltic Sea,
which can be considerably contaminated by the Odra River, have been recently published.
A flood disaster took place in South of Poland in July 1997. Agricultural areas and plenty of
industrial and municipal landfills located along the Odra and over the Odra catchment area
were flooded. Due to that many types of toxic substances could have entered the
surrounding environment. Also sediments from Odra and its tributaries beds were washed
out and re-deposited over flooded areas releasing different toxic substances previously
accumulated. Such sediments would have become a potential threat to people and the
environment.
These investigations were carried out within the frame of International Odra Project
(IOP). Analytical part of this project (concerning interdisciplinary studies of the Odra basin)
refers to the determination of various groups of compounds, organic, in water and in
sediments. Studies performed by Technical University of Gdańsk are concentrated
particularly on organic compounds in aqueous and soil samples, including compounds
belonging to different classes. The results of these studies together with works of German
scientists (describe the German part of Odra River catchment area) concerning the
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investigation of post-flood sediments, were recently published in special issue of Acta
Hydrochimica et Hydrobiologica. The part of these studies is described here.
Over ninety surface sediment samples (0 - 3 cm) in the Odra River estuarine system from the Oderhaff, the Pomeranian Bight, the Peenestrom, the Greifswald Bodden - and the
Arkona Basin between 1994 and 1996 were collected. The contents of polychlorinated
dibenzo-p-dioxins, dibenzofurans (PCDDs/Fs) and biphenyls (PCBs), and DDT including
their metabolites were determined (Dannenberger and Lerz, 1999). The contents of all
investigated organochlorines in the sediments of the western part of Oderhaff (Kleines Haff)
were only slightly higher and more homogenously dostributed compared to the values of the
Pomeranian Bight and the Greifswald Bodden. PCB contents (sum of 23 congeners) in
surface sediments ranged between < 130 and 9 550 pg.g-1 (given for dry weight, dw). The
results of individual PCB congeners showed that high contents of hexa - and
heptachlorinated compounds (PCB 138, 153, 180) were present in the entire area
investigated. Generally, low of PCDDs/Fs, were found in surface sediments of the Odra
River estuarine system due to small industrial activities in the catchment area. Contents of
PCDFs (sum) and PCDDs (sum) varied from 2.5 to 820 pg.g-1 (dw) and from 13 to 2 991 pg.
g-1 (dw), respectively. The congener contents of PCDFs showed a non-uniform picture
between the Oderhaff and the Arkona Basin. In contrast, the congener profiles of PCDDs
showed approximately similar patterns at nearshore and offshore stations, with highest
values of OCDD (octa-CDD). We assume that most of the particulate-bound microcontaminants (PCBs, PCDDs/Fs) are deposited in the eastern part of the Oderhaff (Stettin
Lagoon), wich acts as a temporary trap and "purification" basin for the suspended
particulate matter (SPM). One pathway for further transport of the particles seems to be the
way on a small sedimentation strip along the island of Usesdom via the "Sabnitz-trough"
into the deeper parts of the western Baltic Sea.
The distribution and fate of polycyclic aromatic hydrocarbons (PAHs) were investigated
in surface sediments (0 - 2 cm) and fluffy layer material of the internal and external coastal
waters of the Odra river estuary (north-eastern Germany) (Witt and Trost, 1999). The area
includes the Odra Lagoon (Oderhaff), the Greifswalder Bodden the Pomeranian Bight, and
the Arkona Basin.
Elevated concentrations were observed in the surface sediments of the internal coastal
waters with highest concentrations in the Odra Lagoon. This indicates a significant
contribution of river discharge to the contamination of sediments with PAHs. During the
exceptional Odra flood in the summer of 1997 significantly higher concentrations of PAHs
were found in the fluffy layer material of the Odra Estuary (Table 10.3-15).
Table 10.3-15: PAH concentrations in different sea areas
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Sum of PAHs related
to dry weight [ng.g-1]
Odra Lagoon
Maximum
Minimum
Median
Standard
deviation
1 070
163
395
232
Swina mouth *
715
Peenestrom Greifswalder
289
119
265
69
Bodden
419
121
141
113
Pomeranian Bight
66
5
18
24
Arkona Basin
490
62
199
102
* Only one measurement
The distribution of the individual PAH compounds, varies widely depending on their
structure and molecular weight. A concentration gradient of the lower molecular weight
PAHs was found from the Odra Lagoon to the open sea areas. The concentrations decreased
rapidly from the Oder Haff to the Arkona Basin. These results were found in both sediments
and fluffy layer material. This is attributed to the degradation of the lower molecular weight
PAHs during transport from the urban regions to the sedimentation basins. A decrease of
this magnitude was not found for the higher molecular weight PAHs (i.e. benzo(a)pyrene)
due to their higher persistence. An enrichment of these compounds was measured in the
Arkona Basin.
A seasonal variation in the PAH levels can be observed in the fluffy layer material from
the Odra Lagoon and Pomeranian Bight, with highest concentrations in winter. The
influence of the Odra flood could also be measured: The spreading of the Odra flood plume
was accompanied by a strong increase in the PAH levels in the fluffy layer samples from
the eastern Odra Lagoon and the Pomeranian Bight.
The flood of 1997, as a result of flooding many cites, towns and villages along the Odra
and ground water logging of over 500 000 ha of arable land, caused the increase of the
contamination of the Odra waters (Protasowicki et al., 1999). Many toxic chemical
compounds found the way into the river from flooded rubbish dumps and industrial waste
sites. The aim of the present studies was to compare the heavy metals and polychlorinated
hydrocarbons content in the surface sediments taken after the 1997 flood with their level
recorded in the earlier studies conducted in area of the Eastern and the Western Odra.
The flood in the Odra river in 1997 has led considerable additional pollution of the
Stettin lagoon and the Baltic Sea with contaminated suspended solids (Muller and Wessels,
1999). For some priority substances, the pollutant entries via suspended solids during the
flood period are estimated to be approximately 1/3 of the usual annual load. Among these
priority pollutants there are total organic carbon (TOC), nitrogen, and the heavy metals Cu,
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Pb and Zn. For the concentrations of the priority pollutants in suspended solids
accumulation factors from 2 to 4 in the comparison with normal conditions were observed.
On the basis of the analysis of sediments sampled after the flood, main sources of the
pollutants should be evaluated. As reference area with an industrial background as well as a
typical polutant pattern the region around Glogow / Legnica was proposed.
In contrast to heavy metals and nutrients, organic polltants play an inferior role the Odra
River basin between Frankfurt/Oder and Schwedt than in the Elbe River with exception of
PAHs.
Under the normal conditions of the years 1996/97 the concentrations of organic
pollutants in suspended solids at Frankfurt/Oder and at Schwedt were comparable. With one
exception of PCBs, which were less remarkable during the flood. The PCBs concentration
increases with the factor 3 at the Schwedt site in contrast to Frankfurt. Therefore, at least
one PCB source must exist down river from Frankfurt. Since a dilution effect has been
observed during the Odra flood regarding PCB, the Warthe River must be considered as a
possible PCB source. This is confirmed also by the analyses of the sediments between
Eisenhüttenstadt and Widuchowa.
With regard to priority pollutants such as Pb, Cu, Zn, N, and TOC the pollutants inputs
via suspended solids during the flood were estimated to be approximately 1/3 of the usual
annual load. In the investigation of the pollutant input into the Stettin Lagoon,
sedimentation processes in polder areas must still be taken into account. In these polder
areas a retention of N and P of 5 % and 25 % respectively was estimated.
From the flood results some general consequences can be deduced with regard to further
management measures in the river basin. In order to reduce the load of harmful substances
in the Odra river basin it is necessary to improve wastewater purification technologies both
in municipal and in industrial plants. Furthermore it would be useful to review and
harmonise land uses and landscaping activities on riparian lands and floodplains in the
whole river basin in order to limit of contamination under extreme situations. That includes
agreements a cultivation plan about vegetation and uses as well as use and storage of
harmful substances. Appropriate measures should be organised in action programme of the
International commission for the Protection of the Odra River with regard to the adoption of
flood protection and warning plan for extreme situations.
The concentration of heavy metals (Hg, Cd, Pb, Cu, Zn, Cr, Ni, Mn) and chloroorganic
substances (gamma-HCH, Sum of DDT, PCBs) in surface sediments of the Western and the
Eastern Odra River was analysed after the 1997 flood and compared with data from 1995,
too (Protasowickie et al., 1999).
The research has shown that, like in 1995, the Western Odra sediments were more
contaminated with heavy metals and PCBs than the Eastern Odra ones. In comparison with
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the state of 1995, after the flood in both arms of the Odra, the amount of Cr, Mn, and PCBs
has increased while the amount of Pb concentration decreased. The levels of Cd, Zn, and Ni
have remained unchanged.
The changes of the other pollutants were not so clear. The concentration of Hg and Cu
increased in the Western Odra, while it decreased in the Eastern Odra, changes of gammaHCH and Sum of DDT content were inverted (Table 10.3-16).
The earlier assumption that the Western Odra sediments are more contaminated with
heavy metals than the Regalica was proved correct. However, the flood enriched the
Western Odra and the Eastern Odra sediments with chromium, manganese and PCBs,
lowered the level of lead concentration and remained unchanged the levels of cadmium,
zinc, and nickel content. The level of mercury and copper has increased in the sediments of
the Western Odra while it has decreased in the Eastern Odra. On the other hand changes of
the gamma-HCH and Sum of DDT concentration were inverted - the content of these
substances has decreased in the sediments of the Western Odra but it has increased in the
Eastern Odra.
The changes of organic matter content and increase or decrease of the heavy metals and
chlorinated hydrocarbons concentrations in bottom sediments can result from the run-off or
drifting on of xenobiotics and other substances with the flood water.
On the basis of mentioned above comparison, taking into consideration the glow losses,
the flowing conclusions can be drawn:
●
The bottom sediments of the Western Odra are more contaminated with heavy metals
that the Eastern Odra ones, which proves also the earlier own investigation. In
contrast to earlier studies, in which the content of chloroorganic compounds were
found to be comparable in the sediments of both Odra streams, the present studies
show that the sediments of Western Odra are less polluted with these contaminants
that the sediments of the Eastern Odra;
●
In comparison with the 1995 state, the 1997 flood caused the concentration increase
of Cr, Mn, and PCBs levels in both arms of the Odra with the decrease of Pb level.
The concentration level of Cd, Zn, and Ni remained unchanged. The changes of the
other pollutans were not so clear. The concentration of Hg and Cu increased in the
Western Odra, while it decreased in the Eastern in the Western Odra, changes of
gamma-HCH and Sum of DDT content were inverted.
In the upper part (from Chalupki village to Olawa city) the Odra flows over upland
areas. The Odra tributaries (Ruda, Osobloba, nysa Klodzka, Stobrawa, Olawa) are
mountainous and/or upland rivers. In the upper part of the examined region (comprising the
Odra River to the city of Olawa and Nysa Klodzka tributary), in samples taken in
Skorogoszcz, Brzeg and surroundings of Olawa the exceeding values of total PAHs (over
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200 µg.g-1) were determined (Wolska et al., 1999). The region between Skorogoszcz and
Olawa has developed urbanisation. Numerous highways and motorway are situated along
this part of the Odra. In that area, combustion of fuels (great number of power stations, heat
and power generating plants, industrial and domestic hearths) may generate some PAHs.
The biggest power station in Opole voivodship (in Dobrzyń Wielki, 8 km from Opole) and a
big heat and power generating plant in the Opole city are located in that region.
The low level of PAHs, was found in post-flood sediments in the region between
Krapkowice and Opole. It can be explained by the fact that this area is densely forested and
without industry. Also, there are only a small number of routes with low traffic. Sediments
sampled between Chalupki and Krapkowice are characterised by the average content of
PAHs (between 20 and 200 µg.g-1). In this region, the Odra flows through area with fair
urbanisation but with two big cites (Racibórz and Kedzierzyn). Power plants, metallurgical
and chemical factories are located in Kedzierzyn Koźle. A certain effect on the PAHs
content in sediments may have the fact that this part of the Odra lies close to the largest
industrial district in Poland.
However, the pollution of post-flood sediments with pesticides has not been exceeded in
any examined site, increased level of pesticides (according to Dutch list) was detected in the
region with advanced agriculture (Klodzko valley, the Psina river estuary).
The other investigated area was the region along the Odra, starting from the big urban
agglomeration (Wroclaw) and exceeding up to Ścinawa, and the tributaries of the Kaczawa
and Bystrzyca rivers. In two samples out of the nine collected in a city of Wroclaw, the total
PAHs concentration of 200 µg.g-1 was exceeded. Sample 37 was taken in the vicinity of
Kozia str. (Wroclaw-Maślice), where there is a road leading to a municipal waste site. This
road is characterised by heavy traffic of refuse collection truck. The second sampling point
with high PAHs content was situated near the heat generation plant.
The exceeding level of PAHs content was found in serval points in that region, i.e.,
within Wroclaw and in sampling points WB 8 and 43 located along the Strzegomka river, as
well as in Brzeg Dolny, in estuary of the Kaczawa River and in the Ścinawa city. The points
41 and 42, along the Strzegomka River, are situated in region with extensive agriculture and
low concentration of industry. The highroad with significant traffic and A4 highway, are
parallel to Strzegomka River. Therefore, it can be supposed that such strong pollution of the
examined samples by PAHs (15 µg.g-1 for 41) is affected by road transport. In the sample
taken close to Brzeg Dolny the PAHs concentration exceeds the value of 200 µg.g-1 and the
level of organochlorine pesticides is quite high. It is quite possible that "Rokita" Chemical
Plant (one of the list of the 80 plants of the highest environmental nuisance) contributes to
pollution of sediments in the area close to Brzeg dolny, where-as the advanced level of
pesticides in samples from sampling points 41, 42, and 46 (concentration above average
observed for all samples) may be attributed to the pesticides usage by farmers in that
agricultural region. The road transport may also be responsible for high concentration of
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PAHs in the sample coming from surroundings of the estuary of Kaczawa River (51Prochowice). A certain contribution may have also power industry placed in highly
industrialized city of Legnica, lying in distance of 16 km from the sampling site.
The increased level of pesticides in sample 51 may be asigned to the extensive planting
in the region with strong agriculture, i.e., in north and north-west of Prochowice.
Surroundings of sample 53 collection (road bridge over the Odra in a place of Ścinawa) can
be regarded as strongly polluted with PAHs. Lack of the extensive industry in that region
suggests rhat motor transport and domestic hearts can be a major source of pollution.
The Odra river a city of Ścinawa to a city of Slubice flows over lowland and is
enhanced by the tributaries of Barycz, Bóbr and nysa Luzycka. Agriculture and small food
industry play a predominant role in this region. Surface run-off from fields and wastewater
from such plants as sugar factories, distilleries, fruit-and-vegetable processing plants, and
dairies, discharged into surface water and into grounds, are significant sources of pollution
in that part of Poland. It can be supposed that pesticides are widely used in that region
taking into account high productivity of agriculture.
Areas in the district of Zielona Góra are characterised by large forestage. The forest is
nearly in full arboricultured. Management of forest resources requires use of different
agents to protect vegetation from pests, bacteriosis, etc. It is difficult to find out direct
relationship between forest management and increased concentration of pesticides in that
region, but it can be the reason for increased concentration of pesticides of Stary Zagór.
PAHs permissible concentration given in the Dutch List was exceeded only three
samples collected in this region (samples 64, 65, and 78). The exceeding value of the
maximum allowable concentration for total PAH can result from localisation of sampling
sites. For example, sampling sites in Otyń and Nowa Sól are situated nearby a road with
heavy traffic and, as it has been mentioned before, street traffic may be regarded as one of
the main sources of PAH emissions to the environment. Moreover, oil and natural gas have
been explored in the vicinity of Otyń and can affect the quality of the environment of that
region.
The following conclusions was be drawn based on the study evaluating the pollution
degree by organic compounds of post-flood sediments in upper and medium course of the
Odra:
●
The admissible levels of PCBs and pesticides were not exceeded in all examined
sites. A slight increase of organochloride pesticides level was found in the region
with extensive agriculture.
●
The analysis of PaHs content in the investigated samples indicated that in numerous
cases the regulated level was exceeded. The power plants, domestic heats, and
intensive traffic may be mainly responsible for pollution of the examined sediments.
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●
Volatile sulphur compounds were detected and identified in post-flood samples.
Occurrence of organic sulphur compounds can be attributed mainly to
microorganisms activity.
●
The presence of toluene in some samoles of post-flood sediments is probably also
due to microorganisms activity.
The studies on emission sources of pollutants will be continued (both biogenic and
anthropogenic origin). The investigation will concentrate also on the other no-target
compounds.
Fourteen polycyclic hydrocarbons (PAHs), six monosacharides (SA) formed following
the hydrolysis of polysaccharides, as well as water and organic mater contents were
determined in river sediments sampled in thirteen points in the Odra basin after the
catastrophic flood of 1997 (Bierawska et al., 1999). The water content is related to the water
absorbing capacity of the soil in the Odra catchment area. The PAH content increases
together with the increase in the organic matter (OM) content which suggests that these
species are mainly of anthropogenic origin. On the other hand, SA and OM contents
decrease with increasing water content, which implies that both enhance biological life. The
PAH content tends to decrease when the SA content increases. This relation goes hand in
hand with the quality of water resources, which is greater when the quality of
polysaccharides is higher.
Samples of river sediments contain various amounts of water, between 26 and 40 %,
which seem to be related to the water absorbing capacity of the soil in the Odra catchment
area. Preliminary analysis showed the sediments to be predominantly muddy and sandy,
though sometimes containing a small gravel fraction (sampling points 2, 5, 7, and 12).
The OM content in the mud fractions varies between 7.5 and 14.5 % and seems to be
higher in the sediments formed close to the large urban agglomerations (the highest value
corresponds to the sediment taken in Wroclaw - point 13).
The highest amounts of PAHs were found in the mud fractions of sediments sampled in
industrialised agglomerations like Wroclaw (point 13) or Racibórz (point 1). Nevertheless,
neither the Sum of PAHs, nor the amounts of certain compounds in various sediments vary
substantially which may have been the result of sediment being transported and mixed by
the flood wave. The ratios of the various PAH concentrations to each other, as well as the
predominance of unsubstituted hydrocarbons containing 2-6 aromatic rings over alkylated
hydrocarbons suggest that their main sources are the ash remaining after the combustion of
fossil fuels (mainly coal) and various organic remains. The composition of the PAH fraction
indicates that they originate partially from industrial wastewaters discharged after coal
processing. On the other hand, the relatively small proportion of alkylated homologues
seems to indicate that the source of PAHs was not the combustion of petroleum and its
products (e.g. by motor vehicles). The important thing is to compare our results with those
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reported by others. These quantities of PAH were larger than those found in the sediments
of the Morava, the main river in eastern of the Czech Republic, but were comparable to
those in the Rhine (Europe) and the Charles River (America). These investigations were,
however, carried out after the flood in 1997 and, as mentioned above, in stationary
conditions. This indicates that the flood could have caused some increase in PAH pollution
(assuming that it was originally similar to the river) sediments of the Odra basin.
Analysis of the data obtained for the sediments raises the question whether any relations
between them exist and, if so, what conclusions regarding the features and behaviour of
these complex natural systems can be drawn. Sum of PAHs increases with the increase in
the organic matter (OM) content. This non-linear relationship can be approximated by the
equation:
Sum of PAHs = 0.895 OM (0.220 OM - 1)
in which Sum of PAHs should be expressed in µg.g-1 of dry mass, OM in %, and the units
of numerical values are matched to those of the experimental quantities. Relationship
suggests, as mentioned above, that the organic matter present in the sediments is mainly of
anthropogenic origin.
It is interesting that Sum of PAHs tends to decrease with increasing amounts of
sacharides. As polysacharides originate from natural sources, their higher content may be an
indicator of better environmental quality. On the other hand, polysacharides are nutrients for
bacteria, which consume, among other things, anthropogenic substances such as PAH. A
higher sacharides content could therefore imply the environment´s greater capacity for
renewal.
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Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
10.3.9 Vistula River
The composition and loads of organochlorine pesticides (DDTs, HCB, HCHs, CHLs)
and polychlorinated biphenyls (PCBs) transported with the Vistula River waters to the Gulf
of Gdańsk were measured in 1991-92 (Falandysz et al., 1998, 1999). HCHs were dominating
persistent organochlorines quantified in the Vistula River water (Table 10.3-17). During 12
months period of the study, the total load of DDTs, HCB, HCHs, CHLs and PCBs
transported with the Vistula River water to the Gulf of Gdańsk was assessed on 11, 0.73,
1400, 0.38 and 5.0 kg, respectively. There were large monthly fluctuations of OPCs
concentration in the Vistula River water with HCHs peaking in August and September
1991.
Table 10.3-17: The concentrations of organochlorine pesticides and
PCB in Vistula River water collected at the Kiezmark
site near the city of Gdańsk [pg.l-1]
Compound
HCB
alpha-HCH
beta-HCH
gamma-HCH
HCHs
p,p´-DDE
p,p´-DDD
p,p´-DDT
o,p´-DDT
DDTs
PCBs
Trans-chlordan
Cis-chlordan
Trans-nonachlor
Median
24
1 400
650
1 800
4 200
100
170
26
15
310
190
9.1
3.9
3.6
Mean and S.D.
27 ± 14
48 000 ± 110 000
7 200 ± 15 000
12 000 ± 23 000
67 000 ± 150 000
110 ± 40
250 ± 210
32 ± 25
19 ± 16
410 ± 230
360 ± 280
9.8 ± 5.6
4.5 ± 3.6
4.9 ± 3.6
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Range
7.6 - 52
410 - 310 000
200 - 39 000
930 - 63 000
1 600 - 410 000
57 - 170
43 - 570
3.4 - 91
2.3 - 60
120 - 840
120 - 300
< 4.0 - 19
< 4.0 - 9.1
< 4.0 - 9.6
TOCOEN REPORT
Heptachlor
CHLs
5.5
12
6.1 ± 5.1
15 ± 13
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2.1 - 20
2.6 - 40
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10.3.10 Lakes
Polycyclic aromatic hydrocarbons (PAHs) were measured in superficial sediments from
several high altitude mountain lakes for assessment of contemporary background PAH
pollution levels in Europe (Fernandez et al., 1999). The sediments were obtained by gravity
coring, and the upper 0-1 cm were analysed by GC/MS. Location of the lakes ranged from
western to eastern Europe (see Table 10.3-18), all studied lakes were oligotropic with low
total organic carbon (TOC) in the waters. The parent PAH mixtures were very uniform
regardless of lake location, lake characteristic, and PAH load. The PAH profile was
dominated by parent compounds, from phenanthrene to coronene, with a predominance of
high molecular weight compounds of cata-condensed structures. The uniform sedimentary
PAH profile reflects very well the PAH composition in the atmospheric aerosols collected
at these high attitude lakes. The relative proportion of the compounds more labile to
photooxidation was low. The PAH distribution indicates that the PAH mixtures are not
significantly modified by the water column processes. The PAH profiles in sediments
correspond to airborne combustion mixtures refractory to photooxidation and chemical
degradation.
The PAH concentrations detected in most central European Lakes are intermediate
between contaminated sites near to urban/industrial centres (values of thousand ng.g-1) and
remote marine or lacustrine areas (a few hundred ng.g-1). But the lakes from Tatra
Mountains have PAH levels similar or exceeding the concentrations reported for sediments
near to urban areas. The atmospheric transport of PAHs to these environments is very
significant.
The PAH sedimentation fluxes were calculated from PAH concentrations, sediment
densities and sedimentation rates determined from 210Pb and 137Cs. The lowest flux was
found in arctic Lake Arresjoen, 6.9 µg.m-2.yr-1, the highest in the east European lakes, 960 1 700 µg.m-2.yr-1. The high fluxes found in the lakes from Tatra Mountains are similar to
those found in lakes situated near urban and industrial areas (Table 10.3-19). In contrast, the
fluxes in west and central Europe are lower than those reported in sediments from Northeast
USA remote sites.
Normalisation to TOC shows a uniform pattern in terms of continental influence and
east-west distribution. The lowest PAH/TOC values, 4.6 - 4.9 µg.g-1 were found in lakes
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situated at higher distance from continental inputs. Second group with concentrations 7.2 7.8 µg.g-1 constituted of the western most sites (Iberian Peninsula). Another group with 13 17 µg.g-1 was formed by the Pyrenees and Alps lakes in Central Europe. The highest values
were found in Tatra Mts. (130 µg.g-1). The uniform pattern of TOC normalised PAH
concentration / fluxes is consistent with the annual average atmospheric sulphate deposition
fluxes (correlation coefficient 0.97). These good correspondence points to association with
combustion particles as the main route for PAH transport into high altitude lakes.
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10.3.11 References
Bierawska B., Glód D., Blazejowski J., Lammek B., Szafranek J., Niemirycz E. (1999):
Polycyclic Aromatic Hydrocarbons and Polysaccharides in River Sediments from the Odra
Basin after the 1997 Flood. Acta Hydrochim. Hydrobiol. 5, 350-356.
Bratanova Z., Kovačičová J., Gopina G. (1998): A review of existing data on the
occurence of pesticides in water of the river Danube and its tributaries. Fresenius Envir.
Bull. 7, 495-501.
Brumen S., Medved M., Vončina E., Jan J. (1984): A case of polychlorinated biphenyls
contamination of water and sediment in the Slovenian karst region (Yugoslavia).
Chemosphere 13, 1242-1246.
Bujis L., Uzunov Y., Tčankov K. (1992): Water quality profile of the Danube river along
the Bulgarian-Rumanian stretch. ICWS Report, Amsterdam.
Dannenberger D., Lerz A. (1999): Occurence and Transport of Organic Microcontaminants in Sediments of the Odra River Estuarine System. Acta Hydrochim.
Hydrobiol. 5, 303-307.
Falandysz J., Brudnowska B., Iwata H., Tanabe S. (1998): Polychlorinated biphenyls
(PCBs) and organochlorine pesticides (OCs) in water of the Vistula River at the Kiezmark
site, Poland. Organohalogen Compounds, 39, 215-218.
Falandysz J., Brudnowska B., Iwata H., Tanabe S. (1999): Organochlorine pesticides
and polychlorinated biphenyls in the Vistula River water (in Polish). Roczn. Panstw. Zakl.
Hig., 50, 123-130.
Fernandez P., Vilanova R. M., Grimalt J. O. (1999): Sediment fluxes of polycyclic
aromatic hydrocarbons in European high attitude mountain lakes. Environ. Sci. Technol. 33,
3716-3722.
Fingler S., Drevenkar V., Tkalčevič B., Šmit Z. (1992): Levels of polychlorinated
biphenyls, organochlorine pesticides and chlorophenols in the Kupa River water and in
drinking waters from different areas in Croatia. Bull. Environ. Contam. Toxicol. 49, 805http://www.recetox.muni.cz/old/index-old.php?language=en&id=4371 (1 of 3) [26.1.2007 8:25:36]
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812.
Holoubek I., Čáslavský J., Helešic J., Vančura R., Kohoutek J., Kočan A., Petrik J.,
Chovancová J. (1994): Project TOCOEN. The fate of selected organic pollutants in the
environment. Part XXI. The contents of PAHs, PCBs, PCDDs/Fs in sediments from Danube
river catchment area. Toxicol. Environ. Chem. 43, 203-215.
Jeftič L. (1981): Collected papers of the ecological study of the Rijeka Bay. Thal. Jugosl.
17, 141-380.
Kočan A., Petrik J., Drobná B., Chovancová J., Jursa S., Pavúk M., Kovrižnych J.,
Langer P., Bohov P., Tajtaková M., Suchánek P. (1999): The environmental and human
load in the area contaminated with polychlorinated biphenyls. Prepared by Institute of
Preventive and Clinical Medicine, Bratislava, Slovakia for Ministry of the Environment,
Slovakia, February, 240 pp (in Slovak).
Koci K. (1998): The trend of POP pollution in the Albanian Adriatic Coast. Case study
PCBs (1992-1996). In: UNEP/IFCS, 101-106.
Kořínek P. (1999): The fate of selected chlorinated hydrocarbons in the system watersediment-soil. PhD. Thesis. Masaryk University Brno, Czech Republic (in Czech).
Maldonado C., Bayona J. M., Bodineau L. (1999): Sources, distribution, and water
coloumn processes of aliphatic and polycyclic aromatic hydrocarbons in the north-western
Black Sea Water. Environ. Sci. Technol. 33.
Müller A., Wessels M. (1999): The Flood in the Odra River 1997 - Impact of Suspended
Solids on Water Quality. Acta Hydrochim. Hydrobiol. 5, 316-320.
Nondek L., Frolíková N. (1991): Polychlorinated biphenyls in the hydrosphere of
Czechoslovakia. Chemosphere 23, 269-280.
Picer M., Picer A., Nazansky B. (1981): Persistent chlorinated hydrocarbons in the Rijeka
Bay. Thal. Jugosl. 17, 225-236.
Picer N., Picer M. (1992): Inflow, levels and the fate of some persistent chlorinated
hydrocarbons in the Rijeka Bay area of the Adriatic Sea. Wat. Res. 26, 899-909.
Picer M., Picer N. (1997): DDT and PCBs levels and long-term trends in sediments
collected from the eastern coastal and open waters of the Adriatic Sea. Ogranohalogen
Compounds 32, 198-203.
Polič S., Kontič B. (1987): Report on PCBs remediation in Bela Krajina. World
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Conference on Hazardous Waste, Budapest, Hungary, 925-929.
Polič S., Leskovšek H. (1996): Fate and transport of polychlorinated biphenyls (PCBs)
between water and atmosphere of the polluted Krupa River in Slovenia. Organohalogen
Compounds 28, 35-38.
Protasowicki M., Niedźwiecki E., Ciereszko W., Perkowska A., Meller E. (1999): The
Comparison of Sediment Contamination in the Area of Estuary and the Lower Course of the
Odra Before and After the Flood of Summer 1997. Acta Hydrochim. Hydrobiol. 5, 338-342.
Roots O., Peikre E. (1984): PCB and chlororganic pesticides in the Baltic Sea
environment. Proc. XIV. Conf. Of the Baltic Oceanographers, Gdynia, 2 718-732.
Roots O. (1996): Toxic chloroorganic compounds in the ecosystem of the Baltic Sea.
Ministry of the Environment of Estonia. Environment Information Centre (EEIC). Tallinn,
Estonia, 144 pp.
Šmit Z., Drevenkar V., Kodrič Šmit M. (1987): Polychlorinated biphenyls in the Kupa
River, Croatia, Yugoslavia. Chemosphere 16, 2351-2358.
Veningerová M., Prachar V., Uhnák J., Kovačičová J. (1996): Levels of chlorinated
pesticides in water of the Danube river. Fresenius Env. Bull. 5, 361-368.
Witt G., Trost E. (1999): Distribution and Fate of Polycyclic Aromatic Hydrocarbons
(PAHs) in Sediments and Fluffy Layer Material from the Odra River Estuary Acta
Hydrochim. Hydrobiol. 5, 308-315.
Wolska L., Wardencki W., Wiergowski M., Zygmunt B., Zabiegata B., Konieczka P.,
Poprawski L., Biernat J. F., Namieśnik J. (1999): Evaluation of Pollution Degree of the
Odra River Basin with Organic Compounds after the 1997 summer Flood - General
Comments. Acta Hydrochim. Hydrobiol. 5, 343-349.
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Persistent, Bioaccumulative and Toxic Chemicals in Central and
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Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
10.4 Soils
10.4.1 The contamination of soils in CEE countries
Very complex review of contemporary information on the concentrations, burdens and fate of PAHs was
published by Maliszewska-Kordybach (1999). The widespread occurrence of PAHs is largely due to their
formation and release in all processes of incomplete combustion of organic materials. Changes in their
qualitative distribution suggest that the sources of PAHs shifted from biomass burning to fossil fuels
combustion in last 200 years.
Air contributes in very small degree (< 0.5 %) to the total PAH burden in the environment even though
all PAHs released in the natural and anthropogenic combustion processes enter the atmosphere (Table 10.41). The atmosphere is not a repository and collector of PAH but more likely a transporter, dilutor and reactor.
Table 10.4-1: Partition of some hydrophobic POPs in natural environments
POPs
Sum of PAH
BaP
PCB
Soil
94.4
92.9
89.2
Percent of total
Freshwater sediment
Water
Air
5.4
< 0.01
0.1
7.1
< 0.01 < 0.01
9.9
0.3
0.5
Vegetation
0.1
< 0.01
-
Biota
< 0.01
< 0.01
0.1
PAH concentrations in soils near emission sources are high and vary by orders of magnitude from those
in unpolluted soils. The highest PAH contents correspond to industrially contaminated sites involved with
such activities as gassification / liquefaction of fossil fuels (gas works), coke production, asphalt and coal tar
production, wood treatment and preservation processes (creosote), fuel processing. Very high levels of PAHs
are noted also at military base areas (fuel contamination). Mean contents of PAHs in urban soils are within
the range of about 1 000 - 3 000 ng.g-1 but values of 30 000 to 50 000 ng.g-1 were found in some locations
(see Table 10.4-2). The average PAHs level in rural European soils is rather uniform with median values of
about 300 - 400 ng.g-1. The most abundant compounds are FLA, BbF, BaA, CHR, PYR, BaP, INP and PHE.
Important mechanism influencing the fate of PAHs in soils includes biodegradation, chemical
transformations, volatilisation, leaching, photolysis, and sorption to the soil solid phase and transfer to plants
and grazing animals. The range of PAH half-lives in soils reported in the literature vary from as short as few
days for low molecular weight compounds applied in laboratory experiments to nearly 20 years in the longterm field studies. Incidental ingestion of soil by humans was estimated to contribute in no more than 2 % to
the potential human PAH doses. However, contamination of agricultural soil with PAHs creates a serious
risk of the introduction of these xenobiotics into human food chain.
The evaluation the content of PAHs in arable soils in Poland with special focus on the agricultural areas
exposed to anthropogenic stress was performed as a part of country-wide Agricultural Soils Monitoring
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Programme in the years 1995-1997 (Maliszewska-Kordybach and Terelak, 1998). Soil samples (n = 216) were
collected from an area of about 140 000 km2 (arable lands in Poland) from the upper 0-20 cm layer. The
sampling points distribution was aimed to be representative for agroclimatic regions, typical Polish soil
groups and the regional structures (location). Nearly 50 % samples represented typical rural areas while the
other half corresponded to the territories exposed to anthropogenic activities. The soils under investigation
were mostly slightly acidic, with low organic matter content (median OM content = 1.77 %).
Thirteen PAH compounds (US EPA List excluding naphthalene, acenaphthylene and acenaphthene) were
determined and the results of statistical evaluation of their general contents in arable soils in Poland are given
in Table 10.4-3.
Table 10.4-3: Statistical evaluation of the content of PAHs in arable soil in
Poland [ng.g-1]
PAHs
Sum of PAHs
PAHOM10
BaP
Mean
Median
Standard
deviation
Percentile
90
Range
Measured
Interquartile
520
294
910
1 024
75 - 11 391
187 - 584
2 295
1 380
3 745
4 095
335 - 45 380
845 - 2 570
55
28
115
108
3 - 1 420
15 - 63
For the evaluation of the influence of sampling point location on PAHs content - which was one of the
aims of the study - sample population was divided into four groups similar to those identified in Bavaria and
to five levels of PAHs content in soil (soil classes) (Table 10.4-4).
Table 10.4-4: Criteria for evaluation of soil based on PAHs contents
Contents of Sum of PAHs in soil (soil classes) [ng.g-1]
< 200
200 - 1 000
Samples location
R
200 ng.g-1 - corresponding to Dutch
background value for the model soil
with 10 % OM
Rural location, far from
industrial activities
RC Rural location, close (520 km) to industrial activity
and peripheral areas of towns
1 000 - 3 000 1 000 ng.g-1 - corresponding to Danish
ecotixicological soil quality criterion
K
Location within the influence
of traffic routes
3 000 - 10 000 3 000 ng.g-1 - corresponding to German
precautionary value for soil with
OM < 8%
I
Location within the direct
surrounding area (< 5 km) of
industrial sites
> 10 000
10 000 ng.g-1 - corresponding to
German (Baden-Wurtemberg) plant
protection (PP) level
Nearly 90 % arable land in Poland - including the areas exposed to anthropogenic activity - contained
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PAHs at the level < 1 000 ng.g-1, and about 1/3 these territories - at the level < 200 ng.g-1. Less than 2 % of
the samples represented areas with PAH content above the German precautionary value of 3 000 ng.g-1.
Elevated content of PAHs occurred mainly in soils from areas with strong anthropogenic stress.
Soil samples were collected in 1994 from various sites in a former Soviet army base localised near the
town of Swinoujščie in the north-western corner of Poland and the possible contamination with PCBs was
investigated (Falandysz et al., 1997). Elevated concentrations of PCBs in soil in a former military (mainly air)
base grounds were observed in US base in Vietnam and in the surroundings of many former Soviet army
basis in Poland, former Czechoslovakia, former GDR and former Soviet Union. The former Soviet Union
has two own PCB formulations - Trichlorodiphenyl (with 41 % of chlorine content and average number of
chlorine atoms per biphenyl molecule is 3) and Sovol (53 % of chlorine and 5 chlorine atoms per biphenyl
molecule).
The concentrations PCBs in soil samples from the area of former Soviet army base Swinoujščie ranged
from 32 to 3 400 ng.g-1, with mean of 900 ng.g-1 and median 260 ng.g-1 d.w. The background concentration
for the various types of soil in the nothern part of Poland ranged between 2.3 and 38 ng.g-1 d.w.
Surface soil and sediment samples collected from the cities of Kraków, Katowice and Chorzów city in
southern part of Poland in 1993-1994 were analysed for residue levels of hexachlorobenzene (HCB), isomers
of hexachlorocyclohexane (alpha-, beta-, gamma-HCH), and DDT and its metabolites (DDD and DDE),
chlordane compounds (CHLs) and polychlorinated biphenyls (PCBs) in order to evaluate their
concentrations and distribution (Falandysz et al., 2000). The soil from the city of Katowice is relatively more
polluted mainly by PCBs, but also by the other organochlorines. Both the soil in the cities of Kraków and
Katowice are more polluted by organochlorines than soil from many other places in Poland. The residual
concentrations of the organochlorines indicated on non-existance of the domestic sources of pollution by
CHLs and elevated local contamination with PCBs. Sediment contained PCBs, CHLs and DDTs in a much
higher concentrations than it was found in soil, and in the case of HCHs and HCB the concentrations were of
the same order of magnitude. Composition of DDT metabolites and of HCH isomers were investigated in
detail.
A total of 24 soil and 3 sediment samples were collected at the area of the cities of Kraków, Katowice
and Chorzów. The details of sampling location and dates are given in Table 10.4-5. Sampling locations from
Kraków city are shown in Figure 10.4-1.
Figure 10.4-1: The sampling sites of soil from the city of Kraków
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In soil samples from the city of Katowice PCBs were a major compounds with an average concentration
of 380 ± 300 ng.g-1 dry weight (range were between 67 and 870) quantified and followed by DDTs with
110 ± 89 ng.g-1 (23 - 260), HCB 6.4 ± 9.6 ng.g-1 (0.46 - 30), HCHs 5.9 ± 3.3 ng.g-1 (1.1 - 11) and CHLs
2.7 ± 1.4 ng.g-1 (1.0 - 5.8). In the case of Kraków soil the dominating compounds were DDTs 260 ± 620 ng.
g-1 (4.3 - 2 400), followed by PCBs 53 ± 34 ng.g-1 (4.6 - 110), HCHs 11 ± 29 ng.g-1 (0.36 - 110), HCB 1.7 ±
2.6 ng.g-1 (0.19 - 9.9) and CHLs 0.46 ± 0.53 ng.g-1 (0.07 - 1.9) - see Figure 10.4-2. The soil from the city of
Katowice, the more industrialised sampling site, is more polluted than Kraków soil and mainly by PCBs
(about 8 times higher), but also by the other compounds. Both, the city of Kraków and the city of Katowice
soils are more polluted by polychlorinated biphenyls and organochlorine pesticides when compared to many
other places in Poland (Kawano et al., 2000).
Among various sampling sites in the city of Katowice, order of magnitude higher concentrations of
DDTs were found in samples No. K-1 and from K-5 to K-8, while of HCHs in K-8, and HCB in K-5 and K7. The concentrations of CHLs are comparable in all samples from the city of Katowice, but they are one to
two orders of magnitude higher than those from the area of the city of Kraków. The same situation is in the
case of PCBs, but the residual concentrations of Chlordanes are the lowest and those of polychlorinated
biphenyls are the highest. Those data residual concentrations of CHLs and PCBs do indicate to almost none
use of Chlordanes and Heptachlor and relatively high use of PCBs.
With regard to soil samples from the city of Kraków high concentrations of all analysed compounds were
observed in the centre of the city (sample number K-10). In the case of DDTs it was even 3 order of
magnitude higher than elsewhere. This fact may suggest some point source of organochlorine pesticides.
Sediment concentrations of PCBs, CHLs and DDTs are comparable figures as the relatively high
concentrations detected in soil samples. Although the high concentrations of HCHs and HCB were obtained
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in some samples, the spatial variations of these compounds are not remarkable among samples. These trends
can be supported by their physical-chemical properties such as n-octanol/water partition coefficients (Kow).
The Kow for HCHs and HCB is found to be relatively lower than those of other organochlorines examined in
this study (Table 10.4-5). As persistent chemicals with lower Kow values are considered to be more preferably
distributed in the water phase than in sediments, such compounds are transported and redistributed by the
circulation of water, and subsequently by gas exchange processes between air and water.
Composition of DDT metabolites and HCH isomers were investigated in detail. The DDTs were found to
be in general in the order of p,p´-DDT > p,p´-DDE > p,p´-DDD. The metabolite, p,p´-DDE is produced from
p,p´-DDT under the aerobic conditions such as upland soil. On the other hand, p,p´-DDT is converted to p,p´DDD under anaerobic conditions such as in the aquatic sediment. A much greater DDT/DDE ratio observed
in soils (1.0 - 62) than in sediments (0.8 - 4.3) may suggest the latest use/deposition from the atmosphere and/
or relatively higher persistency of p,p´-DDT under the particular climatic conditions/soil environmental
factors.
As regards to the percentage composition of HCH isomers in this study, the concentrations of HCHs
were in the order gamma-HCH > beta-HCH > alpha-HCH. The alpha-/gamma-HCH ratios were between
0.4 - 0.9 in the soils and 0.78 - 1.1 in the sediments. Those data did indicated on preferable use of Lindane (c.
a. 99 % gamma-HCH) than of the technical HCH in Poland. In the technical HCH, alpha-HCH is the
predominant constituent and alpha-/gamma-HCH ratio range from 4 to 7 (Iwata et al., 1995). Indeed, technical
HCH was only minor formulation and found only specific applications (soil fumigant in the forestry) while
gamma-HCH was a board action and popular insecticide used for various reason in Poland. Gamma-HCH is
noted to be degraded by microorganisms, and also to be photochemically isomerized to alpha-isomer. These
factors may account for the alpha-/gamma-HCH ratios close to 1.0. Another reason of the ratios is explained
by the higher stability for chemical (non-biological) degradation of alpha-isomer than gamma-isomer under
the aerobic and anaerobic conditions, namely, terrestrial upland soil and aquatic sediment environments.
Soils contaminated with PAHs often contain a high level of heavy metals such as zinc and lead due to the
same emission sources of those pollutants. Although it is recognised that the presence of heavy metals can
inhibit the activity of soil microorganisms, there are no data on the biological activity of soils polluted with
both groups of contaminants (Maliszewska-Kordybach and Smerzek, 2000). The aim of the study was to
investigate the influence of PAHs on dehydrogenases activity in sandy soil polluted with heavy metals (Zn,
Pb, Cd) as affected by soil organic matter content.
The possibility of synergistic effects of PAHs and some heavy metals (Zn, Pb and Cd) on soil
microorganisms was investigated in 90-days pot experiments. Two soil materials of different organic matter
content artificially contaminated with a mixture of PAHs (Sum of 4 PAHs = 10 µg.g-1) and Zn (100 µg.g-1),
Pb (50 µg.g-1) and Cd (3 µg.g-1) salts were used in the study. Soil microbial activity was evaluated on the
basis of dehydrogenases activity measurements. Synergistic ecotoxic activity of PAHs and Zn, Pb and Cd
salts mixture was observed in both soils.
The effects of PAHs, heavy metals (Me) and combination of both groups of pollutants (PAHMe) on
dehydrogenases activity (in relation to control, control soil activity = 100 %) in two soils of different Corg
content are presented in Figure 10.4-3. The results indicate that contamination of the soils with PAHs at the
level of 10 mg/kg inhibited strongly dehydrogenases activity. The effect become less distinct with the time,
as the content of PAHs in soils decreased. Soils polluted with heavy metals were characterised by lower DH
values than PAH polluted soils; the differences between ecotoxicological activity of PAHs and Me were
more visible in soil of low Corg content, where PAHs losses were more evident.
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Figure 10.4-3: Dehydrogenases activity in soils contaminated with PAHs and
heavy metals as affected by soil Corg content.
s - PAHMe values statistically (p < 0.05) different from Me
Contamination of the soils with two groups of pollutants (PAHs and heavy metals) caused further
decrease of soil enzymatic activity. This synergistic effect was statistically significant in soil of higher Corg
content. Generally, the enzymatic activity of the soils under study decreased in the order: control > PAHs >
Me > PAHMe. The increase of soil organic matter content reduced the influence of both groups of pollutants
on soil enzymatic activity. The effect decreased with time due to more intensive sorption processes and
lowering of PAH content in soils.
The possibility of synergistic ecotoxic activity of PAHs and some heavy metals should be taken into
account in further studies on soils polluted with both groups of these contaminants.
The distribution and accumulation of PAHs in Estonian soil as well as PAH profiles have been
investigated in areas with different anthropogenic pollution such as the city of Tallinn, the towns of Pärnu
and Kohtla-Järve and some rural areas (Trapido, 1999). PAHs were identified in 147 soil samples (0-10 cm
upper layer) collected in September 1996. The samples were collected at least 25 m away from roads in the
urban areas and at least 150 m from the roadside in the rural ones. Samples were not collected from known
contaminated sites as the territory of power stations and industrial enterprises, etc.
The Sum of PAHs values ranged over 4 orders of magnitude from 11.2 to 153 000 ng.g-1 d.w. Significant
differences (at least one order of magnitude) were observed in Sum of PAHs concentrations between rural
and urban areas. The typical Sum of PAHs level in Estonian rural soils was about 100 ng.g-1 d.w. PAH
concentrations in Tallinn, Pärnu and Kohtla-Järve soil were quite high. The mean Sum of PAHs
concentrations were 2 240, 7 665 and 12 390 ng.g-1 d.w., respectively. The dominant PAHs in soil samples
were pyrene, triphenylene and fluoranthene. 3-4 ring PAHs and 5-6 ring PAHs ratio altered from 5:1 to
1.7:1. The main source of PAHs in Tallinn, especially in its centre is increasing transport and overloaded
transport system. The same problems have all larger cities in CEE countries after the political changes extremely high increase of town traffic and decreasing contribution from former industrial sources as a
results of falling-off of production.
The other two Estonian towns had very high level of PAH contamination. Kohtla-Järve is an industrial
town and probably the most polluted town in Estonia. Unexpected level of contamination in health resort
Pärnu is probably result of individual domestic heating mainly based on wood, coal and peat and again,
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increasing traffic density in the centre of town.
The first information, concerning to the levels of contamination of soil in former Czechoslovakia were
published in the 1992 (Holoubek et al., 1992). In the time of early 90´ many potential sources of these harmful
compounds have existed in Czechoslovakia, many of them were unknown or little known. Soil samples were
collected from TOCOEN model sites (background area Košetice, the surroundings of industrial sources waste incinerators, various types of chemical industry) and some other places (the surroundings of Bratislava
MWI, factory for preparing precoated gravel in North Bohemia.
The soil contents of PCBs in agricultural soils from various Bohemian and Moravian agricultural farms
with permanent problematic quality of milk and with permanent good quality of milk were also described
(Holoubek et al., 1992). The results of determination of PCB contents from various types of soils and sites,
some agricultural and forest soils, the surroundings of an industrial town Brno, the surroundings of a factory
producing paints and lacquers and a factory for preparing precoated gravel in South Moravia and influences
of a Czechoslovak producer of PCBs Chemko Strážské were published, too.
This publication (Holoubek et al., 1992) also describes one specific example in more details. In this case
contamination of soil with 2,3,7,8-TCDD is caused by the substances escaping from the plants producing
2,4,5-trichlorophenol (2,4,5-TrCP) or 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) or by application of
formulations based on 2,4,5-T to agricultural and other purposes.
The production of chlorinated phenols started in Spolana Chemical Company, Neratovice, in 1969.
Mainly the sodium salt of 2,4,5-T, sodium pentachlorophenate, pentachlorophenol (PeCP) and 2,4,5-TrCP
have been produced. Chemical wastes consisting mainly of chlorobenzenes and by-products of 2,4,5-T were
dumped in steel drums distributed in the contaminated area around the facility (Kočan et al, 1991; Zemek,
1992; Zemek and Kočan, 1990).
In 1986 more than one hundred soil samples were collected from the periphery of the plant (at the
distance of 5-15 m from the building). The level of 2,3,7,8-TCDD in the soil samples collected from the
depth of 20 cm ranged from 0 to 29 800 pg.g-1 (0 - 6.0 mg.m-2) and in the samples from the depth of 20 50 cm, the levels ranged from 0 to 70 pg.g-1 (0 - 0.011 mg.m-2).
To compare the level of contamination, the level of 2,3,7,8-TCDD in several samples from "noncontaminated" area in the city of Neratovice, was also determined. These levels were within 0 - 100 pg.g-1
and these values were taken as a background. Samples of soil collected at a distance of 50 - 80 m from the
plant contained from 60 pg.g-1 2,3,7,8-TCDD. These values are essentially background levels. It is shown
that higher amounts of 2,3,7,8-TCDD in soils were only in the immediate vicinity of now defunct plant.
In 1988 new samples from Neratovice and the surroundings of this town were analysed. The level of
2,3,7,8-TCDD in the soil samples collected in Neratovice ranged from 3 to 100 pg.g-1. The samples from the
surroundings of Kaučuk Kralupy and KORAMO Kolín, the surroundings of industrial wastes incinerators
where mineral oils with unknown contents of PCBs were combusted and from background clear site of the
river Želivka (source of drinking water for Prague) were collected. The levels of PCDDs/Fs in these samples
collected in Kralupy ranged from 25 to 454 pg.g-1, in Kolín ranged from 20 to 129 pg.g-1, in Želivka area
ranged from 29 to 50 pg.g-1.
The major groups of PBTs compounds (PAHs, PCBs, PCDDs/Fs) were also determined in the soil from
the surroundings of two industrial sources in the Brno - chemical factory Lachema (4 sampling sites) and
municipal waste incinerator (19 sampling sites) (Holoubek et al., 1994a). Town Brno (more than 400 000
inhabitants) is very industrialised town. Brno MWI was constructed in the year 1989, but without secondary
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and tertiary clean-up stage (it was constructed few years latter). The MWI has three combustion furnaces
with the capacity 3x15 tons municipal waste per hour and is located similar as Lachema chemical company
in suburban residential parts of town.
The contents of PBTs compounds in soil samples from Brno are similar as the contents of these
compounds from urban and industrial areas. The highest contents are mainly connected with effects of local
heating systems (typically in the case of PAHs). The total observed concentrations of PAHs were found in
the ranges from 369.2 to 5 077 ng.g-1, benzo[a]pyrene from 21.3 to 445 ng.g-1, PCBs from 2.0 to 111 ng.g-1
and PCDDs/Fs (TEQ) from 0.018 to 0.140 pg.g-1.
In present time, R - T & A has the following main research projects concerning to soil contamination:
1. study of soil contamination in CR - monitoring type of projects;
2. biomonitoring of stressed soils;
3. study of diversity and activity of soil microbial communities in terrestrial ecosystems stressed by
heterogenous environmental mixtures of POPs;
4. development of methods for identification and assessment of environmental risks based.
Monitoring type of projects is focused on:
●
long-term project,
●
monitoring pilot studies - the surroundings of industrial companies,
●
POPs contamination in czech high-mountain ecosystems.
Long-term project is carried out in the area of observatory of Czech Hydrometeorological Institute in
Košetice, south Bohemia. This observatory is a part of few international scientific programmes (EMEP,
GAW). This locality is a background area of Project TOCOEN (Holoubek et al., 1990; Holoubek et al., 1994b).
The soil samples are collected from 1988, 8 soil sampling sites is located in this area with the frequency
1 times per year. The polycyclic aromatic hydrocarbons (PAHs), some types of chlorinated pesticides (ClPEST), polychlorinated biphenyls (PCBs) and in some cases polychlorinated dibenzo-p-dioxins and
dibenzofurans (PCDDs/Fs) are determined, too.
Part of project which is focused on the monitoring pilot studies and the surroundings of industrial
companies (DEZA Valašské Meziříči a.s. - producer of PAHs, carbon black, phthalates, sampling period
1989 - 1991, 37 sampling sites, type of observed pollutants: PAHs; Sokolovská uhelná a.s. - Gas and coal
fuel company, sampling period 1991 - 1993, 13 sampling sites, type of observed pollutants: PAHs; CVM
Mokrá a.s. (producer of cement with combustion of used motor oil with limited contents of PCBs and tires,
sapling time 1993, 1996, 1997 - 2003, 40 sampling sites, types of observed pollutants: PAHs, PCBs, ClPEST, PCDDs/Fs).
As concerning to PBTs contamination in czech high-mountain ecosystems, this part of our research
projects were performed in the period 1994-1999 (for more details see Chapter 10.5). The goals of this part
were the study of the contribution of long-range transport to the critical loading of environment, the
distribution of selected POPs among air, needles and soils. The main part of sampling sites were located
more than 1 000 m above the see level.
Understanding the changes in size and functioning of microbial communities in stressed soils appears to
be indispensable for reliable evaluation of biological potential and stability of the soil - microflora vegetation system both from retrospective and prognostic viewpoint. The harmful effects on soil microflora
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include mainly reduced structural and functional diversity, declined capability to utilize organic substrates
and increased maintenance energy requirements. The key importance of microbial activities in soil is based
on decomposition of organic matter and regulation of active nutrient pools for plants.
Microbiological parameters associated with mineralization activity and substrate utilization provide the
best interpretation of stress changes from the viewpoint of ecosystem functioning and stability. Furthermore,
evaluation of mineralization capacity of soil microflora makes it possible to assess energetical aspects of
stress influence (Visser and Parkinson, 1989). Therefore, routine evaluation of biological potential of soils
should be incorporated in ecological risk assessment guidelines focused on terrestrial ecosystems
contaminated by PBTs. Numerous microbial parameters have been proved as early indicators of stress
changes in soil ecosystems and it appears possible to detect adverse changes in microbial biomass content
and its activity long before they are detectable in the total organic matter content or by chemical analyses
(Domsch et al., 1983).
Research activities of RECETOX in the field of environmental monitoring of stressed and contaminated
soils deal with application of relevant set of microbial parameters in reliable bioindication of stress influence
in contaminated soils. Here we would like to summarize two case studies documenting (1) reasonable
application of limited set of microbial parameters in multivariate empirical evaluation of soil biological
potential and (2) potential role of estimated of soil mineralization activity as physiological measure for
evaluation of soils contaminated by PBTs. Both the studies were performed in typically contaminated sites in
Czech Republic (anthropogenic soils contaminated by PBTs from local sources, reclaimed sites that
remained after mining and industrial activities).
The main goals of study of diversity and activity of soil microbial communities in terrestrial ecosystems
stressed by heterogenous environmental mixtures of POPs is concerning to:
●
a base for the understanding of various stressors on soil biological potential,
●
assessment of the possible impact of stress factors on soil microbial communities,
●
the combination of different experimental approaches appears to be necessary for:
❍
reliable risk assessment,
❍
prognosis in these systems.
Two different approaches are used:
●
bioindication of soil fertility using an empirical mathematical model for topsoil microbial evaluation
●
the evaluation of microbial biomass carbon content and estimation of parameters associated with
mineralization activity of whole microbial activity of whole microbial community:
❍
respiration rate,
❍
potential respiration response in the presence of saturating amount of glucose,
❍
biomass specific respiration rate.
Important part of our research work is a study of diversity and activity of soil microbial communities in
terrestrial ecosystems stressed by heterogenous environmental mixtures of PBTs. We have selected as a
model ecosystems Norway spruce forests (autochtonous and monocultures) and alluvial meadows. Main
goals of this research work is study the reaction and possible adaptation of soil microflora to PBTs present
and to contaminated plant residues. In present time, we have only limited available data on influence of
environmental mixtures of PBTs in real ecosystems.
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Proposed study assumes that:
●
microorganisms play a key role in redistribution and transformation of PBTs in soil,
●
functional changes due to effect of PBTs can not be necessarily coupled with structural and genetic
shifts within the microbial community, and
●
changes in microbial activities can subsequently affect chemical behaviour and toxicity of deposited
PBTs, mainly due to changed amount and structure of soil.
The main hypotheses are:
●
what are the consequences of the pollution by environmental mixtures of PBTs for diversity of soil
microorganims ?
●
are expected deleterious changes in microbial activities mainly metabolic reflections or consequences
of genotype or structural shifts within the communities ?
●
as evaluated from microbial viewpoint, what is the toxic potential of PBTs released through
decomposition of contaminated plant residues ?
The loads of agriculturally used soils of the Czech Republic with monocyclic aromatic hydrocarbons
(BTX), polycyclic aromatic hydrocarbons (PAHs), organic chlorinated compounds (OCCs) and petroleum
hydrocarbons (PHs) have been investigated (Podlešáková et al., 1998). The samples were taken both in rural
regions and in regions impacted by severe inputs of contaminants. Soil contamination limits (reference
values) have been derived. They reflect the upper boundary of the anthropogenic diffuse background
variation. The comparison of statistically processed data concerning the contents of the above mentioned
organic pollutants, the exceeding of contamination limits and the share of single PAHs in their sum and their
toxicity in relation to benzo(a)pyrene provide an overview of the quantitative and qualitative extent of soil
contamination in ecologically critical regions.
In the Czech Republic concentrations reflecting intervention values can be found only on orphan sites.
The original Dutch B-values are exceeded on cropland only in fluvisols (Podlešáková et al., 1995a;
Podlešáková and Němeček, 1995). In this contribution the attention is focused solely upon soil contamination,
that means the concentration exceeding the background level.
In 560 soil samples from Ap horizons or from the corresponding topsoil depths (0-25 cm) and in 72
fodder plants the following groups of PBTs were determined: BTX (5), PAHs (12), PCBs, HCB, DDT, DDE,
DDD and petroleum hydrocarbons.
Soil contamination limits are based on the comparison of data from non-impact regions and the set of all
data after eliminating the outliers. These reference values correspond to the upper limit of the antropogenic
diffuse background variation (GM, GD2, 90 % percentiles, verification in regional studies) (Podlešáková and
Němeček, 1993; Němeček et al., 1996). The soil contamination with PBTs of the ecologically most critical
regions and sites in the Czech Republic, making use of contamination limits (Němeček et al., 1994), were
assessed. The same study was also carried out for trace elements (total contents) (Podlešáková et al., 1995b).
The investigation of PBTs content in fodder plants was carried out to respond the question if fodder plants
contamination is correlated to soil loads. The retrospective monitoring of PAH (20) was based on the
comparison of samples taken in present samples time and stored from the systematic soil survey (1960 1970).
Proposal of soil contamination limits of PBTs and their comparison with German reference values and
data (Joneck and Prinz, 1993), the original Dutch A-values and UK data (Jones et al., 1989) are presented in
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Table 10.4-6.
The listed background values are very similar and testify about the analogous approaches to
their determination. The present Dutch target values for MAHs and PAHs are based on ecotoxicological
testing.
Both the quantitative and qualitative features of the contamination of impacted regions were
characterized by the statistically processed (geometric means, geometric deviations, maximum values) PBTs
data from 7 representative districts and sites of the Czech Republic (see Tables 10.4-7 and 10.4-8).
The recently flooded fluvisols downstream industrial cities hold the first place in soil loads with all
groups of investigated PBTs especially PAHs and some trace elements (Cd, Zn, Hg, Pb, Cu, Cr) as well
(Podlešáková et al., 1995b). The specific features of PAHs individual compounds manifest themselves in benzo
(a)anthracene, naphtalene and anthracene. Then follows the metropolitan area of Prague with old loads,
orphan sites and traffic impacts. The prevailing components taking part in urban soil contamination were
PAHs. The specific contaminants are benzo(b)fluoranthene, but especially benzo(ghi)perylene, which
reflects the traffic influences. The PAHs load of soils in Prague differed from the other sites also in the
increased participation of benzo(a)pyrene, benzo(a)anthracene, in prevailing participation of most of PAHs
in contaminated sites and their high toxicity. Expressive contamination showed also PCBs (and trace
elements: Cd, Pb, Cu, Zn, Hg). The next position in the contamination sequence takes the north Moravian
region, characterized by metallurgy, black coal mining and coke production (predominately Ostrava, north
and east part of Karviná district and the surroundings of Třinec). The contamination was reflected mainly in
PAHs contents in soils specifically of benzo(a)anthracene, phenanthrene (and trace elements Cd, Zn, Pb)
(Podlešáková et al., 1996).
In the north-west Bohemian impact region the most severe contamination with PAHs (and Cd) in areas
was situated in the Sokolov district and a part of Karlovy Vary district, whereas benzene and PCBs exceed
their limits in the Cheb region (chemical industry). In the North Bohemian area the maximum loads by PAHs
(and Cd) were observed in the north - east part of this region, in districts Most, Teplice and Ústí n.L.
Monoaromatic hydrocarbons indicated the petrochemical industry (Most), and PCBs chemical industry (Ústí
nad Labem). Prevailing anthropogenic contamination with PAHs (and As, Be and Cd), was caused by
combusting of brown coal in both the north - west and north Bohemian regions (Podlešáková et al., 1996).
The residual contamination with DDT and metabolites seemed to be a consequence of application of
pesticides on great state farms in the sixties. The contamination with more than 1 PAH was found only rarely
in rural areas of Šumava mountains and Bohemia - Moravian highlands. The last mentioned regions were
characterized by ubiquitous sequence of PAHs with predominance of fluoranthene, phenanthrene and
pyrene, which were products of all kinds of combustion processes.
The investigation of PAHs profile distribution showed the abrupt concentration decrease in the depth,
except the fluvisols, which were products of sediments accumulations. The retrospective monitoring
(Němeček et al., 1997) pointed to different trends of PAHs accumulation and degradation in fluvisols and
extra-alluvial soils. Whereas in topsoils of fluvisols the accumulation of the specific compounds (benzo(a)
anthracene, anthracene and naphtalene and also benzo(a)pyrene, benzo(b)fluoranthene, benzo(k)fluoranthene
and benzo(ghi)perylene, occurred, in "normal" soils the trend of decline of PAHs contents (except of benzo
(ghi)perylene) was found. This (non-significant) trend can be due to more effective combustion technology
nowadays.
Some other substances were determined in soils of the Czech Republic: chlorphenols, lindan, atrazins,
triazins, substitued urea, but their concentrations come very often close to the detection limits.
The results of these investigations have proved the usefulness of the contamination reference limits of
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PBTs for the identification of their increased inputs into soils and delineation of polluted areas and points.
The contamination limits of PBTs, reflecting the ubiquitous loads of rural areas help also to verify the
relevance of ecologically based harmful reference values.
The levels of HCH in soils of the Slovak Republic were described by Schlosserová (1993). The fate of
HCH residues was studied in soils, mainly in arable lands provenance to different parts of the country.
Consequently agricultural products were analysed in order to study the transport of HCH soils into plants.
These testes were provided under real field conditions. The HCH study started in 1984 and has been
gradually up to 1 711 tested samples altogether. The results indicated a strong degradation during some years
up to ng.g-1 and lower contamination levels, which can no more cause a HCH cumulate in agricultural
products.
The goal of this study was to gain an informative view on Lindane appearance in samples representing
different parts of the Slovak Republic. The fact that the hexachlorocyclohexane residues are highly resistant
to decomposition led the Central Agricultural Controlling and Testing Institute in Bratislava to carry out a
study on HCH occurrence in the soil environment followed by analyses of agricultural products, feeds and
row materials of plant origin from different parts of the country.
The repeated and long-lasting application of Lindane containing pesticides by farmers became a good
reason to start carrying out a study on HCH occurrence. The search started in 1984 (Table 10.4-9), with feed
analyses followed by soil analyses of 695 samples in 1986-1989. A part of the samples was provenanced to
the field trials of the Field testing Stations throughout the country.
Table 10.4-9: Survey of samples analysed on Lindane appearance
Year
Samples
1984
27
feed components
India
35
feeds
Slovak Republic
47
feeds + feed components
India, Hungary
22
feeds
Slovak Republic
1986 - 89
695
soil
Slovak Republic
1991 - 92
152
soil
Slovak Republic
1987 - 89
337
agric. products
Slovak Republic
1992 - 93
396
soil
Slovak Republic
Total
1 711
1985
Commodity
Country
During the years 1987-89, the study was enlarged by 337 agricultural products. The number of analysed
samples has been gradually extended up 1 243 soil samples. Altogether there were tested 1 711 samples of
soils and agricultural products.
The determined HCH levels were evaluated according to limit values given in Table 10.4-10. The
working limit 0.05 µg gamma-HCH.g-1 of air-dried soil was lower than the A-level in the former Holland list
(0.1 µg.g-1).
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Table 10.4-10: Limit values for Lindane
Lindane [µg.g-1]
Notes
0.05
Working limit
domestic: feed dry
0.200
Hygienic Standard
feed fresh
0.100
Hygienic Standard
vegetable
0.100
Hygienic Standard
rapeseed
-
not given
0.500
Hygienic Standard
Commodity
Soil
Agricultural products:
imported: feed dry
The studied soil samples, mainly agricultural soils, were provenanced from different localities of the
Slovak Republic and covered nearly the whole country with a greater stress on the intensive agricultural
regions. The soil study started in years 1986-89 when 695 soil samples were analysed on residues of
chlorinated insecticides (see Table 10.4-11). There were 424 soil samples originated in some agricultural
farms from South and East Slovakia (localities 3, 4, 6, 10, and partly from 7 and 23) including strips of fields
intended for baby production. The rest of the soil samples in number of 271 samples represented 180 strips
of fields in 22 Field Testing Stations throughout the country (localities 1, 2, 5, 8, 9, 11 - 22, 24 - 26 and
partly 7 and 23).
The results of Lindane cumulation levels showed a quite high positive Lindane occurrence (Table 10.411). Only in 6.3 % of samples was not detected HCH at all. Naturally, this result was a consequence of the
long-lasting and systematic utilisation of chlorinated pesticides. The level of Lindane residues differed from
one field strip to the same locality e.g. strips of fields A-VII and A-VIII at the locality Velke Ripnany. These
findings could be a result of the different rates and numbers of applications at different strips of fields.
According to the given limit value in 21.8 % of samples the determined Lindane level exceeded it. It
means that 289 samples were over limit contaminated. Namely in locality Zborov (21) was found the highest
contamination level: 0.11 µg.g-1. The highest appearance of samples with over limited contamination
(28.6 %) and well the highest mean content (0.031 µg.g-1 what was 1.55 higher than in West-Slovakia) was
found in soils referring to East-Slovak agricultural regions (Table 10.4-12). The highest number of Lindane
free samples were found in soil samples from West-Slovakia.
Table 10.4-12: Mean levels of Lindane content and percentage of negative and
overlimited findings of Lindane in soils, 1986 - 1989
Localities
Samples
Mean levels
[µg.g-1]
Findings
Negative
% of overlimited
West
268
0.021
8.9
18.6
Middle
186
0.025
3.2
17.7
East
241
0.031
5.8
28.6
Total
695
0.025
6.3
21.8
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Among the soil samples there were analysed soil samples from gardens situated in the vicinity of the
former HCH factory. The level of Lindane residues fell into the range 0.0109 - 0.0168 µg.g-1 (locality 1 in
Table 10.4-11). This level represented a third of the limit value. There were not found spots with limit
exceeding content. The Lindane occurrence in ground waters from the same sites was not higher than
0.02 µg.l-1. The limit value was much more than higher 3 µg per litre. After a two years interruption the soil
contamination study continued by searching after Lindane residues in localities referring to numbers 27 - 34
in Table 10.4-13. The localities 27 - 32 were studied within the Complex Target Monitoring of pollutants in
the environment of the Slovak Republic. The reasons for the selection of these samples were positive
findings of Lindane residues in feeds or foods provenanced from these localities.
Table 10.4-13: Lindane contamination levels in soil, 1991-92
Locality
Samples
Mean Lindane Content
[µg.g-1]
Negative
Over-limit
Findings [%]
27. Lubisa
29
0.0019
0
0
28. Rosina
22
0.0002
5
0
29. Trnove
6
0.0002
33.3
0
30. Strecno
6
0.0007
16.6
0
31. Turie
20
0.0003
0
0
32. Chor. Grob
7
0.0008
0
0
33. Smolenice
12
0.0013
0
0
34. SW region
40
0.0011
2.5
0
Total
152
0.0009
3.3
0
The south - west region 34 is an intensive agricultural region of the Slovak Republic. The Lindane
appearance in the 40 samples was deeply below the limit value. The mean Lindane content was 0.0011 µg.g1.
The locality 33 represented a paint factory site. The tested soils were sampled from a profile up to the
depth of 6 metres at 5 sampling sites. The greater depth the higher HCH content. It had not exceeded the
level of 0.008 µg.g-1.
The results of 152 soil samples showed a quite low contamination level, about 2 % of the limit value for
the soils. The mean Lindane content in samples tested in this period was 0.0009 µg.g-1. This value had
decreased about thirty times in comparison to the samples studied in years 1986-89:
1986-89
1991-92
1992-93
695 samples
152 samples
396 samples
0.0250 µg.g-1 mean Lindane content
0.0009 µg.g-1 mean Lindane content
0.0009 µg.g-1 mean Lindane content
The more recently analysed soil samples were contaminated by Lindane in very low concentrations. It
confirms the fact, the longer elapsed time after Lindane application, the lower determined levels in soil. The
group of 396 samples tested in 1992-93 was provenanced to strips fields in 16 bioproduction regions. The
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samples were contaminated in ng and less than ng.g-1 levels. The highest finding was 0.0070 µg.g-1 at a strip
of field in the Middle-Slovak locality 47 - Zvolen (see Table 10.4-14).
The conclusion of the soil contamination study on appearance of gamma-hexachlorocyclohexane which
was represented by 1 243 samples tested during the years 1986 - 1993 from different parts of Slovak
Republic is the following: the Lindane appearance in soil performed a remarkable decreasing tendency up to
concentrations on the detection level of the utilised analytical determinations method in the more recent soil
samples.
The measurements of PCBs and OCPs contents in samples of soils were the other part of very unique
study concerning the environmental and human population load in the area contaminated with PCBs (Kočan
et al., 1999).
Summary of results from measurements of soil samples is described in the Table 10.4-15.
Table 10.4-15: Summary of concentrations of PCBs and OCCs in soils [ng.g-1 d.
w.]. Study of environmental and human exposure load in the area
contaminated with PCBs
(Kočan et al., 1999)
Pollutants
Dumps
(n=6)
Factories for
District Michalovce District Stropkov
preparing
(n=11)
(n=4)
of precoated gravel
(n=8)
Sum of PCBs
170 - 8 600
43 - 53 000 000
1.5 - 28
3.6 - 9.2
HCB
< 0.2 - 3.9
< 0.2 - 8.9
0.028 - 3.7
0.57 - 5.1
< 0.009 - 1 080
1.1 - 20
0.65 - 51
1.5 - 490
DDT + DDE
Several times higher values were found close to Chemko and its dumping and storage sites in Strazske
(Vola, Strazske). Somewhat increased levels were observed in towns (Michalovce, Stropkov) what might be
influenced by traffic. PCB concentrations at the remoter sites of Michalovce district were similar to those in
the comparative background area.
Soil samples taken close to the waste disposal sites of Chemko and asphalt-sand mixing plants have
shown PCB levels as illustrated in Figure 10.4-4. The extremely high content of PCBs (53 mg.g-1 = 5.3 %)
was found under PCBs storage tank in area of one this factory.
Figure 10.4-4: PCB levels in soil samples collected at the fields of some
municipalities in Michalovce and Stropkov districts
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As can be seen in Figure 10.4-5, PCB levels in soil samples from the fields of some towns and villages
of are considerably lower than those taken from the neighbourhood of dumps and plants mixing asphalt and
sand (PCBs were used in heat exchangers).
Figure 10.4-5: PCB levels in soil samples collected in the vicinity of storage and
dumping sites of Chemko chemical plant and asphalt-sand mixing
plants
The estimation of content of PCBs in soils in Slovakia based on the higher level of background
contamination (used area of Slovakia and 20 cm to soil layer) is round 50 tons as a result of using of PCBs in
Slovakia and long-range transport from other countries.
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Persistent, Bioaccumulative and Toxic Chemicals in Central
and Eastern European Countries - State-of-the-art Report
Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
10.4.2 References
Domsch K. H., Jagnow G., Anderson T.-H. (1983): Biological concept for assessment of
side-effects of agrochemicals on soil microorganisms. Residue rev. 86, 65-73.
Falandysz J., Kawano M., Wakimoto T. (1997): Polychlorinated biphenyls (PCBs)
contamination of soil in a former Soviet army base in Poland. Organohalogen Compounds
32, 172-177.
Falandysz J., Brudnowska B., Kawano M., Wakimoto T. (2000): Polychlorinated
Biphenyls and Organochlorine Pesticides in Soils and Sediments from cities of Kraków,
Chorzów and Katowice in southern Poland. Arch. Environm. Contam. Toxicol. (submitted).
Holoubek I., Houšková L., Šeda Z., Holoubková I., Kott F., Kořínek P., Boháček Z.,
Čáslavský J. (1990): Project TOCOEN. The fate of selected organic compounds in the
environment - Part I. Introduction. Toxicol. Environ. Chem. 29, 9-17.
Holoubek I., Houšková L., Šeda Z., Holoubková I., Kořínek P., Boháček Z., Čáslavský
J. (1990): Project TOCOEN. The fate of selected organic compounds in the environment Part IV. Soil, earthworms and vegetation 1988. Toxicol. Environ. Chem. 29, 73-83.
Holoubek I., Houšková L., Šeda Z., Kaláček J., Štroufová Z., Vančura R., Holoubková
I., Kořínek P., Boháček Z., Čáslavský J., Kuběna O., Vrtělka V., Vala, J. (1991):
Project TOCOEN. The fate of selected organic compounds in the environment - Part V. The
model source of PAHs. Preliminary study. Toxicol. Environ. Chem. 29, 251-260.
Holoubek I., Šeda Z., Houšková L., Kaláček J., Štroufová Z., Vančura R., Kočan A.,
Petrik J., Chovancová J., Bíliková K., Holoubková I., Zemek A., Kořínek P., Matoušek
M., Mikulíková R., Vávrová M. (1992): Project TOCOEN. The fate of selected organic
pollutants in the environment. Part X. The PCBs, PCDDs and PCDFs in Soils from
Czechoslovakia - Preliminary Study. Toxicol. Environ. Chem. 36, 105-114.
Holoubek I., Čáslavský J., Vančura R., Dušek L., Kohoutek J., Kočan A., Petrik, J.,
Chovancová J., Dostál P. (1994a): Project TOCOEN. The fate of selected organic
pollutants in the environment. Part XXII. The contents of PAHs, PCBs, PCDDs/Fs in soil
from surroundings of Brno municipal waste incinerator. Toxicol. Environ. Chem. 43, 217http://www.recetox.muni.cz/old/index-old.php?language=en&id=4373 (1 of 4) [26.1.2007 8:25:58]
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228.
Holoubek I., Čáslavský J., Helešic J., Kočan A., Petrik J., Chovancová J., Drobná B.,
Kořínek P., Boháček Z., Holoubková I., Kaláčková L., Kaláček J., Vančura R., Šeda
Z., Dušek L., Mátlová L., Kohoutek J., Štaffová K., Zemek A. (1994b): TOCOEN
Project. Centr. Eur. J. Publ. Hlth. 2(2), 122-129.
Holoubek I., Čáslavský J., Vančura R., Kočan A., Chovancová J., Petrik J., Drobná B.,
Cudlín P., Tříska J. (1994): Project TOCOEN. The fate of selected organic pollutants in
the environment. Part XXIV. The content of PCBs and PCDDs/Fs in high-mountain soils.
Toxicol. Environ. Chem. 45, 189-197.
Holoubek I., Tříska J., Cudlín P., Čáslavský J., Schramm K.-W., Kettrup A.,
Kohoutek J., Čupr P., Schneiderová E. (1998): Project TOCOEN. The fate of selected
organic pollutants in the environment. Part XXXI. The occurrence of POPs in high
mountain ecosystems of the Czech Republic. Toxicol. Environ. Chem. 66, 17-25.
Holoubek I., Tříska J., Cudlín P., Schramm K.-W., Kettrup A., Jones K. C.,
Schneiderová E., Kohoutek J., Čupr P. (1998): Project TOCOEN. The fate of selected
organic pollutants in the environment. Part XXXIII. The occurence of PCDDs/Fs in highmountain ecosystems of the Czech Republic. Organohalogen Compounds 39, 137-144.
Iwata H., Tanabe S., Ueda K., Tatsukawa R. (1995): Persistent organochlorine residues
in air, water, sediments, and soils from the Lake Baikal Region, Russia. Environ. Sci.
Technol. 29, 792-801.
Joneck M., Prinz R. (1993): Inventur organischer Schadstoffe in Boden Bayerns. GLA,
Fachberichte 9, Munchen, 1-156.
Jones K. C. et al. (1989): Organic contaminants in Welsh soils, polynuclear aromatic
hydrocarbons. Environ. Sci. Technol. 23, 540-550.
Kawano M., Brudnowska B., Falandysz J., Wakimoto T. (2000): Polychlorinated
biphenyls and organochlorine pesticides in soils in Poland (in Polish). Roczn Panstw. Zakl.
Hig. (in press).
Kočan A., Zemek A., Popl M. (1991): Determination of 2,3,7,8-tetrachlorodibenzo-pdioxin in soil in the presence of large excess of chlorinated hydrocarbons. Collect. Czech
Chem. Commun. 56, 1221-1217.
Kočan A., Zemek A. (1990): In Proceedings of DIOXIN 90, 10-14/09/90, Bayreuth,
Germany, 621-623.
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Kočan A., Petrik J., Drobná B., Chovancová J., Jursa S., Pavúk M., Kovrižnych J.,
Langer P., Bohov P., Tajtaková M., Suchánek P. (1999a): The environmental and human
load in the area contaminated with polychlorinated biphenyls. Prepared by Institute of
Preventive and Clinical Medicine, Bratislava, Slovakia for Ministry of the Environment,
Slovakia, February, 240 pp.
Kočan A., Petrik J., Chovancová J., Jursa S., Drobná B. (1999b): Environmental
contamination following PCB manufacture in Eastern Slovakia. Organohalogen
Compounds 43, 105-109.
Maliszewska-Kordybach B. (1999): Persistent organic contaminants in the environment:
PAHs as a case study. In: Ph. Baveye et al. (eds.), Bioavailibility of Organic Xenobiotics in
the Environment, Kluwer Academic Publisher. The Netherlands, 3-34.
Maliszewska-Kordybach B., Terelak H. (1998): Evaluation of the content of polycyclic
aromatic hydrocarbons (PAHs) in arable soils in Poland. Conference: Persistent Organic
Pollutants; their sources and environmental cycling at national, regional and global scale.
Lancaster, UK, 28-29 April.
Němeček J., Podlešáková E., Firýt P. (1994): Soil contamination in Northern Bohemia by
organic xenobiotics. Rostlinná Výroba 40, 113-121.
Němeček J., Podlešáková E., Pastuszková M. (1996): Proposed soil limits for persistent
organic xenobiotic substances. Rostlinná Výroba 42, 49-53.
Němeček J., Podlešáková E., Pastuszková M. (1997): Some specific features of the
contamination of soils of the Czech Republic with persistent organic xenobiotic substances.
Rostlinná Výroba 43, 365-370.
Podlešáková E., Němeček J. (1993): Background Levels and Contamination limits of
POPs in the Soils of the Czech Republic. In: Proceedings of TOCOEN Conference,
Znojmo, CR, 132 - 135.
Podlešáková E., Němeček J. (1995): Retrospective Monitoring and Inventory of Soil
Contamination in Relation to Systematic Monitoring. Environ. Monitor. Assess. 34, 121125.
Podlešáková E., Němeček J., Hálová G. (1996): Soil Contamination Criteria Used in the
Czech Republic. In: Proc. 9th Conference of the International Soil Conservation
Organisation (ISCO), Bonn, Germany, in print.
Podlešáková E., Němeček J., Hálová G. (1995a): Non-point Contamination and Pollution
of Soils with Persistent Hazardous Substances in Reference to Water Pollution. In:
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Proceedings of IAWQ Conference, Praha - Brno, 13 - 18.
Podlešáková E., Němeček J., Vácha R. (1995b): Contamination and Pollution of Soils in
the Czech Republic. In: Proceedings of Third International Conference on the
Biogeochemistry of Trace Elements, Paris, France, May 1995.
Schlosserova J. (1999): Evaluation of hexachlorocyclohexane residues in different
localities of the Slovak Republic. In: International HCH and halogenated pesticides Forum,
122-129.
Tebaay R. H., Welp G., Brummer G. W. (1993): Gehaltean polycyklishen aromatischen
Kohlenwasserstoffen (PAK) und deren Verteilungsmuster in unterschiedlich belasteten
Boden. Z. Pfl. Ernnahr.Bodenkunde 156, 1-10.
Trapido M. (1999): Polycyclic aromatic hydrocarbons in Estonian soil: contamination and
profiles. Environ. Pollut. 105, 67-74.
Váňa M., Pacl A., Pekárek J., Smítka M., Holoubek I., Honzák J., Hruška J. (1997):
Quality of the natural environment in the Czech Republic at the regional level. Results of
the Košetice Observatory. CHMI Prague, 102 pp.
Visser S., Parkinson D. (1989): Microbial respiration and biomass in a soil of a lodgepole
pine stand acidified with elemental sulphur. Can. J. For. Res. 19, 955-969.
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Persistent, Bioaccumulative and Toxic Chemicals in Central and
Eastern European Countries - State-of-the-art Report
Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
10.5 High-mountain ecosystems
Current studies on the causes of forest decline are focused mainly on the role of inorganic gases
and the resulting acidification of the plant environment, which may lead to direct or indirect injury.
Long-range transport of PBT compounds could influence the vitality of the forest ecosystem and by
exceeding of some critical load, the irreversible injury of ecosystem could occur. These organic
pollutants could effect forest trees either directly by diffusion into interior leave parts or indirectly
through a change in soil properties and soil biota.
One part one TOCOEN project activities is focused on the investigation selected PBT compounds
(PAHs, PCBs, Cl-PEST, PCDDs/Fs) in the air, soils and needles from sampling sites located in Czech
boundary high-mountain ecosystems (Holoubek et al., 1994c, 1998a, b).
Sampling sites were located in the Krkonoše Mts., Šumava Mts., Krušné hory Mts., Lužické hory
Mts., and in the Beskydy Mts. And samples were selected during three sampling campaign in 1994,
1995, 1996.
The first campaign (1994) was focused on the Krkonoše Mountains (Giant Mountains) and soil
samples only (Holoubek et al., 1994). The range of the Giant Mts. lies astride the Czech and Polish
border. Being about 40 km long and 20 km wide, this elevation is marked by slightly undulating relief
showing rounded heights and wide valleys. Two parallel ridges stretched in the west-east direction are
linked in two places by large upland plateaux. The higher Silesian ridge (boundary between Poland and
the Czech Republic) is composed mainly of crystalline schists.
In the Krkonoše Mts., the long west-to-east stretched valleys (windward tunnel valley) gather and
streamline air currents from foothills up to the accelerating summit plateau, thus creating a "nozzle"
between the two parallel ridges; to the east, south-east or north-east of each of these plateaux several
leeward vortex cirques occur.
During the last decades the ecosystems within the A-O systems dramatically changed due to the air
pollution. Increased flow rates of the intoxicated air in the upper parts of the windward valleys affected
the vitality of mountain coniferous forests. In the valley where ash and aerosol particles are being
deposited, decline of the forest proceeds at much larger extent even in lower altitude.
The six experimental ecological research plots (squares 50 x 50 m) of Institute of Landscape
Ecology in České Budějovice were included to Project TOCOEN experimental design. These plots are
located in natural Norway spruce forest stands in western and eastern parts of Krkonoše Mts (see
Table 10.5-1). The main goal of these experiments was recognising the contributions of long-range
transport of PBT compounds to the critical loading of the environment. The long-range atmospheric
transport was dominating source of these pollutants in these experimental sites - there are no local
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sources and these sites are more than 1 000 m a.s.l.).
Table 10.51:
Basic description of research plots
Number of plot
Name of plot
KR-1
KR-2
KR-3
KR-4
KR-5
KR-6
Mumlavská Alžbětinka Pudlava Modrý důl Slunečné Pašerácký
hora
údolí
chodníček
1 220
1 230
1 120
1 200
1 180
1 270
Wind direction
S
NW
SSE
S
SSW
SW
Slope [°]
1
3
15
20
20
8
Altitude [m]
In the west part of the Krkonoše Mts. two plots of similar altitude, differing by exposition have
been compared; in the plot Mumlavská hora, situated on the Silesian ridge, moreover the top
phenomenon and non-permeable bed-rock are outstanding. The plot Alžbětinka is situated in the
windward valley of the river Mumlava. The plot Pudlava, situated in the leeward valley in the middle
of Krkonoše, does not differ much from plot Alžbětinka both plots represent typical examples of
mountain spruce forests in the most exposed part of the Krkonoše Mts. This set of six plots enables less
disturbed forest stand (Modrý důl) to an almost collapsed spruce ecosystem (Mumlavská hora).
The results from this campaign are shown in the Table 10.5-2 (contents of PCBs including planar
non-ortho and mono-ortho PCBs and chlorinated pesticides), Table 10.5-3 (contents of PCDDs/Fs) and
the Figure 10.5-1.
Figure 10.51:
The sampling sites and summary of results
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PBTs
Number of sampling site
1
2
3
4
5
6
Sum of PCB
[ng.g-1]
31
70
69
115
137
42
HCB
[ng.g-1]
0.47
3.2
4.1
4.5
4.8
2.4
Sum of DDT
[ng.g-1]
25
56
55
81
111
26
I-TEQ TCDD
[pg.g-1]
17
24
25
24
29
17
The contents of organochlorines in the Krkonoše forest soil samples can be explained by two
possible inputs. Firstly it is probably long-range transport from the sources inside and outside the
"black triangle" and the secondly can be from forest composting processes.
The total contents of PCBs were from 31 to 137 ng.g-1 dry soil. This amount was very high in
comparison with other sites from former Czechoslovakia (Holoubek et al., 1992). Similarly, the contents
of PCDDs/Fs in these soil samples were high and ranged between 1 250 and 2 050 pg.g-1. The contents
of PCDDs were significantly lower than contribution of PCDFs and they ranged between 205 - 711 and
951 - 1 525 pg.g-1. The predominant congeners were OCDF and OCDD.
Expressed in toxicity equivalents, the total TEQ of PCDDs/Fs ranged between 17.0 and 28.9 pg ITEQ.g-1 and that of PCDDs/Fs and non-ortho and mono-ortho PCBs ranged between 20.1 and 41.2 pg
I-TEQ.g-1. The PCB 77 was predominant from the group of coplanar PCBs.
For non-ortho PCBs Boers et al. (1993) assumed that non-otho PCBs are formed by "de novo"
synthesis mechanism, similar to the formation of PCDDs/Fs. The congener distribution pattern in soil
samples from Krkonoše Mountains was similar as in soil samples from the surroundings of municipal
and chemical waste incinerator, but in lower amounts. PCB 77 occurs in the highest concentrations,
followed by PCB 126 and 169. The non-ortho PCBs in these samples consist from 9.3 to 49.3 % of the
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I-TEQ (see Table 10.5-4).
High contents of chlorinated pesticides, especially DDT and its metabolites DDE and
hexachlorobenzene. Their contents in high-mountain soil samples were from 25 to 111 ng.g-1 in the
case of DDT and DDE and from 0.47 to 4.8 ng.g-1 in the case of HCB. In the both cases, these contents
were probably the results of long-range transport and recent use in the middle European area.
During the following campaigns (1995-6), the ambient air, soils and needles were collected and
analysed. The results will be compared with our older data from other TOCOEN model sites (the
surroundings of industrial sources) and with the value from relatively clean area in south Bohemia
(observatory Košetice) (Váňa et al., 1997). Six sampling sites in the Krkonoše Mts., one in the Šumava
Mts., two in the Krušné hory Mts., one in the Lužické hory Mts., and one in the Beskydy Mts. were
selected for these sampling campaign in 1995, 1996. The basic description of research plots used in the
second and third campaign is given in Table 10.5-5.
Table 10.55:
Number
of site
Basic characteristic of studied areas and forest stands
Mountains
Plot
Bedrock
Altitude
Exposure
[m a.s.
decline [°]
l.]
1
Šumava
Boubín
1 300
NNW/5
2
Krušné
hory
Načetín
760
Červená
jáma
3
Soil type
Age of
growth [y]
Migmatite Cambisol
Podsolic
145
NW/3
Granite
Cambisol
Podsolic
65
870
SE/3
Granite
Cambisol
Podsolic
63
710
NW/24
Granite
Podsol
40
4
Lužické
hory
Jedlová
5
Krkonoše
Mumlava
1 190
SW/5
Granite
Podsol
80
6
Pudlava
1 140
S/12
Granite
Podsol
102
7
Pašerácký
chodníček
1 310
SW/12
Mica
Schist
Cambisol
Cryptopodsol
145
8
Beskydy
Kykulka
900
NW/22.5 Sandstone Cambisol
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Soil samples were collected from humus horizons F and H, from the depth about 3-8 cm, under
grass stands formed by dominant species Calamagrostis villosa. Mobile high-volume samplers
TOCOEN Ltd. with polyurethane foam as adsorbent, were used for the collection of ambient air
samples.
The content of PBT compounds in selected organic horizons and Norway spruce needles were
analysed in eight montane Norway spruce (Picea abies/L./Karst) in these sites. Samples were taken in
adjacent places of the permanent research plots, where the response of forest stands to multiple stress
impacts, have been followed for several years.
The main goals of these experiments were recognising the contribution of long-range transport of
persistent organic compounds to the critical loading of the environment. The advantage of these highmountain plots was the fact, that the long-range atmospheric transport was dominating source of these
pollutants in these experimental sites (all of them are more than 700 m a.s.l., part of them are more than
1 000 m a.s.l.).
The content of PBT compounds in forest soils can be a result of long-range transport from the
sources inside and outside of these regions and the second can be from the forest composting
processes.
The first part of results from the second campaing is shown in Tables 10.5-6 - 10.5-8. Table 10.5-6
describes observed values of groups of PCDDs/Fs homologous concentrations in ambient air, pine
needles and soils, Tables 10.5-7 and 10.5-8 describe the contents of 2,3,7,8-substituted congeners of
PCDDs/Fs in the same types of environmental matrixes from the whole sampling network.
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PCDDs/PCDFs were presented in ambient air (24 hrs sampling time) on all sampling sites. The
values are comparable to the values measured at the Košetice station (mean value in 1994-1995
0.384 pg.m-3 with the slightly decreasing tendency in the recent years). The highest value has been
found again on the locality Lužické hory Mts. (0.816 pg.m-3), second highest was the Krkonoše Mts.
(0.323 pg.m-3) and the third highest has been found in the Krušné hory Mts. (0.264 pg.m-3). Although
we have expected certain increased values in Krkonoše and Krušné hory Mts., the high pollution of
Lužické hory Mts. was surprising. PCDDs dominate in all ambient air samples. Concentrations were in
the range with lowest and highest values of 0.033 and 0.816 fg Sum of TEQ.m-3, respectively. We can
compare this data with data for example from UK where the concentrations of PCDDs/Fs were in the
range with lowest and highest values of 25 and 1 410 fg Sum of TEQ.m-3, respectively (Alcock et al.,
1997).
The concentrations of PCDDs/PCDFs in the spruce needles were more interesting. The highest
value had Beskydy Mts. (14.30 pg.g-1) followed by Lužické hory Mts. again (10.14 pg.g-1) and Krušné
hory Mts. (9.62 pg.g-1). The PCDDs/PCDFs ratios were in the range from 20:1 to 1.6-1.1:1. Only one
exception is Beskydy Mts., where the ratio is quite opposite (1:4.5), which reflects most probably
mining and smelting activities in Ostrava region. The similar ratio PCDDs/PCDFs 1:3.4 we have
observed in the soils from this locality.
Due to long-time accumulation of PCDDs/PCDFs in the soils, their concentration was much higher
compare to the "background value" (5 pg.g-1 TEQ). The highest concentration was in Beskydy Mts.
(3 220.13 pg.g-1; 49.24 pg.g-1 TEQ) followed by Lužické hory Mts. (2 727.13 pg.g-1; 44.01 pg.g1 TEQ), but the highest toxicity has Krkonoše Mts. (53.51 pg.g-1). We will get the value, which should
be monitored at least, from the point of view of the future development of the whole high mountain
ecosystem.
The total amount of PAHs in ambient air was the range from 2.71 ng.m-3 (Krkonoše Mts.) to
9.17 ng.m-3 (Beskydy Mts.) and these values are lower compare to the values of Košetice observatory
(mean value in 1995 was 23.09 ng.m-3). The content of PAHs in the soil reflected much more longterm input of PAHs into the environment. The total amount of PAHs in all sampling sites was
relatively higher (from 1 396.9 to 7 319.7 ng.g-1) compared to the background area Košetice (mean
value in 1996 was 1 753.3 ng.g-1). The highest value revealed Lužické hory Mts. where especially
concentration of benzo[b]fluoranthene was surprisingly high a quite unusual (1 192 ng.g-1). According
our direct observation, the spruce trees on this sampling site were damaged to the large extent. Quite
interesting were higher values for fluorene in all sampling sites.
In the southern part of the "Black Triangle" we have found large amount of p,p´-DDT and p,p´DDE (up to ca 4 µg.g-1 for p,p´-DDT). When we calculate the percentages of the parent substance in
all sampling sites from north-west or north boundary are higher than 70 %. The reason was described
in Chapter 4.3 and was quite certainly a rest of application of DDT in early eighties in the former GDR.
High percentage of parent compounds in Sum of DDTs was result of recent application.
The total amount of PAHs (consisting mainly of fluorene, phenanthrene and anthracene) in spruce
needles at different sites had the opposite tendency compare to the organochlorine compounds (PCBs
and HCHs). The largest amount of PAHs was found in the needles from Šumava Mts., which are on the
Czech side of the Bavarian forest. The reason for the increased amount of PAHs could be either
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increased long-range transport of pollutants (with prevailing content of PAHs from the municipal
incinerators and from the heavy traffic), especially in the altitude around 1 000 m a.s.l. or higher
potential of relatively healthy spruce forest in Šumava Mts. for the sorption of the POPs from the
atmosphere compare to the damaged spruce forest in the nothern part of Czech Republic.
The high mountain spruce forest ecosystem is heavily polluted by POPs, especially mountains in
north part of Czech Republic, mainly Lužické hory, Krušné hory, and Krkonoše Mts. These boundary
mountains represent the southern part of the "Black triangle". The content of POPs in high-mountain
spruce ecosystem was about one order of magnitude higher compared to the lowlands. The measured
concentration have reached the values which should be monitored in order to forecast the future
development of the whole high mountains ecosystem and biological effects of the POPs.
(The work was supported by the Grant Agency of the Czech Republic, grant No. 511/95/1060, and Ministry of
Environment of the Czech Republic, grant No. VaV 340/1/96).
Concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs),
organochlorine pesticides (OCPs) and phenols were determined in samples of topsoil (horizont A),
Scots pine (Pinus sylvestris) needles and lichen thalii Hypogymnia physodes (Migaszewski, 1999).
Nearly all studied PAHs were detected in the examined soil samples. The remaining organic groups, i.
e. PCBs, OCPs and phenols occurred in trace amounts; they were not recorded at every site. They were
noted primarily in the highest parts of the Holy Cross Mts. The maximum total concentrations were
recorded at the tallest mountains of the study region Lysica Mt. (21.36 ng.g-1 PCBs and 244.91 ng.g-1
OCPs). The highest PAH concentrations (maximum 1 905.83 ng.g-1) were recorded within Holy Cross
Mts. National Park (HCMNP) and other elevated sites of the Holy Cross Mts (HCM). The lowest
concentrations were in the southeaster part of the study region, varying from 4.43 to 68.5 ng.g-1. The
content of PAHs in unpolluted cultivated soils of Poland is assessed to be around 20 - 300 ng.g-1. Some
bimodality in the PAH spatial distribution pattern was observed between the northern and southern
slopes at different sites. In the north-western part of the HCM, southern slopes were distinctly enriched
in PAHs, whereas in the north-eastern part northern sampling sites contained much more PAHs. This
bimodality indicates two potential sources of pollution located north / north-east (Kamienna River
industrial area) and west/south-west (Silesian-Cracovian mining-industrial district) of the Holy Cross
Mts. Phenols were extremely scarce, only 4-nitrophenol occurred above detection limits.
In pine needles only phenanthrene occurred in all examined samples varying from 2.03 to 20.05 ng.
The remaining PAHs were at the trace concentrations. Also PCBs and OCPs generally occurred
bellow detection limits. The highest level of PCBs (4.57 ng.g-1) and pesticides (39.33 ng.g-1) was
recorded at Lysica Mt. Of phenols, only 4-nitrophenol (< 4.5 to 29.77 ng.g-1) and pentachlorphenol (<
0.55 to 3.94 ng.g-1) were detected. Phenols were not generally detected in topsoil around pine trees,
from which needles were collected. This fact indicates that 4-nitrophenol and pentachlorphenol might
have been products of metabolism or derived from atmospheric uptake.
g-1.
Benzo[a]anthracene (4.66 to 7.07 ng.g-1), benzo[b]+[k]fluoranthene (25.1 to 49.1 ng.g-1), chrysene
(13.23 to 26.17 ng.g-1), fluoranthene (16.65 to 29.47 ng.g-1) and pyrene (11.1 to 20.7 ng.g-1) were
detected in lichens, the same compounds were recorded in topsoil. Organochlorine pesticides in lichens
were represented by aldrin (3.4 to 10.89 ng.g-1), 4,4´-DDD (2.32 to 3.4 ng.g-1), 4,4´-DDT (15.84 to
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22.48 ng.g-1) and endosulfan I (4.64 to 17.18 ng.g-1), and PCBs by PCB-153 (1.33 to 2.21 ng.g-1).
Aside of 4,4´-DDD all these compounds occurred in topsoil, but not in pine needles. The highest
concentrations of PAHs and PCBs in lichens were recorded at Lysica Mt. No phenols were found in
the examined lichens.
In conclusion, PAHs were the predominant contaminants in all studied type of samples, PCBs,
pesticides and phenols were generally scarce.
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Persistent, Bioaccumulative and Toxic Chemicals in Central
and Eastern European Countries - State-of-the-art Report
Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
10.5.1 References
Alcock R. E., Coleman P., McLachlan M., Jones K. C. (1997): Reconstructing of air and
deposition fluxes of PCDDs/Fs in the UK. Organohalogens Compounds 33, 88-92.
de Boers (1993):
Holoubek I., Čáslavský J., Vančura R., Kočan A., Chovancová J., Petrik J., Drobná B.,
Cudlín P., Tříska J. (1994): Project TOCOEN. The fate of selected organic pollutants in
the environment. Part XXIV. The content of PCBs and PCDDs/Fs in high-mountain soils.
Toxicol. Environ. Chem. 45, 189-197.
Holoubek I., Tříska J., Cudlín P., Čáslavský J., Schramm K.-W., Kettrup A.,
Kohoutek J., Čupr P., Schneiderová E. (1998): Project TOCOEN. The fate of selected
organic pollutants in the environment. Part XXXI. The occurrence of POPs in high
mountain ecosystems of the Czech Republic. Toxicol. Environ. Chem. 66, 17-25.
Holoubek I., Tříska J., Cudlín P., Schramm K.-W., Kettrup A., Jones K. C.,
Schneiderová E., Kohoutek J., Čupr P. (1998): Project TOCOEN. The fate of selected
organic pollutants in the environment. Part XXXIII. The occurence of PCDDs/Fs in highmountain ecosystems of the Czech Republic. Organohalogen Compounds 39, 137-144.
Migaszewski Z. M. (1999): Determining organic compound ratios in soils and vegetation
of the Holy Cross Mts., Poland. Water, Air and Soil Pollution 11, 123-138.
Váňa M., Pacl A., Pekárek J., Smítka M., Holoubek I., Honzák J., Hruška J. (1997):
Quality of the natural environment in the Czech Republic at the regional level. Results of
the Košetice Observatory. CHI Prague, 102 pp.
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Persistent, Bioaccumulative and Toxic Chemicals in Central
and Eastern European Countries - State-of-the-art Report
Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
10.6 Aquatic wildlife
10.6.1 Adriatic Sea
The Adriatic Sea, as semiclosed body of water, is of special interest for an evaluation of
the entry, extent and fate of the pollution by chlorinated hydrocarbons such as PCBs and
chlorinated pesticides. There are many baseline studies to measure the existing levels of
these contaminants in various component of the marine ecosystem. However, mussels, as
very popular and widespread indicator organisms, were analysed most frequently in
comparison with other species. Based on this approach, mussels were collected from
various sampling stations located in the Istrian coastal waters, Croatia. On this campaign
were performed during period 1972 to 1990 (Picer and Picer, 1994, 1995). The aim of this
study was to describe the levels and trends of DDT, dieldrin and PCBs in mussels from the
western Istrian coastal waters. Mussels were collected manually or by dredging in intertidal
or very shallow waters.
Concentrations of chlorinated insecticides and PCBs ranged from 0.3 to 337 µg.kg-1 for
DDT and from 0.3 to 771 µg.kg-1 for PCBs on wet weight basis and from 17 to 32 000 for
DDT and from 21 to 56 900 mg.kg-1 on extracted organic matter basis. Total DDT and
PCBs concentrations did not exhibit Gaussian distribution in the investigated area and
collecting period, so it is necessary to be very careful in the interpreting the concentration
data using parametric statistics. Very often, the pollutant levels in mussel tissue differ
dramatically in samples collected at the same time at nearby stations.
The similar study was performed in the southern Adriatic coastal area, Croatia. The
levels of PCBs and DDTs were investigated in the samples collected between 1976 and
1990. Mussels (Mytilus galloprovincialis) and oysters (Ostrea edulis) were collected
similarly as in previous study. Mass fractions of DDTs and PCBs in mussels ranged from
ND (< 0.5) to 172.4; in oysters from ND (< 0.1) to 46.7 for DDTs and from ND (< 0.5) to
467.2 in mussels and in oysters from ND (< 0.5) to 113.1 x 109 wet weight for PCBs. The
used method (in both studies) was successfully intercalibrated during seven international
intercalibration exercises.
The results were evaluated using of statistical methods and their analysis led the authors
to the following conclusions. Very often, the pollutant levels in bivalves tissue differ
dramatically in samples collected at the same time at nearby stations. This frequently has a
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considerable influence on the means and their confidence intervals. Total DDT and PCB
mass fractions do not exhibit Gaussian distribution in the investigated area and collecting
period, so transforming the data to log values has the advantage of further normalising the
data, a prerequisite for the use of parametric statistics.
Results on one way analysis of variance of halogenated hydrocarbons mass fractions in
bivalves samples depending upon the collection area, period and seasons show very high
significance level for areas and period of bivalves collection for DDTs mass fractions and
for PCBs mass fractions for seasons of bivalves collection. In spring and autumn levels of
PCBs are significantly higher in comparison with summer and winter. These higher levels
are observed both on wet and lipid weight basis.
Statistically significant negative correlation coefficients are obtained by comparing the
values of total DDT mass fractions based on wet and EOM (extractable organic matter)
weight. For PCBs, positive correlation coefficients are obtained but they are not statistically
significant. The trend of DDTs levels is more similar to an exponential function than a
linear one, so the linearization of the level is achieved by transforming the data
logarithmically as performed for mussel samples from the Rijeka Bay, western Istrian and
middle Adriatic coastal waters or in sediments from the eastern Adriatic coastal waters.
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Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
10.6.2 Baltic Sea
The Baltic Sea as a virtually enclosed and fairly shallow sea is particularly vulnerable to
the toxic organic pollutants (Roots, 1996, 1999). It takes tens of years for all the water in the
closed system to be renewed. It is also a cold sea with a short reproductive season. Lower
water temperature and lower concentration of bacteria in marine waters, and low exchange
rates of the water body, means that the Baltic Sea ecosystem trends to trap and accumulate
PBT compounds. There are then either absorbed into the sediments or accumulated,
especially in marine mammals and sea birds. Above-mentioned facts are some of the
reasons why the sea is sensitive to disturbance by these types of toxic organic chemicals
(Roots, 1996).
The Baltic Sea is the final destination of discharges and land run-off from many
industrialized countries. The Baltic Sea countries have under the Helsinki Convention
adopted the decision, that the protection of the sea area from pollution can involve the use
of appropriate technical means, prohibitions and regulations of the transport, trade,
handling, application and final deposition of products containing such substances as DDT,
PCBs, PTCs etc.
Contents and fate of PBT compounds were intesively studied in the Baltic region by
various groups of scientists (HELCOM, 1996). The bioaccumulation in various species and
food chains and effects of these pollutants are very important topics for long-time. With the
aim of prediction of further condition of the pollution of sea-fish with PBTs and that of
studying the distribution of these compounds between certain elements of the ecosystem,
one part of various studies were focused on the contents of PBTs in objects of nourishment
for the Baltic herring and sprat - in zooplankton (Roots, 1996; Falandysz, 1984; Falandysz and
Rappe, 1996; Falandysz et al., 1997b, e). As the transfer of toxic chlororganics between
biological objects is effected partly through food chains, concentrations of toxic compounds
contained in zooplankton determine the intensity of accumulation of chloroorganic
substances in fish (Roots, 1996).
By an extensive analysis of zoplankton, the polluted areas and their extent exactly
enough and give a comparative estimation of pollution degree of different areas of the sea in
time and space, were determined. Geostatistical analysis did not give a definite answer to
what the minimum distance between stations should be in order to obtain independent
samples, but indicate that 700 to 1 400 m would be sufficient in most case. As plankton in
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itself comprises of a great number of various taxonomic and trophic units, a detailed
analysis is necessary.
The concentrations of toxicants in the plankton are likely to depend on several factors,
such as the wind direction, air and water temperature, sea water salinity, intensity of rain,
dry deposition from the atmosphere etc., as well as on the species composition of the
plankton.
The distribution of PCBs and DDTs concentrations in the plankton is uneven. However,
the highest concentrations have been registered in the open part of the sea (Gotland Deep
and Gdaňsk Bay). The concentration of pollutants in the plankton is likely to depend on the
species sizes, as large species of the plankton accumulate less DDTs and PCBs than the
small ones.
Based on the decision of the Baltic Marine Environment Protection Commission, a
systematic monitoring of PBTs in selected fish species of the Baltic Sea, was performed in
many Baltic countries. PBT compounds inclined to bioaccumulation in fish organisms have
attracted the greatest attention among the environmental pollutants (Roots, 1996). OCPs and
PCBs accumulating in hydrobionts penetrate into the human organism along the trophic
chain. That is the reason, why their determinations and investigations are necessary.
PBT compounds accumulation, mainly chlorinated of them, does not lead to death of
fish, but the research of bioaccumulation after-effect seems necessary as the substances
noted above have a specific trophity to the reproductive system of hydrobionts and
subsequently can promote lethal mutations and abnormalities, retard individual evolution
processes, increase death rate at different stages of spawn growth and result in the birth of
non-vitable young stock, giving scantly or badly reproductive biologically defective
offspring.
Many authors consider the Baltic herring (Clupea harengus membras L.) to be a good
indicator of the Baltic Sea ecosystem pollution by PBTs (Roots, 1996; Falandysz, 1984;
Falandysz et al., 1997d, f). Its role as a bioindicator is currently increasing. This selection
were proceeded from four principles:
●
Baltic herrings has a largest populationin the Baltic Sea and it is also the most caught
fish in the Baltic Sea,
●
Baltic herring is spread all over ther Baltic Sea,
●
although the distribution of the spread of herring from all over the Baltic Sea to
single populations is relative, one can still take into account the locations of the
populations when taking samples (14 populations of spring spawning herring are
distinguished in the Baltic Sea),
●
Baltic herring belongs to the last link of the trophic chain water-plankton-man.
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The Baltic herring, sprat and cod shares in the total catch were 42.4, 23.5 and 20.9 % in
1973, and equalled respectively 52.2, 11.0 and 28.8 % in 1988 according to the preliminary
data (Roots, 1996). The sampling was begun in 1969, a number of herrings were collected
from different catches in various areas of the Baltic in 1969-1973. Now, it is very hard to
compare these older data mainly from the analytical reasons. They are the same problems,
which are described in Chapter 10.10.1.
Temporal and spatial variations were investigated. Let us hereby observe the
concentration changes of PBTs in time during the period 1972-1988. Concentrations of
PCBs and DDTs were decreasing in Baltic herring muscle tissue in the western part of the
Gulf of Finland in 1978-1982, and in the southern part of the Baltic Sea in 1972-1988
(Bignert et al., 1993; Roots, 1996). It seems, however, that the decrease in PCBs and DDTs
levels in the beginning of the 1980ies was not any more rapid than that presented for the
years 1972-1978. The contents of some OCPs in the muscle tissue of herring rose during the
years 1983-1986 due to DDT used in East Germany (see Chapter 4.3) and due to the load of
toxicants dumped intothe Gdaňsk Bay via Vistula River. The regional pattern is, on the
whole, verified by studies reported by various authors. Bignert et al. (1993) state, that the only
biological matrix that - with a responsible effect - can be used for spatial variations in the
entire studied area is herring. For all organochlorines studied, the highest values were found
in the Baltic Proper and the lowest in the northern Gulf of Bothnia and at Swedish west
coast.
Bottom vegetation as an indispensable link in the ecosystem of the participants in its
self-purification, provides shelter for the benthic fauna, serves as a place for their
reproduction and as a substrate of spawning for several species of fish. Since algae are not
included in the monitoring programme of the Baltic Sea, their OCCs content has been so far
insufficiently studied (Roots, 1996). Several factors such as seasonal variability, changes in
pollutant content depending on growth stages, and the variation of concentration in different
parts of seaweed thalli complicate the use of benthic macrophytes as pollution indicators.
The variation of salinity is considered to be the main factor in determination of the character
of horizontal distribution of algae in the Baltic Sea. The vertical distribution of bottom
vegetation depends mainly upon the quality and quantity of light and the existence of a
favourable substratum. Benthic vegetation, especially the macroalgae along the coasts are
utilized in many countries as indicators of environmental changes. Long-term observation
series are available for the estimation of trends. Two main processes were observed - the
change in species composition, biomass and areal density and the depth range of the
vegetation zone.
The problem of using algae as a bioindicator undoubtedly needs further research. Much
more information is needed on seasonal variations of concentration. The algae species used
as bioindicators should be widely distributed in the monitoring area, respond very quickly to
the changes in the environment and the responses (concentration variances) must occur in
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intervals, which could be measured by the presently available analytical methodology.
One of the most widespread bioindicators for the evaluation of marine environment
pollution with OCPs and PCBs are various species of bottom fauna. They are a part of the
food chain in the ecosystem of the sea, in which pollutants circulate. They feed on seston
from the lower layers of water and detritus from the surface of bottom sediments, and they
themselves serve as a food for fish. Although the biomass of zoobenthic organisms in the
Baltic Sea waters is relatively low, the role of the zoobenthos in the food of fish is relevant.
The fish feeding on zoobenthos form one-third of the total number of fish caught from the
Baltic Sea (for comparison - in the Azov Sea - 21 %, in the North Sea - 19 %, in the
Caspian Sea - 16 % and in the Black Sea - 7 %).
The advantage of the Baltic Sea is the fact, that nearly all zoobenthos is edible for fish.
With their sedentary life and steady locations, they give information about local sources of
pollution with OCCs. Bottom fauna pollution with PCBs and DDTs demonstrated, that
higher pollutant concentrations were measured in the species, which are main or important
food for cod and flounder (and adult herring) (Roots, 1996). This verifies author´s claim, that
besides two- or three-year-old dwart herring feeding on the plankton on the surface layer
and bottom feeding cod and flounder of the same age, observations should also be
performed on older herring, over five years in age, which has passed to the feeding in the
near bottom layer.
Among various marine environments, the Baltic Sea and its nearby waterbodies have
been reported to be polluted heavily by organochlorine chemicals in recent years and
evidence suggests the existence of recent inputs of these contaminants in parts of marine
ecosystems (Kannan et al., 1992; Falandysz et al., 1994a). The presence of considerable levels
of organochlorines in biota from the Baltic Sea and the North Sea may have implications for
contamination in the western Atlantic Ocean as well as remote polar waterbodies by water
currents, and possible atmospheric movement of pollutants from the lower latitude
countries. The biological samples (cod-liver oil) representing similar ecological niches in
the southern Baltic proper, western Baltic Sea, North Sea, Norwegian Sea and the Icelandic
North Atlantic Ocean, were collected and analysed. The main topic of this study was to gain
better insight into the possible sources and pathways of OCCs in the Baltic Sea and its
nearby oceans on a global scale. The concentration ratios of DDT metabolites, HCH
isomers and CHL compounds in the samples were used to trace the possible sources and
pathways of transport.
Cod (Gadus morhua), is a predatory fish of the continental shelf, which inhabits waters
at a latitude of 45 °A and depths of up to 600 m. Cod accumulates lipophilic
organochlorines in the fatty liver from relatively large waterbodies because of its extensive
annual migration cycle. As a predatory fish of the continental shelf, cod provide an
integrated picture of the marine pollutants that accumulate in detritus near the bottom of the
sea. The cod from the continental shelf around the all selected sampling sites is the same
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species, but breeds only locally. No mixing of cod populations occurs over long distances,
although small-scale mixing occurs in local breeding populations. This feature can be help
in understanding the spatial distribution of contaminant concentrations. Moreover,
organochlorine concentrations in fish often reflect existing concentration at the site of
pollution due to the equilibrium partitioning; hence cod caught in different areas should
reflect pollution at the collection site. (Falandysz et al., 1994a).
Previous study (Kannan et al., 1992) clearly illustrated declining trends for DDTs, very
slow reduction rates for HCB, CHLs, heptachlorepoxide and dieldrin and a steady state for
HCHs and PCBs in cod-liver oil from the southern Baltic. The study published in 1994
(Falandysz et al., 1994a) covered a wider geographical area (as was described above) to
determine spatial differences and possible sources of OCCs in cod-liver oil from these
marine areas in the 1980s.
Of the organochlorine insecticides, Sum of DDTs was present at highest concentration
in cod liver oil from all geographical locations. On average, southern Baltic cod-liver oil
had a maximum DDT concentration of 6.3 µg.g-1, which was more than twice that in
samples from the western Baltic and the North Sea. The lowest concentrations were found
in oil originating from Icelandic shelf (0.86 µg.g-1).
The DDT concentrations in cod-liver oil followed the order: southern Baltic > western
Baltic > North Sea > Norwegian Sea > Shelf of Iceland > Northwest Atlantic. This pattern
clearly suggests a decreasing concentration gradient from east to west of the Atlantic Ocean.
The atmosphere is considered an important pathway for global transport and deposition
of anthropogenic PBT compounds. The riverine transport of OCCs may be pronounced in
the coastal zone. However, it is less significant in the open ocean and in remote areas (Barrie
et al, 1992). DDT was withdrawn from agricultural and other major uses in Baltic states and
western European countries, as well as in the USA and Canada during the 1970s and the
early 1980s (Goldberg, 1991) and was used on a limited scales only in gardening in Iceland
(Bengtson and Sodergren, 1974). Therefore, any signs input of DDT in the describes study
area (Falandysz et al., 1994a) could be attributed to the long-range atmospheric transport
from the Southern Hemisphere countries of Africa, tropical Asia, and Latin America, which
were heavy consumers of DDT in the 1980s (Forget, 1991). Although widely banned in
Europe, DDT was used in 1983-4 to control insect pests in coniferous trees in forests in the
northern part of East Germany. This would have been a source of contamination in the
Baltic Sea and some other part of region (Ericsson et al., 1989; see to the Chapter 4.3 of this
Report).
The other observed pollutants had the same local levels as was described in the case of
DDT. It is shown in the Table 10.6-1.
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The presence of considerable levels of organochlorines in fish products is of concern
with regards to its suitability as food for human consumption. The observed concentrations
of certain OCCs in cod-liver oil have exceeded the tolerance levels of most countries. A few
earlier investigations in the 1980s reported that the cod-liver of Baltic origin was unsuitable
for human consumption (Falandysz et al., 1994). More detailed results concerning the PCBs
in the samples from the Baltic area, were published in other paper (Falandysz, 1994b, c, d;
Falandysz et al., 1992).
Chlorinated insecticides such as DDT and fungicide such as HCB were intensively used
in Poland (Falandysz et al., 1997c). A recent data on DDTs contents in fishes (herring, perch)
collected from the Gulf of Gdaňsk has indicated on relatively elevated concentrations of this
pesticide when compared to herring and perch from the various sites of Gulf of Bothnia, in
the northern part of the Baltic Sea. For investigation of concentrations of DDTs, HCB and
PeCBz and their spatial distribution in a coastal area of the south-western part of the Gulf of
Gdaňsk were used stickleback Gasterosteus aculeatus as suitable indicator organism for this
type of study. The fish samples were collected from four sites in the beach zone in the southwestern part of Gulf in 1992. The samples contained DDTs (o,p´-DDT, p,p´-DDT, o,p´DDD, p,p´-DDD, o,p´-DDE, p,p´-DDE, DDMU), HCB and PeCBz in the concentrations
between 1 300 and 2 600, 18-40 and 4.8-8.2 ng.g-1 lipid weight, respectively. A relatively
elevated concentrations of DDTs and HCB were found in samples collected at a site with a
possible impact of the contaminated with those substances water of the Dead Vistula River
Channel, and at a site neighbourhood to the port and shipyards area was a relatively higher
concentration of PeCBz.
The same compounds were also determined in a pelagic food chain including mixed
phyto- and zooplankton, herring (Clupea harengues) and harbour porpoise (Phocoena
phocoena) collected from the southern part of the Baltic Sea (Falandysz et a., 1997f). Except
o,p´-DDE in fish and mammal, and DDMU and PeCBz in mammal, the BAF and BMF
values of all other compounds determined were higher then 1; p,p´-DDT and PeCBz
showed the highest bioaccumulation potential in herring (the factors 16 and ~ 8,
respectively) and p,p´-DDE in harbour porpoise (factor 10). Harboure porpoise when
compared to herring, its main food item, seems to posses much better potential to
metabolise p,p´-DDT and also a high capacity to metabolise PeCBz.
The several studies have documented the environmental occurrence of coplanar PCBs
and possible impact on biota, little is known of their clearance rate in biota due to the lack
of archived historical samples. Estimating the levels of these toxic PCBs congeners in
environmental samples over time can assist the understanding of temporal variations in both
concentrations and clearance rates (Falandysz et al., 1994b).
The liver of cod (Gadus morhua) is rich in fat and is used for the production of cod liver
oil, which is an important product in the medical industry as well as in the human diet.
Temporal trend investigations using cod liver oil from the southern Baltic Sea showed a
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very slow decline in PCBs levels (Kanann et al., 1992). The toxic potential and historical
trends of three highly toxic non-ortho coplanar PCBs in cod liver oil of southern Baltic
origin were studied (Falandysz et al., 1994c). Cod liver oil samples from Gadus morhua
caught in the southern Baltic Sea were collected in 1971-1989 (in pharmacy shops or in
processing plant).
The residue concentrations of non-ortho coplanar PCBs in cod liver oil were very high
on a product weight basis, with mean values (ranges) shows in the Table 10.6-2 together
with value of TEQ for these three congeners.
Table 10.62:
The residue concentrations and TEQ values (mean and
range) of non-ortho coplanar PCBs in cod liver oil from
the southern Baltic Sea (Falandysz et al., 1994b)
Concentrations
[ng.g-1]
PCB 77
PCB 126
13 ± 6
(4.7-23)
3.2 ± 1.6 0.59 ± 0.24
(1.3-6.7) (0.20-0.95)
2378-TCDD TEQ 130 ± 56 320 ± 160
(47-230) (130-670)
[pg.g-1]
PCB 169
13 ± 12
(10-43)
Sum of coplanar PCBs
17 ± 7
(6.3-31)
480 ± 220
(200-940)
The estimation of selective enrichment factors (SEFs) for these congeners during
selected time periods indicated a faster clearance of PCB 77 than of the other two
congeners. The SEF is the total normalised concentration of the PCB of interest in a
biological sample, divided by the total normalised concentration of the same PCB congener
in an equivalent mixture of Kanechlor 300, 400, 500 and 600 (Borlakoglu et al., 1990, Kannan
et al., 1993). Enrichment factors more than one´s suggest that accumulation of the congener
exceed their removal, presumably by metabolism and excretion. As we can see in Table of
SEF from Falandysz study (Table 10.6-3) (Falandysz et al., 1994b), the SEF for PCB 77
remained less than unity throughout the period studied, indicating its metabolism and/or
excretion in fish. The SEF for this congener appeared to increase (possibly indicating
increasing inputs, exceeding rates of metabolism and excretion) until early 1980s, and
declined thereafter.
Table 10.63:
Selective enrichment factors for non-ortho coplanar
PCBs and total PCB concentration in cod liver oils from
the southern Baltic Sea during different time periods
(Falandysz et al., 1994b)
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IUPAC No. of congener
77
126
169
Total PCBs
[ng.g-1]
1971
0.14
4.7
67
9 100
1975
0.26
9.0
130
13 000
1980
0.31
12.0
230
14 000
1985
0.28
12.0
200
11 000
1989
0.21
9.6
230
10 000
Year
The temporal trends of non-ortho coplanar PCBs suggested that the lower chlorinated
PCB congener (77) followed the same pattern as was observed for total PCBs, whereas the
hexachlorobiphenyl (169) showed a steady-state enrichment, posing potential long-term
toxic threats to biota.
Congener-specific analysis of PCBs in some species of fish collected at Gdynia, western
part of the Gulf of Gdaňsk, were done in 1992. The results showed that the level of PCBs in
fish from the southern part of the Baltic Sea were still relatively high and from 1 700 to
11 000 ng.g-1 lipid weight was noted in the species such as flounder, eelpout, round goby,
perch, pikeperch, sanddeel, lamprey and cod (Falandyszet al., 1997d). These results also
confirmed that the fish from the Baltic proper usually contain total PCBs in higher
concentration than the specimens from other areas of the North Atlantic Ocean basin.
However, till now there is no inventory of the sources, and also a net budget of those
substances in a whole area of the Baltic proper is unknown.
Falandysz et al. performed also some other studies focused on congener-specific
analysis of polychlorinated biphenyls in white-tailed sea eagles (Haliaeetus albicilla)
(Falandysz et al., 1994c) and common porpoise (Phocoena phocoena) (Falandysz et al.,
1994d). White-tailed sea eagle is a top predator around the Baltic Sea. The purpose of this
study was to determine the concentration of a full range of PCBs in white-tailed sea eagles
(breast muscles, collected dead) from two breeding sites in Poland 1982-1990, and to
determine the relative contribution made by highly toxic coplanar PCBs to calculated TEQ.
Fish (herring, cod, eelpout, round goby, flounder, perch, lamprey, pikeperch, sand eel
and lesser sand eel) caught in the Gulf of Gdańsk in 1992 did contained the residues of
penta- (PeCBz) and hexachlorobenzene (HCB) in concentrations from 0.09 to 0.75 and
from 0.36 to 3.7 ng.g-1 wet weight (3.3 - 14 and 6.5 - 41 ng.g-1 lipid weight), respectively
(see Table 10.6-4) (Falandysz et al., 2000).
The other part of Baltic Sea region, the eastern Estonian coastal water (Gulf of Finland,
Gulf of Riga, West-Estonian Archipelago Biosphere Reserve) is a subject of long-term
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scientific activities of Roots and co-workers (Roots and Aps, 1993; Roots, 1995; Roots, 1996;
Roots and Talvari, 1997, 1999; Roots, 1998; Roots, 1999). In the first period (1974-1994) the
main activities in this region was focused on deposition and ambient air concentration
together with the studies on the distribution of PBT compounds among water, plankton,
fish, algae, seals etc. In the second period (after 1994) the aim of the study was to search
reasons for the increase in Baltic seal population.
The seals were chosen to be the subject of this research work because living at the
highest level of the food chain of the Baltic ecosystem, they accumulate many kinds of the
highly toxic compounds. The main attention was done on grey seal (Halichoerus grypus)
(Roots, 1999). In the late 1970s, fewer than 2 000 grey seals were registered in the Baltic
Sea. Since then, the general annual population of grey seal increased in the northern part of
the Baltic Proper (area in North Gotland) and in the Gulf of Bothnian by 8-12 %.
As compared to the end of 1970s and the beginning of 1980s, at least the PCBs and
OCCs concentrations obtained by food in grey seals in West-Estonian Archipelago Reserve
must have decreased. This is probably the result of natural changes in the last twenty years
(decrease in salinity and oxygen concentration in the Gotland Deep) (Roots, 1998).
Comparing the food chain of grey seal in the Central Baltic in the beginning of 1970s and
species content during examination catches in spring 1995, we can assume that nowadays
the grey seals caught from Estonian monitoring sites, cannot have as much fat fish - cod,
salmon and sea trout as in the end of 1970s and in the beginning and in the middle of 1980s
(Roots, 1998).
Low salinity and oxygen concentration began to affect the evaluation of grey seals (also
cod and salmons) main food, Baltic herring and sprat. The mean weight of herring and sprat
has been decreasing in all regions of the Baltic Sea. The studies concerning the feeding of
herring and sprat carried out during the years 1982-1992 in the north-eastern part of the
Baltic Sea showed changes in fish diet and also the rising number of fish with a empty
stomach (Roots, 1996; Roots, 1998; Roots, 1999). It is especially hard to predict the
consequence of the next very strong inflow of brackhish water from the North Sea to the
Baltic Sea.
A study of persistent chlorinated hydrocarbons in the Baltic herrings and sprat muscle
tissue was carried out in the Eastern Baltic in 1975-1997, 1986 and 1991. In the Baltic Sea
the surface layer PCB components adsorb on the surface of plankton (Roots and Aps, 1993).
The highest concentration of PCBs and DDTs were registered in the open part of the sea.
The concentration of pollutants in the plankton is likely to depend on several factors, such
as the direction of wind, air, and water temperature, seawater salinity, intensity of rain, dry
deposition from the atmosphere, as well as on the species composition of the plankton. The
increase of plankton PCB concentration depends on its diurnal movement (at night rises to
the surface).
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Two- or three-year old mature herring (and sprat) feeds on the plankton in the surface
water layer. There was a clear tendency that the open sea herrings contained more PCBs and
DDTs than the gulf herrings (in the period 1976-1977), but in 1986 the higher PCB
concentrations were detected in the eastern part of the Gulf of Finland Table 10.6-5 (Roots,
1995).
The Riga Bay is the location of one of three most important seal populations of the
Baltic Sea. It was the main reason for the selection of this region and study of PCBs and
OCCs in seals and their ecosystem. The comparison of PCB contents of seals in different
part of the Baltic Sea led to the state that based on the distribution of these pollutants, the
northern part of Riga Bay is the reference area for the Baltic Sea (see Table 10.6-5). As you
can see from the table, the different situation is in the case of organochlorine pesticides.
The confirmation of the thesis the reference area, were made in 1994 (Roots and Talvari,
1997). Two samples of grey seals were taken in Väinameri Sea (north part of Gulf of Riga)
and for comparison one sample in the Vilsandi National Park - open Baltic Sea. The content
of PCBs and OCCs in grey seals caught in near past of Estonian coastal waters (northern
part of Gulf of Riga and the Väinameri Sea) did not exceed 50-70 ppm, which has been
considered as a critical limit of the seals reproductive ability.
Important factor for the contamination is also migration of the seals, especially
migration of the grey seals, younger than 1 year, to the southern part of the sea. In the
southern part, the food has higher PCB concentrations than in the northern part of the sea
(Roots, 1999a). The female grey seal´s milk contains 60-80 % of fat and a large amount of
lipid soluble contaminants are passed from mother to pup.
Study of PCB content at two sites of the West-Estonian Archipelago Biosphere Reserve
revealed as the most important PCB congeners 138, 153 and 180 with the range of
concentrations 2.3 - 25.5 µg.g-1, 2.9 - 44 µg.g-1 and 1.5 - 24 µg.g-1 extracted lipid weight in
blubber of 2-8 years old grey seals (Roots, 1999b). The animals with a poor nutritional status
had significantly higher concentration of pollutants than other groups. This is probably due
to the fact that these seals had used the fat as a source of energy without being able to
metabolise or excrete the pollutants at the same rate.
At the present time, long-range transport of PCBs from southern sources outside Estonia
dominate, as is reflected by decreasing south-to-north gradient of compounds in
atmospheric deposition and fish. Calculations of back trajectories identified different parts
of Central Europe as source areas. Around 1995 the deposition load of PCBs in fifteen
stations around the Baltic Sea ranged from 1.2 to 17.9 ng.m-2.day-1. The deposition loads of
PCBs in the Estonian EMEP stations, Vilsandi and Lahemaa (northern part of Estonia,
70 km east of Tallin) were 2.2 ng.m-2.day-1 and 1.8 ng.m-2.day-1. The loads can be
considered as background for the Baltic Sea.
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The European otter (Lutra lutra) is a widespreade species on the Euroasian continent.
Since the 1950s some European otter populations have declined dramatically. There are
however significant differences in the otter population density between different areas
(Sjőásen et al., 1997). Many different explanations for the decline had been presented: e.g
habitat destruction and direct or indirect influences of eutrophication, acidification and toxic
chemicals. In the beginning of 1980s, PCBs were suggested to be an important reason for
the otter population decline. Based on the results of various studies, PCBs seemed to be an
important agent for the explanation of the otter decline and the present distribution in
Europe.
In Latvia, otters are present in all kinds of watercourses. The Latvian otter population
was estimated of more than 4 000 specimens in 1993. In comparison, the Swedish otter
population was estimated of 500 - 1 000 specimens in an area approximately seven times
larger. There was remarkable difference in otter population densities between Latvia and
Sweden. The aim of one study was to investigate whether or not PCB pollution varied
between these two areas. The samples of otter and otter food from the both areas, such as
fish and amphibians, were analysed (Sjőásen et al., 1997).
The mean concentrations of PCBs and DDTs on a lipid weight basis, in otters from
Latvia were 2.3 µg.g-1 and 0.22 µg.g-1, respectively. There were no significant differences
between the two areas in Latvia, similarly in the case of fish and frog. The Swedish samples
contained similar concentrations of PCBs and DDTs. The concentrations of PCBs and
DDTs in otters from Latvia were low, compared to those given in the available data from
literature concerning otters from other countries of Europe (see Table 10.6-6). The
concentration in the samples from Latvia were even lower than concentrations in otters
from the coast of northern Norway an area considered to have dense otter populations
(Sjőásen et al., 1997).
The dense otter population and low concentration of PCBs in Latvian otters of today
indicate that the population has been less exposed to PCBs than the otters in many other
European countries.
In earlier 1990s was established a model to calculate PCB levels in otters and minks
from food levels. Recently two additional models were published with some additional
physiological factors incorporated. PCBs levels in scats showed good correspondence with
relative status of order populations. Estimating PCBs in otter livers from concentrations in
fish or scats would be of a very great advantage as, in general, only a limited number of
dead otters, mostly killed by traffic accidents or drowned in fish nets, become available for
chemical analysis (Gutleb and Kranz, 1998).
The PCBs residues in fish, scats and in otter livers were used for validation of this
model. The otter samples were collected in the Waldviertel, Austria and the adjacent area in
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the Czech republic. The otters in this area form the strongest population in Middle Europe.
The observed level is in previous Table 10.6-6. This value was in very good agreement with
calculated value.
There was a wide variation in total PCB residue concentrations among eagles from
various breeding sites, with the Baltic Sea coast registering the highest concentrations. TEQ
of 2378-TCDD for non-, mono- and di-ortho coplanar PCBs were very high (8.0 - 72 µg.g-1
wet wt) in white-tailed sea eagles from breeding sites of the coastal area of southwestern
Baltic Sea, and relatively lower (0.69 - 4.0 µg.g-1 wet wt) in other birds (including two
specimens from breeding sites of inland Poland, which died because of acute lead
poisoning). The concentrations of coplanar PCBs in adult white-tailed sea eagles were the
highest ever reported in wildlife. PCBs observed in high concentrations in body tissues of
female white-tailed sea eagles are directly connected with high contamination of potentially
produced eggs and may be associated with eggshell thinning and low reproduction success
of eagles. A total lack of reproduction among white-tailed sea eagles in the coastal area of
southwestern Baltic in the 1960s, and a very low rate in the 1970s with the productivity of
0.17 may be partially related to high concentrations of coplanar PCBs in tissues of adult
eagles indicated in this study (Falandysz et al., 1994c).
The second study described the results of PCB congener-specific analysis of blubber,
liver and muscles of three female common porpoise Phocoena phocoena collected from the
Puck Bay (inner Gulf of Gdaňsk, Poland) in 1989-1990 (Falandysz et al., 1994d). The total
2378-TCDD TEQ for 13 coplanar PCBs in blubber was 1 500 ± 470 pg.g-1 wet wt.
PCB 118 was the most contributing individual congener of PCBs in blubber, while
PCB 156 was absent. Concentrations of total PCBs in lipids of the blubber ranged from 26
to 47 ng.g-1 and were comparable or lower than reported earlier for common porpoise from
the Baltic Sea, North Sea, and Atlantic Sea by other authors.
Concentration and spatial distribution of chlordanes (CHLs, 12 components and their
metabolites) and some other cyclodiene pesticides (aldrin, dieldrin, endrin, isodrin,
endosulfan 1 and 2, mires) in Baltic plankton were also studied by Falandysz et al.
(Falandysz et al. 1998). Some constituents of technical chlordane, as well as metabolites
(oxychlordane and heptachlorepoxide) are compounds very persistent under environmental
conditions they are bioaccumulated in animals and humans and are chiral (Falandysz et al.,
1998).
These compounds were quantified in mixed subsurface phyto- and zooplankton
collected at four spatially distant sites in the southern part of the Baltic Sea. The CHLs
concentrations in plankton were very low, i.e. 5.3, 8.7, 9.2 and 8.7 ng.g-1 lipid in Gdaňsk
Depth, Gotland basin, Bornhol Basin and Pomerenian Bay, respectively. Chlordane
compounds showed similar distributions and patterns in plankton at all four sampling sites.
The trans-nonachlor to cis-nonachlor ratio (A:C) in plankton was between 0.76 and 1.0
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which clearly indicates pollution from distant source due to long-range transport. The
relatively high concentrations of heptachlor epoxide seem to be related to local sources of
pollution around the Baltic Sea. Dieldrin was the major cyclodiene pesticide quantified and
its concentration was uniformly distributed in the plankton sampled and ranged from 23 to
42 ng.g-1 of lipid. While all other observed compounds were undetected.
Falandysz and co-workers also studied the contents of OCPs (DDTs, PeCBz, HCB)
(Falandysz et al., 1997b) and PCBs (Falandysz et al., 1997e) and their spatial distribution in
subsurface mixed phyto- and zooplankton collected in the southern part of the Baltic Sea in
1992. The 1992 concentrations of DDTs were five to eight times lower than was found in
mixed plankton collected from the same regions of the Baltic in 1983, and in parallel there
was also high reduction of the concentration of HCB, while PCBzs remained undetected. A
large reduction of the concentrations of DDT and HCB in plankton over the period from
1983 to 1992 seems to indicate on decreased deposition rates of these compounds from the
atmosphere into the southern part of the Baltic Sea in recent years (Falandysz et al., 1997b).
A congener-specific analysis of PCBs in the same matrix, a mixed phyto- and
zooplankton collected from four spatially distant sites in the southern part of the Baltic Sea
(Gdaňsk Depth, southern part of the Gotland Basin, Bornholm Basinand the Pomerian Bay),
were performed in 1992. Revealed on higher concentration and a somewhat different
pattern of those chemicals in two samples from the coast orientated sites when compared to
those from the open sea (Falandysz et al., 1997e). Because of the very similar fingerprint of
PCBs in two an open sea plankton samples (Gotland Basin and Bornholm Basin) apart to
the atmosphere also contaminated river water can be an important route of transportation
and source, and especially of lower chlorinated PCB congeners in a specific areas (such as
the Gdaňsk Basin) in the southern part of the Baltic Sea.
Organochlorine cyclodiene pesticides such as chlordane and its metabolites and dieldrin
are common contaminants quantified in Baltic biota. Recently also mirex was identified in
the Baltic Sea environment (Falandysz et al., 1998b; 1999). Both chlordane and dieldrin were
used in small quantities in the past in some of the Baltic States, while mirex was not
registered. Dieldrin is known as extremely toxic compound. A very high environmental
persistency and relative abundance of dieldrin in various biota from the Baltic Sea the 1990s
is a somewhat amazing.
Chlordanes (CHLs: trans- and cis-chlordane, trans- and cis-nonachlor, oxychlordane,
heptachlor, heptachlor epoxide, MC4, MC5, MC6, MC7 and U82) aldrin, dieldrin, endrin,
isodrin, endosulfan 1, endosulfan 2 and mirex were quantified in mollusc, crustacean and
fishes from the Gulf of Gdańsk in order to clarify concentrations, compositional pattern,
spatial distribution and possible sources of pollution.
Blue mussel (Mytilus trossulus), crab (Carcinus means) and fishes: herring (Clupea
harengus), cod (Gadus morhua), pikeperch (Stizostedion lucioperca), perch (Perca
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fluviatilis), round goby (Neogobius melanostomus), sand-eel (Hyperoplus lanceolatus),
lesser sand-eel (Amodytes tobiasus), lamprey (Lampetra fluviatilis), flounder (Platichthys
flesus) and stickleback (Gasterosteus aculeatus) were collected from a several sites in the
south-western part of the Gulf of Gdańsk in summer and autumn 1992. A pooled samples of
the soft tissues of mussel, a whole crab and fish were subjected to chemical analysis.
Only chlordane compounds and their metabolites and dieldrin could be quantified in
biota examined (Table 10.6-7). It was found that CHLs and dieldrin showed similar
concentrations in mussels and in most of the fishes sampled.
Trans- and cis-chlordane, trans-nonachlor, oxychlordane, heptachlor epoxide, MC5 and
MC7 were found in blue mussel and crab. The concentrations of CHLs and dieldrin both in
blue mussel from the site Gdynia (Gdy) and Orłowo (Orł), and crab were relatively low.
Trans- and cis-chlordane, trans- and cis-nonachlor, oxychlordane, heptachlor epoxide,
U82, MC4, MC5, MC6 and MC7 were quantified in all fish examined. The pattern of CHLs
determined in flounder, stickleback, perch and lamprey from spatially different sites in the
Gulf of Gdańsk was similar. Also similar pattern of CHLs was observed between different
species of fish examined.
In earlier studies chlordane (trans- and cis-chlordane, trans-nonachlor and
oxychlordane) was quantified in Baltic herring in concentration 520 ng.g-1 lipid (1970),
600 ng.g-1 lipid (1978), 560 ng.g-1 lipid (Archipelago of Turku, 1982), 190 - 200 ng.g-1
lipid (1979-87), 44 ng.g-1 lipid (Gulf of Finland, 1985-89) and 46 - 96 ng.g-1 lipid (Gulf of
Bothnia, 1991) (Falandysz et al., 1999).
Chlordane is widely distributed in the marine ecosystems and is easily bioaccumulated
and biomagnified by marine biota. Apart from this studies CHLs in low concentration were
found in sediment from the Baltic coast of Poland in 1990, and in flounder from the Gulf of
Gdańsk in 1990 (3.1 ng.g-1 wet weight). A similar pattern, low concentrations and
decreasing trend of CHLs quantified in fish and other matrices from the Baltic Sea did
indicated that there is no fresh inputs of that pesticide. On the other hand dieldrin seems to
be much more stable compound in the Baltic Sea environment (Falandysz et al., 1999).
PCDDs/Fs were determined in plankton, mussel, crab, fishes, aquatic birds, birds of
prey and marine mammals collected in 1991-1993 from the southern part of the Baltic Sea
(Falandysz et al., 1997a). The biota examined seem to be only slightly contaminated with
PCDDs/Fs. The I-TEQs due to PCDDs/Fs were 18 pg.g-1 lipid in plankton, from 23 to
590 pg.g-1 in mussel, 42 pg.g-1 in crab, from 3.8 to 67 pg.g-1 in fishes, 5.6 pg.g-1 in blubber
of harbour porpoise, and 110 pg.g-1 in the breast muscles and 420 pg.g-1 in liver of black
cormorant, while for an adult white-tailed sea eagles in the breast muscles and liver were
from 470 to 870 pg.g-1, and for the juveniles from 13 to 77 pg.g-1. The observed
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concentrations of PCDDs/Fs in biota from the Polish coast of the Baltic Sea, were a
consequence of the background contamination of the coastal marine environment probably
from atmospheric input and did not indicate on an existence of the important local sources
of emission at least in the western part of the Gulf of Gdaňsk. A relatively higher
concentrations of PCDDs/Fs found in the breast muscles and liver of adult black cormorants
as well as white-tailed sea eagles indicate on biomagnification potential of those substances
in a particular marine food webs.
Tetra- to hepta-CNs have been detected at higher concentrations in adult white-tailed
sea eagles (range 0.69 - 2.6 mg.g-1 lipid wt in liver) and black cormorants (range 0.17 0.26 mg.g-1 lipid wt in liver) nesting on the southern Baltic coast as well as in crab, fishes
with large and fatty livers (round goby and cod) when compared to many other animals
(Falandysz, 1998; Falandysz et al., 1996, 1997g). There are no data on mono-, di and tri-CNs in
wildlife. At sites with background pollution, tetra-CNs are the most abundant homologue
group in river sediments and in biological matrices with lower drug-metabolising potential
(plankton and mussels), and also in plankton-feeding fish (three-spined stickleback, lesser
sand eel, sand eel, herring). Predatory and bottom feeding fish (flounder, round goby,
eelpout, perch, pike-perch, cod), crab and an adult white-tailed sea eagle showed a higher
abundance of penta- than tetra-, hexa- or hepta-CNs. Juvenile (or immature) white-tailed sea
eagle and black cormorant also contained a relatively higher proportion of tetra-CNs.
The fingerprint of PCNs in various biological samples can be very characteristic and
indicative of the relative persistence of several congeners under environmental conditions
(Falandysz, 1998; Falandysz et al., 1997g). The fingerprint of PCNs in biological samples
collected from the sites locally polluted with these substances can somewhat resemble that
of the corresponding exposure situation, and still the most persistent among the tetra-CNs
(1,3,5,7-TCN, No. 42) or penta-CNs (1,2,3,5,7-/1,2,4,6,7-PeCN, Nos. 52 and 60), were
relatively more abundant in fish than in the corresponding abiotic matrix.
PCNs were also determined in a pelagic food web including mixed subsurface plankton,
Baltic herring (Clupea harengus), and harbour porpoise (Phocoena phocoena) (Falandysz
and Rappe, 1996; Falandysz et al., 1996, 1997g). Nearly all theoretical possible tetra- through
hepta-chlorine substituted naphthalene congeners were identified and quantified in all
samples examined. The concentration, profile, and patterns of PCNs found in spatially
different plankton samples indicate that the atmosphere as a dominating long-range
transportation and deposition route of these pollutants into the southern Baltic proper.
Biological matrix-dependent variations found in the compositional pattern of PCN
congeners indicate selective and structure-dependent metabolism as well as the retention of
some PCNs within a pelagic food chain studied. Herring is the main food item for harbour
porpoise. Only recently has it been indicated that this marine mammal species, due to the
presence and activity of PB-type and 3-MC-type (MC-type) isoenzymes of the P-450
monooxygenase system, has the capacity to metabolise many congeners of PCBs (Bruhn et
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al., 1995).
The fingerprint and also pattern of the particular PCN homologue groups differ
largely between harbour porpoise and herring, which can indicate metabolising possibilities
of this mamma for many of PCN congeners (Falandysz and Rappe, 1996). Only the
congeners 66/67 seem to be biomagnified in the food chain including herring and harbour
porpoise. These two PCN congeners are known due to their high bioaccumulative potential
in rats and wildlife (Asplund et al., 1994; Falandysz and Rappe, 1996).
Tris(4-chlorophenyl)methane (TCPM-H) and tris(4-chlorophenyl)methanol (TCPMOH) are environmental contaminants recently identified in high trophic level organisms
(Falandysz et al., 1999) and some other commodities. TCPM-H, which is a possible substrate
to TCPM-OH, was first quantified in peregrine falcon (Falcon peregrinus anatum) eggs in
the US and in blubber and liver of ringed seal (Phoca hispida) from the Baltic Sea (Jarman
et al., 1992, Zook et al., 1992). The concentration of TCPM-OH in a archived samples of
beluga whale and harp seal fat collected in 1952 was 2.0 - 4.0 ng.g-1 lipid, while in aquatic
birds and some other species of marine mammals ranged from 1.0 to 6 800 ng.g-1 lipids
(Jarman et al., 1992). The concentration of TCPM-H/OH quantified in human milk was
4.1 ng.g-1 lipids, and in fish oils it was between 36 and 54 ng.g-1.
The all members of group of DDTs are highly lipophilic compounds (log Kow ~ 6).
There is no data available on log Kow values or other physicochemical or environmental
properties of TCPM-H/OH. TCPM-OH is more polar than TCPM-H, and due to their
structure, both compounds seem to be more hydrophobic than DDTs.
studied the spatial distribution of TCPM-H/OH and their
relationships with DDTs in blue mussels and fish from the Gulf of Gdaňsk and later
examined if there are any differences/similarities in distribution and pattern of pollution,
bioaccumulation and biomagnification potential, persistency, and relationship of TCPM-H/
OH to p,p´-DDT and its metabolites in Polish coastal areas in the Baltic Sea using surface
sediment, plankton, mollusc, crustaceans, fish, lesser sand-eel, eelpout, three spined
stickleback, perch, pikeperch, round goby, flounder, birds and marine mammals (Falandysz
et al., 1999).
Falandysz et al. (1998)
TCPM-H/OH were not detected in sediments, plankton, blue mussel, and crab (< 0.3 ng.
g-1 on a dry weight or lipid weight basis, respectively). These compounds were identified
and quantified in fishes (4.1 - 37 ng.g-1 lipids), fish-eating birds (120 - 630 ng.g-1 lipids),
and marine mammals (13 - 37 ng.g-1 lipids) from the southern part of the Baltic Sea. The
highest concentrations were found in some specimens of adult white-tailed sea eagles (eggs
and tissues) from the Baltic coastal (< 13 - 130 000 ng.g-1 lipids). The species of whitetailed sea eagles from the breeding sites of inland Poland were less contaminated (< 1 1 500 ng.g-1 lipids).
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This paper (Falandysz et al., 1999) as a first indicated the high bioaccumulation and
biomagnification rates both of TCPM-H and TCPM-OH in marine food web (including a
coastal and freshwater top predator such as white-tailed eagle). This study showed that both
TCPM-H and TCPM-OH can be found in significant amounts in edible fish species about
apparently indicate the transfer of these xenobiotics through the marine and human food
chains. Assuming that technical DDT is a main source of TCPM-H and its metabolite
TCPM-OH, both these compounds are considered as very persistent under environmental
conditions, and their environmental residence times can be much higher than those of
DDTs, including most persistent metabolite p,p´-DDE.
To the top | last update: 22. 01. 2007
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Persistent, Bioaccumulative and Toxic Chemicals in Central and
Eastern European Countries - State-of-the-art Report
Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
10.6.3 Inland waters
Polychlorinated biphenyls were on of the most serious contaminants in former Czechoslovakia.
The determination of contents of PCBs in various environmental compartments, foods and human
population from Czech and Slovak Republics confirm that this contamination has been dropping
very slowly (Kočan et al., 1999; Hajšlová et al., 1997; Gregor and Hajšlová, 1998; see also the other
Chapters).
Various scientific and monitoring programmes select for study of occurrence, fate, trends and
risks of PBT compounds specific indicators. Fish can be useful as bioindicator of these types of
pollutants in the aquatic ecosystem (Hajšlová et al., 1997). The few this type of studies in the Czech
Republic which performed by group of Prof. Hajšlová from Prague (Hajšlová et al., 1997; Gregor and
Hajšlová, 1998). The purpose one from them was to determine the characteristic patterns of
persistent organochlorine contaminants in several fresh water fish species. These species were
obtained from the lake located in area where no primary source of pollution was detected and to
choose the suitable bioindicator for the monitoring of the contamination trends in this proposed
background site. Omnivorous fishes (carps, Cyprinus carpio L., breams, Abramis brama L.) and
predatory fish (pike-perches, Stizostedion lucioperca, L.) were obtained from Mušov Lake located
in southern Moravia, Czech Republic. Indicator congeners (28, 52, 101, 118, 138, 153 and 180)
and other major congeners (31, 44, 66, 70, 74, 105, 110, 114, 128, 149, 158, 163 and 170) were
determined together with chlorinated pesticides (HCB, HCHs, DDTs).
The summary of reported concentrations of observed pollutants is shown in the following
Table 10.6-8. The concentrations of analytes are reported both as lipid-normalised values and on a
fresh weight basis.
The reason for this statement was not only existing characteristics differences in lipid content
among investigated fishes (muscle tissue of pike-perch is inherently less fatty than that of carp and
bream), but also the variations in fatness during particular seasons - in dependence on food
availability - have to be anticipated. The importance of detailed specification of sample
preparation procedure should be emphasised on this occasion (Hajšlová et al., 1997). For instance,
the removing of the skin which is usually rich in fat may contribute to the reduction of PCBs
findings in analysed fillets and, consequently, underestimation of residue levels in edible portion
of fish (which in common perception contains skin) may occur.
Although the content of contaminants within the each set of samples varied an a wide range,
their mean values in fat were not so different among individual species, the lowest content of
organochlorine contaminants was found in carps. Regardless of their position in the food chain, the
PCBs patterns were very similar in tested samples. This was rather in contradiction to some
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literature data (Parkerton et al., 1991), nevertheless, the differences in the dietary exposure of
omnivorous fish and predator one represented by pike-perch is not so significant.
While the PCBs profiles determined in this study, were very similar to those found in carps
taken from other areas involved in Czech monitoring programme that are considered as "clean"
with only background contamination. The carps collected in sites with accidental pollution
contained significantly higher levels of lower chlorinated congeners of PCBs (trichlorobiphenyls
are dominating) (Hajšlová et al., 1997).
Relationships between the data obtained in this study were tested by general linear model
procedure using a linear regression analysis. From the results of this analysis one important for this
monitoring programme - an extremely close correlation was found between the content of
OCB 153 and the sum of indicator PCBs (correlation coefficient 0.981). From practical point of
view, this extremely persistent congener could be monitored as a representative indicator of the
extent of total PCBs contamination. To confirm this assumption, the data from regular monitoring
were processed (PCBs in 25 the dam characterised with relatively high contamination). The
correlation coefficient of this relationship was again high (0.911).
Relatively high levels of indicator and planar, dioxin-like PCBs were found in various fish
species collected at some of sampling sites involved in monitoring programme funded by the
Czech Ministry of the Environment (Gregor and Hajšlová, 1998). Following samples of pooled fish
(fillets, skin removed) collected in autumn 1997 were analysed: barbel caught in Elbe river,
locality Hřensko - close to the German border; yellow eel, from the same sampling site; roach
caught in Skalica river, locality downstream from Rožmital and roach caught in Skalice river
upstream from Rožmitál.
Skalice was further river concern as regards potentially increased incidence of PCBs in fish. 12
years ago, a serious breakdown pollution by Delor 103 (Czechoslovakia name of PCBs containing technical PCBs mixture with 48 %, w/w, chlorine) occurred at the locality Rožmital.
Roach, which is the most abundant fish among locally available species, was sampled close to the
site of PCBs leakage. Observed values indicate unequivocally continuing high PCBs input at
sampling site downstream from Rožmital. Ten-fold higher total TEQs were found in fish living
here compared to that collected upstream. The concentrations of non-ortho and mono-ortho
substituted PCBs determined in barbel from Elbe river even exceeded values reported for some
freshwater fish (pike-perch, perch) collected in seriously polluted Rhine, Meuse and their siderivers. Hence, considering results obtained for barbel from Czech part of Elbe, may be assigned
among the strongest PCB-contaminated waters in Europe (Table 10.6-9).
The measurements of PCBs and OCCs contents in samples of biota were the other part of very
unique study concerning the environmental and human population load in the area contaminated
with PCBs (Kočan et al., 1999) (see also to Chapter 10.1). Summary of results from measurements
of fish samples is described in the Table 10.6-10.
The levels of PCBs in District Michalovce are again similar as in the case of abiotic samples
higher than in District Stropkov which were used for the comparison. The numbers in the Table
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10.6-10 are data from mixtures of various species. These mixtures were not the same as far as
amounts of fish in various samples. But for illustration of level of contamination in these two
regions we can used them.
Likewise the sediment, fish from Michalovce waters contained much higher PCB levels than
those from Stropkov waters (Chapter 10.3.3). It was confirmed that predators are more exposed
than fish feeding on plankton or benthic food. The environmental pollution of Michalovce district
with PCBs is reflected in exposure of forest and field wildlife, as well (Figure 10.6-1).
Figure 10.6-1: PCB levels in benthic and planktonophage and predatory
fish caught in Michalovce (Zemplínská Šírava Lake,
Laborec River) and Stropkov (Domaša Lake, Ondava River)
districts (Kočan et al., 1999)
While the contamination of aquatic ecosystem by "classical" PBT type of compounds has been
well documented over the past decades, "musk compounds" have so far escaped from appropriate
attention (Hajšlová et al., 1998). Synthetic musks are widely used as fragrance substances in
detergents, cleaning agents and cosmetic products.
Extensive release of musk compounds from household use as well as from industry
(contaminated waste waters) occurred during the years of their use. The first report on the presence
of these substances in aquatic ecosystem dates from 1981. Japanese scientists identified musk
ketone and musk xylene in carp and subsequently in shellfish from Tokyo Bay. In following years
musk compounds were found as contaminants not only in freshwater fish but also in human
adipose tissue. Since the biodebradability of nitro musks is low and their lipophility is relatively
high (log Kow for musk ketone is 4.9 and for musk xylene is 4.2), accumulation in abiotic and
biotic part of environment including biomagnification in food chains may easily occur (Hajšlová et
al., 1998).
Data on the levels of these compounds in biota are rather sporadic, the routine monitoring of
these compounds in abiotic or biotic matrixes is not common. Similarly to many other countries,
no comprehensive information on environmental musks is available in Czech Republic. One study
to implement analytical method applicable for simultaneous determination of musk xylene, musk
ketone (the nitro musk group), galaxolide and tonalide (the polycyclic musk group) in fish samples
collected at Elbe River, was performed (Hajšlová et al., 1998).
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Two localities upstream and downstream from industrial cities representing potential source of
this type of pollution were sampled. These industrial cities were Pardubice and Ústí nad Labem in front of and beside the two important centres of Czech chemical industry. Breams, perches and
chubs, 20 pieces each, were collected in these localities.
In all the examined fish samples collected from Elbe River, the presence of targeted nitro- and
polycyclic musks was proved. The levels of galaxolide and tonalide were generally distinctly
higher than those of nitro musks (similar findings were obtained for all other fish species). Highest
concentration of tonalide and galaxolide (3 194 µg.g-1 and 1 289 µg.g-1, on the fat basis) were
recorded at the locatility Hřensko (downstream of Ústí nad Labem). This may be due to the wastes
from detergents producing factory located upstream from this locality. This assumption
corresponds to lower levels of analytes found in fish upstream from this potential source of
pollution. Similarly, increasing levels of polycyclic musks, probably due to the municipal wastes,
were determined in fish collected downstream from urban area Pardubice (Hajšlová et al., 1998).
Some differences, both qualitative and quantitative, were found in fish representing various
trophic levels. Nevertheless, the contribution of food chain (biomagnification) to the
bioaccumulation of musk compounds in examined fish was not statistically significant. The levels
in juvenile species and adults were almost the same, some biodegradation and/or elimination of
these contaminants occurs (Hajšlová et al., 1998).
The deals with HCH spread in different trophic levels of Babeni Lake biocenoses using
samples from these trophic, were studied in Romania (Toader and Chitimiea, 2000). The
bioaccumulation level in the top ring - fish - of Lindane and metabolites are established, as well as
their spread in different parts of the trophic levels. The trophic levels of Babeni Lake biocenoses,
which were taken into account and analysed, are: phytoplankton; zooplankton; benthos - biological
death; nekton - fish; periphyton. Average bioaccumulation factors are calculated and a ranking of
them in biocenoses for active compound - Lindane - and for its metabolites (congeners alpha, beta,
delta - HCH) is done.
For assessing the bioaccumulation factors of HCH in different trophic rings from the studied
ecosystem, different samples have been taken and analysed: plankton - the entire zoo- and
phtoplankton organisms; macrophyte - bulrush - Tycha sp.; fish - carp - Carassius auratus;
periphyton - microplants from the stones. In order to estimate the bioaccumulation level a simple
model is used:
dCp/dt = K1 * Ca - K2Cp
Where: Cp - toxic compound concentration in the searched organism; Ca - the compound
concentration in water; t - time; K1 and K2 - constants which defines the accumulation and release rate.
Models of this sort, although don´t succeed to offer satisfactorily the dynamics of the
accumulation complex process, allow to establish some useful parameters in order to characterise
the experimental figures. In this way, the bioaccumulation factor is defined FBC = K1/K2 as the
ratio between accumulation and release rate. In the conditions of accumulation process equilibrium
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(dCp/dt = 0) the bioaccumulation factor can be expressed as well as the concentrations ratio in
organisms and water: K = Co/Cw. HCH analysis is done by gas-liquid chromatography with proper
parameters using ISO/DIS 6468.2 method.
HCH quantities, up-taken by aquatic organisms from water depend on the certain trophic level.
Surprisingly, not the fish is the ring which accumulate the highest quantity of HCH but periphyton,
followed by plankton, both for active compound - Lindane - and all the others congeners which
appear from metabolism and less from the bio-accumulation from water. The least present
congener is delta-HCH which, usually, is higher in animal organisms with high level effect. The
congener with the highest quantity between these three congeners alpha, beta, delta- HCH is the
alpha-HCH congener. This one appears in a quantity almost as high as in water underling that it is
bioaccumulated as it is from water and it is less from gamma-HCH biodegradation. Anyway,
Lindane is the most toxic from the four analysed congeners, and that´s why its percentage from the
whole quantity has been followed. In fish, Lindane is only 26 %, but in plankton and bulrush the
percentage is 40 - 50 %. These quantities are different because of the different metabolism of the
analysed trophic levels. The more complex the organism metabolism is, the less HCH is
recovered. It seems that metabolism process leads not only to Lindane biodegradation, but to
complete release from organism. The phenomenon is repeated in a similar way but in smaller
percentage at organisms with simpler metabolism - plankton, bulrush (Table 10.6-11).
Table 10.6-11:
HCH accumulation in biocenoses [µg.g-1 x 10-3]
Trophic ring Sum of HCH alpha-HCH beta-HCH gamma-HCH delta-HCH
plankton
33 520
4 137
9 595
13 700
6 087
bulrush
11 440
5 480
80
5 880
0
fish
17 940
4 146
4 570
4 941
4 280
periphyton
53 580
46 980
1 360
380
4 860
4.52
0.75
2.32
0.91
0.54
water
HCH may be accumulated in bulrush, both from water and from sediments. That´s why,
different parts, the root and the bulrush leaves have different quantities of Lindane and HCH.
Although, in sediments, HCH quantities are usually one thousand times greater than in water, the
bulrush root has less than 50 % HCH, while the leaves have more than 50 % Lindane or HCH,
making easier concentration of those ones in fish because leaves are fish food while the root is not
(Table 10.6-12).
Table 10.6-12:
HCH spreading [%]
Trophic ring alpha-HCH beta-HCH gamma-HCH delta-HCH Sum of HCH
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bulrush root
51
0
44
0
47
bulrush leaves
49
100
56
0
53
fish tissue
38
49
38
49
43
fish organs
62
51
62
51
57
In a similar way, HCH distribution between tissue and organs (liver and bowels) in fish are
noticed. Lindane in tissue (the used part) presents only 38 % in comparison with the liver which
has an almost double Lindane load. Speaking about HCH (all congeners), the situation is more
serious because tissue has 43 % HCH. This figure is not really a surprise because the tissue
contains fatty layer, where beta and delta congeners are accumulated more than gamma congener
(Table 10.6-12).
Bioaccumulation factors in different rings of the trophic chain, characteristic to the studied
ecosystem for HCH and Lindane, are calculated (Table 10.6-13). Periphyton has the highest
bioaccumulation factor and this owns to the sampling place (from stones) which brings further
HCH quantities set on the surface through adsorption and not only to HCH absorbed through the
specific metabolism of the certain trophic ring. In decreased order, plankton followed by fish gives
the highest affinity for HCH. If the bioaccumulation factors values are followed, a ranking of HCH
bioaccumulation ability in the studied biocenoses (Table 10.6-13) can be established: periphyton >
plankton > fish > bulrush. Although HCH values are high enough, the third place for fish (the
upper ring) in this ranking proves the ability of this trophic level to release the toxic compound
through different methods.
Table 10.6-13:
Bioaccumulation factor (BCF) in trophic´s chain rings
BCFHCH
BCFLindane
plankton
7401
15055
macrophyte (bulrush)
2526
6462
nekton (fish)
3961
5430
periphyton
11830
418
Trophic rings
The selective bioaccumulation of HCH congeners reveals that plankton accumulates more than
40 % alpha HCH congener and about 30 % beta HCH congener. Bulrush doesn´t accumulate delta
HCH congener and some beta HCH congener, but it concentrates almost equal quantities of alpha
and gamma HCH (Lindane) congeners both in leaves and in roots. Fish accumulates in rather
unequal quantities the four congeners in organs and tissues. Periphiton concentrate almost 90 %
alpha HCH congener and only 9 % delta HCH congener. Fish, due to the high level of
accumulated HCH, are a real danger for man as food source. (alpha + beta) HCH quantities are
about 60 times bigger than the maximum allowed concentration limit for food and health (0.15 µg.
g-1) approved by actual acts, and for gamma HCH (Lindane) is 25 times more than the same limit.
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All the results reveal that organochlorine compounds are and will be in the short and middle future
a problem for Romanian environment.
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Persistent, Bioaccumulative and Toxic Chemicals in Central
and Eastern European Countries - State-of-the-art Report
Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
10.6.4 References
Asplund L., Jakobsson E., Haglund P., Bergman A. (1994): Chemosphere 28, 20752086.
Barrie L. A., Gregor D., Hargrave B., Lake R., Muir D., Shearer R., Tracey B.,
Bidleman T. F. (1992): Arctic contaminants. Sources, occurrence and pathways. Sci. Total
Environ. 122, 1-74.
Bengtson S.-A., Södergren A. (1974): DDT and PCB residues in airborne fallout and
animals in Iceland. Ambio 3, 84-86.
Bignert A., Gothberg A., Jensen S., Litzen K., Udsjo T., Olsson M., Reuthergardh L.
(1993): The need for adequate biological sampling in ecotoxicological investigations: a
retrospective study of twenty years pollution monitoring. Sci. Total Environ. 128, 121-139.
Borlakoglu J. T., Wilkins J. P. G., Walker C. H., Dils R. R. (1990): Polychlorinated
biphenyls in extracts from manx shearwaters. Bull. Environ. Contam. Toxicol. 45, 819-823.
Bruhn R., Kannan K., Petrick G., Schulz-Bull D. E., Duinker J. C. (1995):
Chemosphere 31, 3721-3732.
Eriksson G., Jensen S., Kylin H., Strachan W. M. J. (1989): The pine needle as a
monitor of atmospheric pollution. Nature 341, 42-44.
Falandysz J. (1984): Organochlorine pesticides and PCB in herring from the southern
Baltic, 1981. Z. Lebensm. Unter. Forsch. 179, 20-23.
Falandysz J. (1994): Polychlorinated biphenyls concentration in cod-liver oil: evidence of
a steady-state condition of these compounds in the Baltic area oils and levels noted in
Atlantic oils. Arch. Environ. Contam. Toxicol. 27, 266-271.
Falandysz J. (1998): Polychlorinated naphthalenes: an environmental update. Environ.
Pollut. 101, 77-90.
Falandysz J., Rappe C. (1996): Spatial distribution in plankton and bioaccumulation
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features of polychlorinated naphthalenes in a pelagic food chain in southern part of the
Baltic Sea. Environ. Sci. Technol. 30, 3362-3370.
Falandysz J., Yamashita A., Tanabe S., Tatsukawa R. (1992): Isomer-specific analysis
of PCBs including toxic coplanar isomers in canned cod livers commercially processed in
Poland. Z. Lebensm. Unters. Forsch. 194, 120-123.
Falandysz J., Kannan K., Tanabe S., Tatsukawa R. (1994a): Organochlorine pesticides
and polychlorinated biphenyls in cod-liver oils: North Atlantic, Norwegian Sea, North Sea
and Baltic Sea. Ambio 23, 288-293.
Falandysz J., Kannan K., Tanabe S., Tatsukawa R. (1994b): Concentrations, clearence
rates and toxic potential of non-ortho coplanar PCBs in cod liver oil from the southern
Baltic Sea from 1971 to 1989. Mar. Pollut. Bull. 28, 259-262.
Falandysz J., Yamashita A., Tanabe S., Tatsukawa R., Ručinska L., Mizera T.,
Jakuczun B. (1994c): Congener-specific analysis of polychlorinated biphenyls in whitetailed sea eagles Haliaeetus albicilla collected in Poland. Arch. Environ. Contam. Toxicol.
26, 13-22.
Falandysz J., Yamashita N., Tanabe S., Tatsukawa R., Ručinská L., Skóra K. (1994d):
Congener-specific data on polychlorinated biphenyls in tissue of common porpoise from
Puck Bay, Baltic Sea. Arch. Environ. Contam. Toxicol. 26, 267-272.
Falandysz J., Strandberg L., Berqvist P.-A., Kulp S. E., Strandberg B., Rappe C.
(1996): Polychlorinated naphthalenes in sediment and biota from the Gdaňsk Basin. Baltic
Sea. Environ. Sci. Technol. 30, 3266-3274.
Falandysz J., Florek A., Stranddberg L., Strandberg B., Berqvist P.-A., Rappe C.
(1997a): PCDDs and PCDFs in Biota from the Southern part of the Baltic Sea.
Organohalogen Compounds 32, 167-171.
Falandysz J., Strandberg B., Danisiewicz D., Strandberg L., Berqvist P.-A., Rappe C.
(1997b): Spatial distribution of DDT, HCBz and PCBz in plankton in the southern part of
Baltic Proper. Organohalogen Compounds 32, 349-353.
Falandysz J., Danisiewicz D., Strandberg L., Strandberg B., Berqvist P.-A., Rappe C.
(1997c): DDTs, HCBz and PCBz in Stickleback from various sites in the Gulf of Gdaňsk.
Organohalogen Compounds 32, 353-357.
Falandysz J., Dembowska A., Strandberg L., Strandberg B., Berqvist P.-A., Rappe C.
(1997d): Congener-specific data of PCBs in some species of fish from the Gulf of Gdaňsk,
Baltic Sea. Organohalogen Compounds 32, 358-363.
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Falandysz J., Dembowska A., Strandberg L., Strandberg B., Berqvist P.-A., Rappe C.
(1997e): Chlorobiphenyls in Baltic plankton. Organohalogen Compounds 32, 364-369.
Falandysz J., Danisiewicz DD., Strandberg L., Strandberg B., Berqvist P.-A.,Rappe C.
(1997f): Pentachlorobenzene, HCB and DDTs in apelagic food chain in the Baltic Sea.
Organohalogen Compounds 32, 370-373.
Falandysz J. (1997g): Bioaccumulation and biomagnification features of polychlorinated
naphthalenes. Organohalogen Compounds 32, 374-379.
Falandysz J., Strandberg B., Strandberg L., Berqvist P.-A., Rappe C. (1998a): Spatial
distribution of TCPM-H and TCPM-OH in blue mussels and fish from the Gulf of Gdaňsk,
Baltic Sea. Bull. Environ. Contam. Toxicol. 61, 411-418.
Falandysz J., Strandberg B., Strandberg L., Berqvist P.-A., Rappe C. (1998b):
Concentrations and spatial distribution of chlordanes and some other cyclodiene pesticides
in Baltic plankton. Sci. Total Environ. 215, 253-258.
Falandysz J., Strandberg B., Strandberg L., Rappe C. (1999): Tris(4-chlorophenyl)
methane and tris(4-chlorophenyl)methanol in sediment and food webs from the Baltic South
Coast. Environ. Sci. Technol. 33, 517-521.
Falandysz J., Strandberg B., Strandberg L., Bergqvist P.-A., Rappe C. (1999):
Cyclodiene pesticide residues in molluscs, crustaceans and fish in the Gulf of Gdaňsk,
Baltic Sea. Organohalogen Compounds, 43, 147-151.
Falandysz J., Strandberg L., Strandberg B., Bergqvist P.-A., Rappe C. (2000):
Pentachlorobenzene and hexachlorobenzene in fish in the Gulf of Gdańsk. Pol. J. Environm.
Stud. 9, in press.
Forget G. (1991): Pesticides and the third world. J. Toxicol. Environ. Hlth. 32, 11-31.
Goldberg E. D. (1991): Halogenated hydrocarbons. Past, presence and near-future
problems. Sci. Total Environ. 100, 17-28.
Gregor P., Hajšlová J. (1998): Planar PCBs in selected freshwater fish from Czech
Republic. Ogranohalogen Compounds 39, 249-252.
Giesy J. P., Jude D. J., Tillitt D. E., Gale R. W., Meadows J. C., Zajicek J. L.,
Peterman P. H., Verbrugge D. A., Sanderson J. T., Schwartz T. R., Tuchman M.
(1997): PCDDs/Fs, PCBs and 2,3,7,8-TCDD equivalents in fishes from Saginaw Bay.
Michigan. Environ. Toxicol. Chem. 16, 713-724.
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Gutleb A. C., Kranz A. (1998): Estimation of PCBs levels in livers of the otter (Lutra
lutra) from concentrations in scats and fish. Water, Air and Soil Pollut. 106, 481-491.
Hajšlová J., Schoula R., Kocourek V., Holadová K., Poustka J., Kohoutková J.,
Svobodová Z. (1997): Polychlorinated biphenyls and other persistent chlorinated
contaminants in fish as indicators of pollution of aquatic ecosystem in Czech Republic.
Toxicol. Environ. Chem. 59, 279-291.
Hajšlová J., Gregor P., Chládková V., Alterová K. (1998): Musk compounds in fish from
Elbe River. Organohalogen Compounds 39, 253-256.
HELCOM (1996): Third periodic assessment of the state of the marine environment of the
Baltic Sea, 1989-1993; background document. Baltic Sea Environment Proceedings, No.
64B. Helsinki Commission Baltic Marine Environment Protection Commission.
Jarman W. M., Simon M., Norstrom R. J., Burns S. A., Bacon C. A., Simoneit B. R. T.,
Risebrough R. W. (1992): Global distribution of tris(4-chlorophenyl)methanol in high
trophic level birds and mammals. Environ. Sci. Technol. 26, 1770-1774.
Järnberg U., Asplund L., de Wit C., Egeback, A.-I., Widequist U., Jakobsson E.
(1997): Distribution of polychlorinated naphthalene congeners in environmental and sourcerelated samples. Arch. Environ. Contam. Toxicol. 32, 232-245.
Kanan K., Falandysz J., Yamashita A., Tanabe S., Tatsukawa R. (1992): Temporal
trends of organochlorine concentrations in cod-liver oil from the southern Baltic proper,
1971-1989. Mar. Pollut. Bull. 24, 358-363.
Kannan K., Tanabe S., Borell A., Aguilra A., Focardi S., Tatsukawa R. (1993): Isomerspecific analysis and toxic evaluation of polychlorinated biphenyls in strped dolphins
affected by an epizootic in the western Mediterranean Sea. Arch. Environ. Contam. Toxicol.
25, 227-233.
Kočan A., Petrik J., Drobná B., Chovancová J., Jursa S., Pavúk M., Kovrižnych J.,
Langer P., Bohov P., Tajtaková M., Suchánek P. (1999): The environmental and human
load in the area contaminated with polychlorinated biphenyls. Prepared by Institute of
Preventive and Clinical Medicine, Bratislava, Slovakia for Ministry of the Environment,
Slovakia, February, 240 pp.
Parkerton T. F., Connolly J. P., Thomann R. V., Uchrin C. G. (1991): Do aquatic
effects or human health endpoints govern the development of sediment-quality criteria for
non-ionic organic chemicals ? Int. Toxicol. Chem. 12, 507-523.
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Picer M., Picer N. (1994): Levels and long-term trends of some high molecular chlorinated
hydrocarbons in mussels collected from the Western Istrian coastal waters - Northern
Adriatic. Chemosphere 1994:26:
Picer M., Picer N. (1995): Levels and long-term trends of polychlorinated biphenyls and
DDT in bivalves collected from the south Adriatic coastal waters. Chemosphere 30, 31-38.
Roots O., Aps R. (1993): Polychlorinated biphenyls and organochlorine pesticides in Baltic
herring and sprat. Toxicol. Environ. Chem. 37, 195-205.
Roots O., Talvari A. (1997): Bioaccumulation of toxic chloroorganic compounds and their
isomers into the organism of Baltic grey seal. Chemosphere 35, 979-985.
Roots O., Talvari A. (1999): Bioaccumulation of toxic organic compounds and their
isomersinto the organism of seals in West-Estonian Archipelago biosphere reserve. Environ.
Monitor. Assessm. 54, 301-312.
Roots O (1995): Organochlorine pesticides and polychlorinated biphenyls in the ecosystem
of the Baltic Sea. Chemosphere 31, 4085-4097.
Roots O. (1996): Toxic chloroorganic compounds in the ecosystem of the Baltic Sea.
Ministry of the Environment of Estonia. Environment Information Centre (EEIC). Tallinn,
Estonia, 144 pp.
Roots O. (1998): Biogeomonitoring of toxic chloroorganic compounds in the ecosystem of
the Baltic Sea. Ecological Chem. 7, 55-64.
Roots O. (1999a): Persistent, bioaccumulative, toxic chemicals in the ecosystem of the
Baltic Sea (Estonian data). Proceedings of extended abstracts of 27th ACS National
Meeting, Division of Environmental Chemistry. Anaheim, CA, USA, March 21-25, 1999,
165-167.
Roots O. (1999b): Did natural changes save the grey seal of the Baltic Sea ? Hypothesis or
reality. Toxicol. Environ. Chem., 69, 119-131.
Sjőásen T., Ozolins J., Greyerz E., Olsson M. (1997): The otter (Lutra lutra) situation in
Latvia and Sweden related to PCB and DDT levels. Ambio 26, 196-201.
Toader C., Chitimiea, S. (2000): HCH bioacumulation in Babeni Lake biocenoses. C.
Europ. J. Occup. Hlth, in press.
Zook D. R., Buser H.-R., Bergqvist P.-A., Rappe C., Olsson M. (1992): Detection of tris
(4-chlorophenyl)methane and tris(4-chlorophenyl)methanol in ringed seal (Phoca hispida)
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from the Baltic Sea. Ambio 21, 557-560.
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Persistent, Bioaccumulative and Toxic Chemicals in Central
and Eastern European Countries - State-of-the-art Report
Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
10.7 Terrestrial wildlife
The levels and effects of PBT compounds are studied also in terrestrial ecosystem. A
large amount of data on PCBs and chlorinated pesticides contamination in biological
material, especially in the bird tissues, has been published. The main reason for
performance of these studies was the fact that a sudden decrease in populations of prey
birds had occurred. This effect was given to relationship with the high concentrations of
organochlorines in the birds´ bodies. These high levels of PCBs, DDTs and other pollutants
can bioaccumulate and have effects on bird reproduction.
The concentrations of organochlororine insecticides and PCBs were measured in eggs,
brains, livers, carcasses and stomac contents (wet weight) and lipids of house sparrow
(Passer domesticus) and tree sparrow (Passer montanus) nestlings in 1988-1989, and in
1995 only in brains of mature and one-year birds (Niewiadowska et al., 1998). The study was
conducted in suburban areas of Warshaw characterized by small farms and houses
surrounded by gardens and fields. These fields were treated with DDT in 1950s and 1960s.
In Poland concentrations of DDT and its derivatives in animal tissues have declined 10-20
fold since 1975. It was widely used in years 1955-1975 to fight against the Colorado beetle.
It was banned from retail trade in 1971 and withdrawn from use by 1974.
The concentrations of chlorinated hydrocarbons observed in the brains of the fledged
sparrows captured in 1995 differed from those recorded in the brains of the nestlings taken
from the same suburban area in 1988-1989. Gamma HCH was completely absent in
sparrows in 1995, but were always present in detectable levels (but low concentration, up to
0.039 mg.g-1, mean 0.006-0.019 mg.g-1) in birds taken at the earlier period. Minimal
concentrations of PCBs were detected in only 4 birds out of 27 (mean 0.003 mg.g-1, max
0.022 mg.g-1) in 1995, but were always present and often at high concentrations in both the
brains (range between 0.321 and 36.426 mg.g-1 for tree sparrows and between 0.328 and
191 mg.g-1 for house sparrows) and carcasses of nestlings of the two species captured in the
years 1988-1989. The food ingested by birds, irrespective of its composition, contained
significantly smaller amounts of PCBs in 1995 compared to the previous sampling period.
The recorded concentrations of p,p´-DDE in the brains of sparrows of the two species
taken in 1995 were not as high as in 1988-1989. But after elimination of individuals with
exceptionally high levels of this compound were concentrations of p,p´-DDE rather stable
in the brains and carcasses of all the analysed birds regardless of the year (total means
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0.035 - 0.916 mg.g-1, max 0.09 - 1.544 mg.g-1).
The observed differences in the contamination of birds by organochlorine pesticides
may be ascribed to land-use changes during 1989-1995, i.e. decline in the area of cultivated
fields.
In Poland DDT had been withdrawn from use by 1975. Limitations and then ban on the
use of lindane (gamma-HCH) were only introduced in the period 1980-1989.
Concentrations of DDT and its derivatives in animal tissues have declined 10-20 fold since
1975, but are still widely present in the tissues of livestock and wild animals, as well as in
human fat and milk.
The contamination of whole bodies and brains of house sparrow (Passer domesticus)
and tree sparrow (Passer montanus) as indicators of contamination with organochlorine
pesticides and PCBs were studied in rural and suburban areas near Warshaw (Pinowski et al.,
1999). Between 1950s and 1975, both study areas were treated with DDT in an efford to
combat the Colorado beetle.
The samples were divided into three groups: 1) samples with no residues of
organochlorine compounds; 2) samples with concentration the maximal residue limit
(MRL); and 3) samples with concentrations higher than the MRL. The values for the MRL
were greatest residual concentrations permissible in Polish law, which were taken from
Dziennik Ustaw No. 43, item 273 from 1997, while in the case of PCBs, the proposed
permissible value of 0.5 ppm was adopted. HCB and alpha-HCH and gamma-HCH were
present at concentrations bellow the MRL in all samples. p,p´-DDE residues were detected
in all the birds, concentrations exceeded the MRL in all the suburban birds and in almost
three quarters of those from agricultural areas. p,p´-DDD and p,p´-DDT residues were
present in all samples from the suburban area and in most samples from the agricultural
areas, albeit at sub-MRL levels. PCBs were found in all samples, but the MRL was only
exceeded in 2 females from agricultural areas.
The mean concentrations of HCB, p,p´-DDE and p,p´-DDD in lipids were greater in
birds from the suburban area (means 0.008, 13.2 and 0.053 ppm lipid fraction) than from
the true rural areas (means 0.003, 2.82 and 0.009 ppm lipid fraction). There was no
significant difference for p,p´-DDT, alpha-HCH and PCBs, the concentrations of gammaHCH were on average higher in the rural than in the suburban area. All the studied samples
of lipids from House Sparrows were found to contain PCB congeners, the highest
concentrations were noted for PCB 153, 138 and 180. Significant differences between the
suburban and rural areas were only found for the PCB 28 congener, did not occur in
sparrows from the former and 201, whose concentrations were ca. 50 % higher in sparrows
from the suburban area.
From the organochlorine pesticides only p,p´-DDE was measurable in all brain samples
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(higher in the suburban area) and p,p´-DDD in brains from suburban area. 51 % of the
brains of house sparrows and 67 % of the brains of tree sparrows were not found to contain
PCB congeners. p,p´-DDE was found in all tree sparrow brains (conc. 0.018 - 0.168 ppm).
The concentrations of all pesticides were greater in the lipid of males from a given area,
as opposed to females, this difference was statistically significant for HCB and alpha-HCH.
Also the concentrations of p,p´-DDE and p,p´-DDD (in house sparrows) in brain were
higher in males than females. Lower concentrations in females can be partly explained by
excretion of lipid-soluble toxins together with eggs.
The PCB concentrations in sparrow brains in period 1994-1995 (0.001 - 0.005 ppm)
were less than one-hundredth of those noted in the years 1988-1989 (2.739 - 2.797 ppm).
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Persistent, Bioaccumulative and Toxic Chemicals in Central
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Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
10.7.1 References
Niewiadowska A., Barkowska M., Juřicova Z., Literák I., Pinowski J., Pinowska B.,
Romanowski J. (1998): Chlorinated aromatic hydrocarbons in the brains of sparrows
(Passer domesticus, Passer montanus) from suburban areas of Warsaw. Proc. Latvian Acad.
Sci., Section B, Vol. 52. Supplement.
Pinowski J., Niewiadowska A., Juricova Z., Literak I., Romanowski J. (1999):
Chlorinated aromatic hydrocarbons in the brains and lipids of sparrows (Passer domesticus
and Passer montanus) from rural and suburban areas near Warshaw. Bull. Environ. Contam.
Toxicol. 63, 736-743.
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Persistent, Bioaccumulative and Toxic Chemicals in Central
and Eastern European Countries - State-of-the-art Report
Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
10.8 Vegetation
Many recent studies have used vegetation which bioaccumulates organic pollutants for
monitoring studies (Larsen et al., 1985; Reischl et al., 1989; Moser et al., 1991; Kylin 1994;
Simonich and Hites, 1995). Vegetation has been used to indicate ubiquitous pollutant
contamination levels. In order to determine the general contamination level of cities,
countries, and continents, many samples from variety of locations are required in order to
minimise the effect of point sources and overcome the inherent variability of samples from
the same size.
The mechanism of vegetation uptake of organic pollutants is governed by the chemical
and physical properties of pollutant (such as their molecular weights, aqueous solubilities,
and vapour pressures), environmental conditions (the atmospheric temperature), and the
plant species and structure (Simonich and Hites, 1995). Vegetation can be used to
qualitatively indicate organic pollutant atmospheric contamination levels as long as the
mechanism of accumulation is considered. Vegetation has been used to identify point
sources of pollutants and to determine regional and global contamination patterns.
There are several pathways through which organic pollutants enter vegetation. The
pollutant may enter the plant by partitioning from contaminated soil to the roots and be
translocated in the plant by the xylem. Organic pollutants may also enter vegetation from
the atmosphere by gas-phase and particle-phase deposition onto the waxy cuticle of the
leaves or by uptake through the stomata and be translocated by the phloem.
These pathways are a function of (a) the chemical and physical properties of the
pollutant, such as its lipophilicity, water solubility, vapour pressure (which controls the
vapor-particle partitioning), and Henry´s law constant; (b) environmental conditions, such
as ambient temperature and the organic content of the soil; and (c) the plant species, which
controls the surface area and lipids available for accumulation.
Many researchers have used pollutant concentrations in vegetation to qualitatively
indicate atmospheric contamination levels. Vegetation integrates contamination over time,
and vegetation samples are much easier to collect than air samples, especially in remote
locations. Vegetation has been used to identify point sources of organic pollutants, to
determine regional contamination within cities, countries, and continents, and to determine
the global contamination of organic pollutants (Simonich and Hites, 1995).
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Many studies have monitored the atmospheric deposition of both heavy metals and
organic pollutants by epiphytic mosses (Oehme et al., 1985). Mosses do not have a root
system, so that the uptake of nutritive substances and pollutants therefore occurs exclusively
via the atmosphere. The annual rate of growth is easily detectable, which allows the
determination of air pollutants collected during one growth period.
Vegetation has been used to indicate ubiquitous pollutant contamination levels. In order
to determine the general contamination level of cities, countries, and continents, many
samples from a variety of locations are required in order to minimize the effect of point
sources and overcome the inherent variability of samples from the same site.
This paper describes a study in which moss and pine needle samples were collected
from the field sites of Project TOCOEN (Holoubek et al., 1990a) - from the surroundings of
two industrial factories (The Coal and Gas Fuel Company Vřesová - in the period 19911993, TOCOEN study area No. 10 - see Chapter 9.3.4, and DEZA Valašské Meziříčí - 19901991, TOCOEN study area No. 5 - see Chapter 9.3.3) and from a background site at the
Košetice observatory (1988 - up to date, TOCOEN study area No. 3 - see Chapter 9.3.2).
The Košetice observatory of the Czech Hydrometeorological Institute was established as
a regional station of the integrated background monitoring network of the United Nations
Environmental Programme (UNEP) project Global Environmental Monitoring System
(GEMS). The observations were launched at the end of the 1970s, the building of the
observatory was completed in 1988 (Váňa et al., 1997).
The major local source of PAHs is the Corporation DEZA Valašské Meziříčí (No. 5)
(Holoubek et al., 1991). Crude tar and benzene are processed by the manufacturing plant of
DEZA and a rich assortment of products results. Crude benzene processing yields pure
benzene, pure and varnish toluene, xylene, and solvent naphtha. Tar distillation produces
road tar for road surfaces and tar being used as a binding agent in the building industry. A
large number of fractions are semi-finished products, which are transferred from the tar
distillation department to another manufacturing department, e.g. to the department
producing pure anthracene. Another manufacturing department, which produces technical
naphthalene supplies the phthalic anhydride manufacture with initial material. Phthalic
anhydride is a parent material for dioctyl phthalate which is used as a plasticizer. Oil
furnace black is also produced in significant quantities in 37 sampling sites were establishe
for the collection of air, sediments, soils, earthworms, needles, mosses and aquatic biota.
The measurements were started in 1989.
The Coal and Gas Fuel Company Vřesová is situated in the Sokolov coal basin between
the cities Karlovy Vary and Sokolov (No. 10). This company carries out lignite mining in
this part of the coal basin and produces briquettes, city gas, power, heat, tar, crude benzene,
phenol concentrate, liquid ammonia and other products. The Company is an important
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producer of fuels and power, which enables the company to contribute to the improvements
of the social and economic life of the region. On the other hand, the Company has the
negative effects, the worst are the ecological ones resulting from the concentration of
different industrial activities in a relatively small area. The surroundings of the Company
have been selected as a study site No. 10 - a source of PAHs. Measurements here were
started in 1991. Twenty-one sampling sites were established around this facility for the
collection of air, sediments, soils, earthworms, needles, mosses and aquatic biota.
Mosses (Hypnum cuprresiforme L. ex Hedw.) and pine needle (Pinus silvestris) samples
were collected at the area of observatory Košetice (5 sampling sites for mosses and 6 sites
for needles), in the surroundings of DEZA Valašské Meziříčí (5 and 8 sampling sites), and
the Coal and Gas Fuel Company Vřesová (9 and 6 sampling sites) (Holoubek et al., 1990b;
Holoubek et al., 1991). Samples from the observatory Košetice were collected annually from
the year 1988, while samples from the surroundings of factories were collected during the
years 1989-1991 in the case of DEZA Valašské Meziříčí and during the years 1991-1993 in
the case of the Coal and Gas Fuel Company Vřesová (annually again).
The moss samples were collected on the ground outside the crown projection of trees.
Pine needles (3 years old) were collected in the same way and wrapped in aluminium foil,
air-dried at ambient temperature and stored in paper and sealed polyethylene bags in the
dark, at room temperature until analysis. Mosses and pine needles from the observatory
Košetice, were analyzed for PAHs, PCBs and organochlorinated pesticides (OCPs), mosses
and pine needles from the surroundings of companies in Vřesová and Valašské Meziříčí,
resp., were analyzed for PAHs only.
Regional and local observations of PAHs levels in the Czech Republic
The mean and range concentrations of PAHs measured in moss and pine needle samples
at each site are reported in Tables 10.8-1 and 10.8-2. Typical mixtures of PAHs are shown
for each sampling area in Figure 10.8-1 - 10.8-3.
The Sum of PAHs content in mosses ranged from < 0.3 to 4 700 ng.g-1 dry weight
(mean value 609) in the background site (TOCOEN study area No. 3). Concentrations were
elevated above this range at the industrial sites: 229 to 10 222 ng.g-1 (mean value 3 060) in
TOCOEN study area No. 5, and < 0.3 to 16 730 ng.g-1 (mean value 3 670) in study area
No. 10.
Acenaphthene, anthracene, chrysene, and indeno[1,2,3-c,d]pyrene dominated the PAHs
burden of samples from the background sampling sites. In contrast naphthalene, fluorene,
phenanthrene, fluoranthene, benzo[a]anthracene, chrysene, benzo[b]fluoranthene and benzo
[a]pyrene dominated near the local source in study area No. 3 and acenaphthylene,
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acenaphthene, benzo[a]pyrene, indeno[1,2,3-c,d]pyrene, and benzo[g,h,i]perylene near the
local source in study area No. 10.
The Sum of PAHs content in pine needles ranged from < 0.3 to 18 590 ng.g-1 dry
weight with (mean value 1 345) at background site and from < 0.3 to 16 733 ng.g-1 (mean
value 5 731) and from 85 to 19 251 ng.g-1 (mean value 8 325) at the two industrial sites.
The mixtures of PAHs were rather different in the needles compared to the mosses as
shown in Figure 10.8-2.
Since the exposure time for both mosses and pine needles is practically same, the
differences between their mixtures presumably reflects differences in the relative
importance of compound capture from the atmosphere.
A study of the spatial distribution and mixture of PAHs in pine needles sampled across
the UK (Tremolada et al., 1996) showed that phenathrene was the predominant compound in
PAH mixtures. This predominance was not observed in needles from CR. The detection of
PAHs in all of the PAHs analysed in the moss and needle samples from those regional
background site can be - similarly as for example in UK (Tremolada et al., 1996) - interpreted
as evidence for widespread diffusive PAH contamination throughout the troposhere, which
is supplemented in some areas by elevated inputs. Evidence for widespread diffusive inputs
and environmental occurrence of PAHs in both countries (CR and UK) has been published
previously (Holoubek et al., 1990b; Holoubek et al., 1991; Tremolada et al., 1996).
Near the local sources in study areas 3 and 10, the moss and pine needle samples were
collected on four transects, along the main wind directions. The distance between points on
the transects was variable, depending on the occurrence of mosses and needles. Four
transects for mosses and two for pine needles were used in the surroundings of the source in
area 3 and two for mosses and pine needles transects were used in area 10. These two
sampling areas have different types of PAHs contamination. The source in area 3 is
typically a point source and dominant as a source of PAHs in this area. The main
contamination is close to the factory and decreased with distance from the source. The
source in area 10 is located in the very heavily polluted region of the North Bohemia (the
western part of the so called Black Triangle), with many industrial sources of pollution
(electric power plants, chemical industry, coal mining system, traffic.) and here PAH
contamination of moss and needle samples is more "diffusive". Concentrations do not
decrease with distance from the observed source up to distance of 15 km.
Regional observations of OCPs and PCBs levels in the Czech Republic
reports means and ranges of OCPs and PCBs in mosses and pine needles
from the background area. The HCB content in mosses from the background area ranged
Table 10.8-3
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from < 0.1 to 18 ng.g-1 (mean value 1.6) and from < 0.1 to 6 ng.g-1 (mean value 2.63) in the
needles. In the case of gamma-HCH in mosses from these sampling sites, the range was
from < 0.1 to 5.9 ng.g-1, with a mean value of 1.28 ng.g-1, and in the case of needles ranged
from < 0.1 to 9.2 with a mean value 1.98 ng.g-1 dry weight. DDT and its metabolite DDE
were detected only in the moss samples and ranged from < 0.1 to 6.8 ng.g-1 (mean = 1.14)
and from < 0.1 to 0.4 ng.g-1 (mean = 0.15) (DDE), respectively.
The selected PCB congeners (28, 52, 101) were detected in moss samples in the range
from < 0.1 to 0.6; 0.3 and 0.2 ng.g-1 dry weight, respectively, with mean values of 0.17;
0.18 and 0.09 ng.g-1 dry weight.
A series of papers by Kylin and co-workers (Kylin et al., 1994; Strachan et al., 1994;
Eriksson et al., 1989; Jensen et al., 1992) has outlined the use of Scots pine (P. Sylvestris L.)
needles to determine the regional contamination of organochlorines in Europe. Jensen et al.,
(1992) collected pine needles from France, Switzerland, Germany, Denmark, Poland,
Czechoslovakia, Sweden, and Norway in 1986 and analysed them for chlorinated pesticides
and PCBs. They tracked elevated DDT concentrations in needles to the use of DDT in the
former East Germany, while most HCHs, PCBs, and HCB were ubiquitous throughout
Europe. However, the concentrations of pentachlorophenol were elevated in needles from
Sweden, and lindane was elevated in samples from southern France.
These researchers collected needles again in 1989 from some of the same sites and
analyzed them for the same compounds (excluding PCBs) (Strachan et al., 1994). The results
were similar to the previous study. Lindane concentrations in needles decreased slightly
from the south to north, while the concentrations of alpha-HCH and HCB were uniform
throughout the sites. The ratio of DDT to DDE decreased from south to north, and the
concentrations of PeCP in north Sweden samples remained high. This study also showed
that sampling at a consistent height within the tree is preferred, that there is no difference in
needle pollutant concentration of trees facing different directions, and that the age of the
tree does not influence the needle pollutant concentration.
used pine needles to determine regional contamination of DDT,
HCHs and HCB in Europe. Samples were collected from Italy, Holland, Austria,
Czechoslovakia, Finland, and Greece. The measured needle organochlorine concentrations
were compared to previous studies in other European countries. These authors suggested
that the organochlorine distribution pattern, or "fingerprint", in pine needles from a given
country is dependent on use of the compounds in that country and on its socioeconomic
conditions.
Calamari et al. (1994)
shows the organochlorine insecticide concentrations in needles from some
of the countries investigated by Calamari et al. (1994) compared to the background
observatory Košetice. There is a wide range in organochlorine concentrations among the
Figure 10.8-4
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countries. The Figure shows that parts of former Czechoslovakia (southwest Slovakia) was
the most contaminated of those sampled, while the Košetice background region (CR) and
Finland were much less contaminated.
The Czech and Greece fingerprints were not characterised by any particular insecticide,
while the Finland was relatively high on alpha-HCH and the Italy was characterised by high
p,p´-DDT.
Although most of these studies analysed a relatively small number of vegetation
samples collected from a limited number of sampling sites, they show that vegetation can be
used as an indicator of regional contamination levels.
Table 10.8-4 compares recently published data with data from this current study for the
Czech Republic.
Table 10.84:
Compounds
The comparison of concentrations [ng.g-1] of selected
chlorinated pesticides and PCB congeners in the wax
of the needles
Finland 1
Germany 2
UK 3
CR 4
alpha-HCH
0.46 - 1.93
< 0.1 - 1.4
gamma-HCH
0.40 - 1.71
< 0.1 - 9.2
HCB
0.21 - 0.73
< 0.1 - 6
PCB 28
0.48 - 27.03
0.21 - 25.56
< 0.1
PCB 52
0.46 - 13.05
0.42 - 5.73
< 0.1
PCB 101
0.47 - 12.05
2.17 - 5.38
< 0.1
Sum of PAHs
19 - 3 090
1
The vicinity of metal reclamation plant (Sinkkonen et al., 1995)
2
The vicinity of the Ruhr industrial area (Strachan et al., 1994)
< 0.3 - 19 251
3
Study of spatial distribution of PAHs in UK atmosphere using pine needles
(Tremolada et al., 1996)
4
This study
As Lead and co-workers clearly described (Lead et al., 1996), the various plant species
are ideal biomonitors. They play an important role in the global cycling of POPs since they
cover over 80 % of the earth´s land surface, the surface area of plants is generally much
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greater than the area of the ground they cover, and the vegetation has a high lipid fraction
which is likely to accumulate lipophilic persistent organic compounds.
The collection of mosses and pine needles for determination of airborne persistent
organic pollutants is a suitable technique for monitoring of these compounds. Mosses are
suitable for these three reasons and also because they depend entirely on the atmosphere for
delivery of nutrients and lack both cuticle and internal transport mechanisms. The waxy
surface of the pine needles traps gaseous airborne pollutants and also traps particulates and,
thus, pollutants associated to the particles to a certain extent (Kylin et al., 1994).
Epiphytic mosses and conifer needles have been used for monitoring both local and
regional distribution of POPs. They can be particularly useful for identifying of unknown
point sources of pollutants as shown recently by Hermanson and Hites, (1990) for the
determination of historical PCBs contamination (Wagrowski and Hites, 1997) and for PCDD/
F contamination from pentachlorophenol wood preserving factories (Safe et al., 1992). All
these studies indicate that vegetation can be used to pinpoint local pollutant sources.
The results of this study can be interpreted in terms of regional use, and the collection of
mosses and pine needles can be readily and repeatedly done from trees in a given location
(Strachan et al., 1994). In the case of PAHs, mosses reflect more the differences between
background locality and polluted areas, suggestive of continuing / ongoing sources of these
compounds.
Acknowledgements
The research was supported by funds from the Czech Ministry of the Environment (Project
VaV 340/2/96), Czech hydrometeorological Institute, DEZA Valašské Meziříčí, Coal and Gas Fuel
Company Vřesová, Grant Agency CR (Project No. 511/95/10/60), and Project TOCOEN and was
performed as a part of research programme of European Scientific Foundation (ESF) Research network on
Persistent, Bioaccumulative and Toxic Chemicals.
The study of the pathway of benzo(a)pyrene (BaP) migration from bulk deposition to
soil and vegetation, with special emphasis on the forest ecosystem, was performed in
Lithunia (Milukaite, 1998). BaP uptake from the soil by vegetation was studied. The uptake
of BaP by vegetation occurs mostly by the soil-roots-leaves and is related to BaP
concentrations in soil. Plants of different species assimilate BaP from the soil in different
efficiencies. The partition coefficient of BaP among the roots and soil is 10-25 times higher
than that of leaves and soils for some plants (Agrostis vulgaris), whereas in others the
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concentrations in flowers, leaves and roots were similar (Thymus serpyllum).
High concentrations of BaP were determined in various organs of Scots pine (Pinus
silvestris) growing at 20 m from the highway with traffic intensity of about 1 000 vehicles
per hour. A BaP concentration of 87 µg.kg-1 was measured in pine bark, this concentration
is about 2 times higher than in the needles and 10 times higher than in the wood. Different
concentrations of BaP in various organs of pine may be explained by different contents of
lipids in various organs of pine. A concentration of 24.3 µg.kg-1 BaP was observed in
needles at a distance of 200 m from the road and between 103 and 280 µg.kg-1 closed to the
road (up to 10 m).
Mosses accumulate BaP and may be used for quantitative evaluation of BaP deposition
during the warm season of the year. Low concentration of BaP in the forest soil and a high
partition coefficient between moss and soil (Kp = 4) suggest that moss may accumulate
directly from the atmosphere. The long residence time (3-5 years) allows moss to
accumulate high quantities of BaP. The concentrations of BaP in moss samples varied from
3.1 µg.kg-1 to 896 µg.kg-1. Concentrations between 10 - 50 µg.kg-1 were observed in more
than 50 % of all moss samples from Lithuania.
To determine BaP stability in moss, BaP concentrations in various parts of moss were
measured. A flux of up to 2 µg.m-2mo-1 occur over more than 50 % of the Lithuanian
territory, greater flux was observed near the large towns (Vilnius, Kaunas, Šiauliai), the
seaport of Klaipeda, and the regions of Kedainiai and Jonava, where the fertiliser industry is
developed.
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Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
10.8.1 References
Calamari D., Tremolada P., Di Guardo A., Vighi M. (1994): Chlorinated hydrocarbons
in pine needles in Europe: Fingerprint for the past and recent use. Environ. Sci. Technol. 28,
429-434.
Eriksson G., Jensen S., Kylin H., Strachan W. M. J. (1989): The pine needle as a
monitor of atmospheric pollution. Nature 341, 42-44.
Hermanson M. H., Hites R. A. (1990): PCBs in tree bark. Environ. Sci. Technol. 24, 666671.
Holoubek I., Houšková L., Šeda Z., Holoubková I., Kott F., Kořínek P., Čáslavský J.,
Boháček Z., Bezačinský M., Mikeš C., Horák M., Kočan A., Petrik J. (1990a): Project
TOCOEN. The fate of selected organic compounds in the environment - Part I.
Introduction. Toxicol. Environ. Chem. 29, 9-17.
Holoubek I., Houšková L., Šeda Z., Holoubková I., Kořínek P., Boháček Z., Čáslavský
J. (1990b): Project TOCOEN. The fate of selected organic compounds in the environment Part IV. Soil, earthworms and vegetation 1988. Toxicol. Environ. Chem. 29, 73-83.
Holoubek L., Houšková L., Šeda Z., Kaláček J., Štroufová Z., Vančura R.,
Holoubková I., Kořínek P., Boháček Z., Čáslavský J., Kuběna O., Vrtělka V., Vala J.
(1991): Project TOCOEN. The fate of selected organic compounds in the environment Part V. The model source of PAHs. Preliminary study. Toxicol. Environ. Chem. 29, 251260.
Jensen S., Ericsson G., Kylin H., Strachan W. M. J. (1992): Atmospheric pollution by
persistent organic compounds: monitoring with pine needles. Chemosphere 24, 229-245.
Kylin H. (1994): Airborne Lipophilic Pollutants in Pine Needles. Doctoral Disertation.
Environmental Chemistry, Wallenberg Laboratory Stockholm University, Stockholm,
Sweden.
Kylin H., Grimvall E., Ostman C. (1994): Environmental monitoring of PCBs using pine
needles as passive samplers. Environ. Sci. Technol. 28, 1320-1324.
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Larsen B. R., Lokke H., Rasmussen L. (1985): Accumulation of chlorinated
hydrocarbons in moss from artificial rainwater. Oikos 46, 423-429.
Lead W. A., Steinnes E., Jones K. C. (1996): Atmospheric deposition of PCBs to moss
(Hylocomium splendens) in Norway between 1977 and 1990. Environ. Sci. Technol., 30,
524-530.
Milukaite A. (1998): Flux of Benzo(a)pyrene to the ground surface and its distribution in
the ecosystem. Water, Air, and Soil Pollut. 105, 471-480.
Moser T. J., Baker R., Tingey D. T. (Eds.) (1991): Ecological exposure and effects of
airborne toxic chemicals: an overview. US EPA Report No. 600/3-91/001. US EPA,
Environmental research Laboratory, Corvallis, OR 97 333, March 1991
Oehme M., Mano S., Thomas W. (1985): Quantitative determination of sub-ppb traces of
polychlorinated compounds and pesticides in moss samples. Fresenius Z. Anal. Chem. 321,
655-659.
Reischl A., Reissinger M., Hutzinger O. (1989): Organic Micropollutants and Plants.
Ecological Studies. Vol. 77, Ch. 3-B (E.-D. Schultze, O. L. Lange, R. Oren, Eds.). SpringerVerlag Berlin Heidelberg.
Safe S., Brown K. W., Donnelly K. C,. Anderson C. S., Markiewicz K. V., McLachlan
M. S., Reischl A., Hutzinger O. (1992): PCDDs/Fs associated with wood- preserving
chemical sites: Biomonitoring with pine needles. Environ. Sci. Technol. 26, 394-396
Simonich S. L., Hites R. A. (1995): Organic pollutant accumulation in vegetation. Environ.
Sci. Technol. 29, 2905-2914.
Sinkkonen S., Rantio T., Vattulainen A., Aitola J.-P., Paasivirta J., Lahtipera M.
(1995): Chlorohydrocarbons, PCB congeners, polychlorodioxins, furans and
dibenzothiophenes in pine needles in the vicinity of a metal reclamation plant.
Chemosphere, 30, 2227-3339.
Strachan W. M. J., Eriksson G., Kylin H., Jensen S. (1994): Organochlorine compounds
in pine needles: methods and trends. Environ. Toxicol. Chem. 13, 443-451.
Tremolada P., Burnett V., Calamari D., Jones K. C. (1996): Spatial distribution of PAHs
in UK atmosphere using pine neddles. Environ. Sci. Technol. 30, 3570-3577.
Váňa M., Pacl A., Pekárek J., Smítka J., Holoubek I., Honzák J., Hruška J. (1997):
Quality of the natural environment in the Czech Republic at the regional level. results of the
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Košetice Observatory. Czech Hydrometeorological Institute, Prague, CR.
Wagrowski D. M., Hites R. A. (1997): PAHs accumulation in urban, suburban, and rural
vegetation. Environ. Sci. Technol. 31, 279-282.
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Persistent, Bioaccumulative and Toxic Chemicals in Central
and Eastern European Countries - State-of-the-art Report
Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
10.9 Foods, transfer studies
The transfer of PBT compounds as environmental contaminants through the placenta
and milk to newborn and suckling animals is well established. The placenta restricts the
transfer to some extent, so that breast-feeding is the major transfer route of lipophilic
contaminants from mother to infants. Besides, dairy products also significantly contribute to
the total exposure through dietary intake, which is the main route for human exposure (Vrecl
et al., 1996).
The bioconcentration and migration of particular PBTs, mainly organochlorines is
highly structure dependent. The bioconcentration, which is correlated with lipophilicity on
the basis of the a-octanol/water partition coefficient in its logarithmic form - log Kow,
increases with increasing lipophilicity (McLachlan, 1993; Gobas et al, 1993; Travis and Arms,
1988; Shaw and Connell, 1984). The transfer of individual compounds into milk may be
further influenced by some physico-chemical (molecular weight, steric effects and the
extent and nature of interactions with individual blood constituents) and maternal (level of
exposure, milk fat content) properties. The transportation of organochlorines in various
tissues could also be influenced by enentioselectivity. Furthermore, any adsorption/
desorption non-singularity could considerably affect the fate and transfer of these
compounds. As most studies have been performed with technical PCB mixtures, data on the
distribution pattern of individual planar and non-planar compounds in various tissues is
scarce in the literature.
have examined the differences in distribution of two pairs of tetra- and
hexachlorobiphenyls, corresponding to the planar and non-planar conformation, HCB and
4,4´-DDE in the blood of mothers and infants, as well as in the milk of sheep during
lactation. The individual PCB congeners used were symetrical, thus excluding differences
in distribution by enantioisomerism. Attention was further focused on the levels of toxic
congeners in milk, a process in which the transport between blood and milk could play an
important role. The sheep was chosen as an experimental animal because it is an
economically important species with high fat and protein-rich milk.
Vrecl et al. (1996)
The milk/blood ratio on a fat basis was close to 1 for HCB, over 1 for 4,4´-DDE, PCB155, and -169 and below 1 for PCB-54 and -80. It was speculated that the deviation from
the ratio 1 results from the interactions of organochlorines with (lipo)proteins in blood and/
or milk. In milk, the enrichment of 4,4´-DDE, PCB-155 and -169 was observed. The
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relative toxicity expressed by the toxic equivalent (on a fat basis) was approximately
2.5 times higher in milk than in blood.
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10.9.1 References
Gobas F. A. P. C., Mccorquodale J. R., Haffner G. D. (1993): Intestinal absorption and
biomagnification of organochlorines. Environ. Toxicol. Chem. 12, 567-576.
McLachlan M. S. (1993): Mass balance of polychlorinated biphenyls and other
organochlorine compounds in a lactating cow. J. Agric. Food. Chem. 41, 474-480.
Shaw G. R., Connell D. W. (1984): Physicochemical properties controlling
polychlorinated biphenyl concentration in aquatic organisms. Environ. Sci. Technol. 18, 1823.
Travis C. C., Arms A. D. (1988): Bioconcentration of organics in beef, milk, and
vegetation. Environ. Sci. Technol. 22, 271-274.
Vrecl M., Jan J., Pogačnik A., Bavdek S. V. (1996): Transfer of planar and non-planar
chlorobiphenyls, 4,4´-DDE and hexachlorobenzene from blood to milk and to suckling
infants. Chemosphere 33, 2341-2346.
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10.10 Human exposure
10.10.1 Chlorinated pesticides and polychlorinated biphenyls
The serious contamination of food chains by PCBs occurred in the past in the Czech and
Slovak Republics. The main source of local dietary exposures were meat, milk, dairy
products, and eggs produced by farms where paints with content of PCBs for coating of
silos, sheds and other agricultural facilities were used. The composition of a commercial
technical mixture Delor 106 that was contained in these paints corresponds to Aroclor 1254
(Hajšlová et al., 1993).
Monitoring programme in former Czechoslovakia established in the middle of 80ties
revealed remarkably high levels of PCBs in human milk. However, the content of
contaminants used to be expressed at that time as "total PCBs". It should be noted that the
comparability of generated data was rather poor, reflecting different "quantification
strategies" applied by individual laboratories. Implementation of congener-specific method
at the beginning of the 90ties made possible to get more information about the PCBs
patterns in samples from various programmes (Schoula et al., 1996).
Kočan et al. published (Kočan et al., 1994) the comparison between levels of PCBs and
HCB found in human adipose tissue and blood samples from former Czecho-slovakia
(CSFR) and some other countries. Unfortunately, the comparison between present analytical
results and older data is questionable because of different analytical approaches which
include: total PCBs versus congener-specific analysis; packed column versus capillary
column separation; lower versus higher precision and accuracy. The importance of PCB
analysis has increased after the dioxin-like toxicity of planar had been reported.
In many papers, which were published during last 15 years, levels of lipophilic analytes
in human blood samples are reported on a whole blood or a blood serum basis but not on a
lipid basis. This may be due, in part, to problems encountered in the quantitative isolation of
blood serum lipids. However, many published procedures for the analysis of halogenated
aromatics giving the results on a blood basis are actually also based on lipid isolation but
the isolated lipids are not weighed. Unfortunately, this approach makes the comparison
between the levels in lipids from adipose tissue, blood and milk impossible although a high
correlation between the levels in blood and adipose tissue lipids or milk lipids has been
observed.
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PCBs and other OCCs are most often monitored in human fat and human adipose
tissues, but human serum or other tissues (placenta, liver, heart) can be used as well (Černá
and Bencko, 1999). The results concerning human biomonitoring of PCBs in the former
Czechoslovakia, and in the Czech and Slovak Republics published during last two decades
were summarized and reviewed by Černá and Bencko (1999).
Extensive analyses have been made of PCBs levels in human milk. The first data
concerning analysis of PCBs in body fluids and tissues of Czech population appeared in the
literature in 1985. The concentration of sum PCBs (related to the standard commercial
mixture Delor 106) in 63 human milk specimens collected in Northern Bohemia found the
mean concentration of 2.83 mg.kg-1 fat (i.e. 0.105 mg.kg-1 milk with substantial interindividual differences) (Ševčík et al., 1985).
In 90ties, the previous presentation of PCB results as total PCBs was replaced by
analysis of individual congeners. In the Czech and Slovak Republic were found higher
levels of PCBs during WHO/EURO study in the region where the PCBs technical mixtures
were produced (District Michalovce, Eastern Slovakia) or intensively used (District
Uherské Hradiště, Eastern Czech Republic) (Table 10.10-1).
Table 10.10-1: The mean concentration of indicator congeners 138,
153 and 180 in human milk of the Czech and Slovak
populations [µg.kg-1 fat; samples pooled from 11
(Czech) and 10 (Slovak) individual samples (WHO/EURO,
1996; Bencko et al., 1998)
Locality
Uherské Hradiště
Year
1991-3
Kladno
Michalovce
Nitra
1
1993-4
PCB 138 PCB 153 PCB 180 Sum of PCBs 1
341.5
424.8
294.0
1 802.5
171.9
215.0
137.4
897.4
279.2
434.9
284.8
1 698.0
139.8
207.7
137.9
825.2
not very convenient sum as (PCB 138 + PCB 153 + PCB 180) * 1.70 factor
Since 1994, the levels of indicator congeners in human milk have been systematically
followed in the frame of System of Monitoring the Environmental Impact on Population
Health of Czech the Czech Republic. The results obtained in years 1994-1996 confirm the
tendency to a decrease - see Table 10.10-2 (Kliment et al., 1997).
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Table 10.102:
Locality
Monitoring
1
The mean and (median) concentration of indicator
congeners 138, 153 and 180 in human milk of the
Czech populations [µg.kg-1 fat]
PCB 138
PCB 153
PCB 180
Sum of PCBs 1
1994 282 236 (190)
398 (352)
308 (255)
1 601 (1 355)
1995 395 212 (178)
350 (323)
272 (248)
1 418 (1 273)
1996 285 184 (163)
230 (201)
150 (125)
959 (831)
Year
n
Sum as (PCB 138 + PCB 153 + PCB 180) * 1.70 factor
The concentrations of PCBs and OCCs have been determined in human milk samples
from the three regions in the Czech Republic by group of Prof. Hajšlová (Schoula et al.,
1996). The results were generated by the congener-specific analyses and compared with the
similar studies from other European countries.
The following table (Table 10.10-3) compares the levels of indicator PCBs in human
milk from Czech Republic (Prague subset) with similar studies from Norway, UK, the
Netherlands and Germany (Schoula et al., 1996).
The sum of indicator PCBs was higher in Czech samples compared to those of foreign
origin while the content of lower chlorinated PCBs (congeners no. 28 and 52) as well as
pentachlorobiphenyl no. 101 were below the limit of quantification (i.e. 5 ng.g-1 in fat).
This fact may be attributed to different contamination pattern of Czech diet and,
consequently, different dietary exposure. Technical mixtures with prevailing content of
hexachloro- and heptachlorobiphenyls were mostly the primary source of environmental
pollution if former Czechoslovakia. PCB 153 was the dominant congener in all the samples.
Regarding the composition of market basket of countries listed in previous Table, fish
and fish products are consumed here in higher rate. The consumption statistics in Norway,
UK, the Netherlands and former Czechoslovakia in the end of 80ties were as follows 41.1,
19.9, 9.2 and 6.8 kilograms of fish and fish products per capita and year, respectively (FAO,
1993). Relatively high contents of PCBs were often reported in fish from Baltic and Nothern
Sea. Since the biodegradation of PCBs in fish is very limited, higher intake of lower
chlorinated PCBs (that are typically accumulated in these biota) via this commodity may be
reflected in elevated levels in human milk (Schoula et al., 1996).
Comparison of PCB levels in human milk was carried out in three different regions in
the Czech Republic: Prague represents industrial urban agglomeration, Kladno is a small
industrial city near to Prague and Uherské Hradiště is a locality characterised by high
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environmental burden of PCBs due to their outbreak from paints producing plant and wide
use of these paints in local agricultural facilities.
The following results clearly illustrate the levels of PCBs in the later locality with
higher extent of pollution (Table 10.10-4). The comparison of similar areas of Czech
Republic locally produced crops, these regions are more contaminated and thus their
consumption results in higher mothers burden. The levels of PCBs in Prague and Kladno
were lower, no distinct differences were recorded between these regions. As to the
chlorinated pesticides, the higher content of DDT (and its metabolite DDE) in Uherské
Hradiště may be attributed to its wide use in this agricultural region in the past. Levels of
HCB, which may be formed in various combustion processes were slightly higher in
industrial area such as Prague and Kladno. The contents of beta-HCH was similar in all sets
of examined samples (Schoula et al., 1996).
Table 10.104:
Content of PCBs and OCCs in human milk comparison of various regions in Czech Republic [ng.
g-1 in fat]
Region Sum of PCBs
beta-HCH
DDTs HCB
Number
of samples
Prague
1 096
71
998
639
17
Kladno
860
79
832
570
17
Uherské
Hradiště
1 529
80
1 283
482
12
Sum of PCBs - sum of congeners no.: 28, 66, 70, 74, 105, 118, 138, 153, 156,
170 and 180.
DDTs = p,p´-DDE + p,p´-DDE
The newer study (Schoula et al., 1998) is focused on distribution of PCBs and OCCs in
the various human tissue samples from selected regions of the Czech and Slovak Republic
and comparison with the results from other foreign and local studies.
The sets of samples consisting of various human tissues originating from three regions,
two of them representing cases with very high environmental contamination (Uherské
Hradiště, Cz and Michalovce, Sk) and one (Prague) represents industrial urban
agglomeration with intensive anthropogenic activities and many potential sources of
pollution, were analysed. The results were used to assess the PCBs and OCCs body burden
of whole Czech and Slovak population. The biotic samples were collected during postmortem examination of people who were killed by car-accidents (Michalovce and Prague)
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or died natural deaths (Uherské Hradiště). Following tissues were taken for analyses:
abdominal adipose tissue (from subcutaneous area), liver, kidney, heart muscle (in the case
of region Uherské Hradiště only) and adipose tissue from mesenterial area (only in the sets
from Prague and Michalovce).
These measurements (Schoula et al., 1998) confirmed again that the organochlorine
residues in the tissues of Czech and Slovak origin are often higher (especially for PCBs and
DDTs) than levels in humans from other countries. The sum of indicator PCBs in samples
from Michalovce and Uherské Hradiště was substantially higher compared to corresponding
data from for example Finland, UK or the Netherlands.
With exception of the Slovak origin samples, in all other studies tri- and
tetrachlorobiphenyls (PCB 28 and 52) are present at trace concentrations (upper limit about
10 ppb). Surprisingly, high amounts of these congeners were found in the specimens
collected in Michalovce. The elevated levels of lower chlorinated congeners in human
tissues indicate actual exposure to PCB technical mixtures with the low chlorine content
(Luotamo et al., 1991). On the other hand, when only PCB 28 and 74 (most persistent
congeners among low chlorinated PCBs) are present in the highest amounts, the long-term
occupational exposure to such technical mixture in the past time is indicated (Schoula et al.,
1998). Occurrence of both mentioned types of exposures in the locality Michalovce are
highly probable, nevertheless, the data on the profession of donors were not available. The
study showing vegetables to play an important part in the intake of lower chlorinated PCBs
due to the ambient air contamination in the locality should be mentioned. However,
relatively high concentrations of PCB 28 found in Michalovce seem unlikely to be
associated with the high consumption of discussed commodity.
Biological monitoring of different human tissues indicated that concentrations of PCBs
in blood, adipose and muscle tissues were about the same calculated on a lipid basis. In this
study (Schoula et al., 1998) higher PCB levels were found in the tissue richer in fat such as
adipose. Distribution patterns of PCBs revealed in other analysed tissues similarity to those
found for the DDT group. HCH isomers are predominantly accumulated in the both liver
and kidney their concentrations being here several fold higher (2.5-5 and 2-3 times more,
respectively) than in fatty adipose tissue. Similarly, HCB tends to be accumulated rather in
the soft tissue.
In the subset of samples from the region Uherské Hradiště the determination of 38
individual chlorobiphenyls congeners was carried out. The contribution of individual
chlorobiphenyls in adipose tissue was slightly different from other materials (liver, kidney
and heart muscle) typically containing higher amounts of more polar lipids (phospholipids).
The PCB pattern in later matrices was almost equal. The levels of relatively more polar
lower chlorinated congeners were higher in these tissues in comparison with the adipose.
Nevertheless, highly chlorinated PCBs, those with the sign of persistence i.e. 2,4,5chlorines in one ring and at least one chlorine in 4 position in the second one (namely
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congeners No.: 138, 153, 170 and 180), were the prevalent congeners in all the analysed
samples. This indicates long-term environmental exposure in the inspected region. Their
contribution to the total amount of PCBs exceeded 70 %.
For the normal population, food represents the main route of environmental exposure to
PCBs/PCDDs/Fs (Černá et al., 2000). According to the System of Monitoring the
Environmental Impact on Population Health of the Czech Republic, the intake of PCBs
(expressed as sum of 7 indicator PCB congeners) for the average Czech population in the
year 1996 was calculated at 86 ng per kg body weight. The population exposure to 11 toxic
PCB congeners for the year 1998 was estimated to 12.3 pg I-TEQ per kg body weight
(Ruprich, 1997 - 1999). The levels of indicator PCB congeners in the human milk show a
declining time trend (Černá and Bencko, 1999; Černá et al., 2000). The levels of PCDDs/
PCDFs in the pooled human milk samples collected in 1998 were about 10 pg TEQ/g fat. In
the last years, also the analysis of PCDDs/PCDFs in the human adipose tissue has been
included into monitoring system to determine the background exposure to these compounds.
In the years 1996 - 1999, adipose tissue samples were collected at autopsy according to
a specific protocol in four districts of the Czech Republic, two of them more industrial (PM,
UL), two other more rural and recreational (BN, ZR). The basic characteristics of sampled
persons are summarized in Table 10.10-5.
Table 10.10-5: Characteristics of analyzed samples
Locality
Lower polluted regions
Higher polluted regions
Overall
BN
ZR
PM
UL
n
12
14
12
23
61
Males
4
12
7
8
31
Females
8
2
5
15
30
Avg age
52.8
45.4
60.1
62.0
56.2
40 - 62
27 - 60
45 - 74
42 - 84
27 - 84
Range
Average age - males
Average age - females
51.3
61.0 *
* p<0.01
Polychlorinated dibenzo-p-dioxin (PCDD) and polychlorinated dibenzofuran (PCDF)
levels, selected PCB congeners with dioxin toxicity (77, 126, 169, 123, 14, 105, 167, 156,
157, and 189) as well as the indicator PCB congeners (28, 52, 101, 118, 138, 153, 180),
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were determined in the fat melted off from homogenised samples of human adipose tissue.
For the calculation of dioxin toxic equivalency (TEQ), the toxicity equivalency factors
(TEFs) proposed by Van den Berg et al. (1998), were used.
The mean total TEQ values for the overall study as well as the data with respect to age
and gender are summarised in Table 10.10-6. Because of log-normally distribution, median
values were used in descriptive statistics. The sum of all PCDDs was about twice as high
than the sum of all PCDFs. Concentration of PCDDs/Fs/PCBs correlated with age (r=0.47,
p<0.01). Gender differences in concentrations as well as in TEQ values with slightly higher
values obtained in female group were not significant in spite of the fact that the mean age of
the female group was almost 10 years older than that of the male group and that this age
difference was significant (p<0.01).
The apportionment of the total dioxin toxicity (TEQ) into the PCDD, PCDF, and PCB
groups is presented in Table 10.10-7. PCDDs (median value) contributed with about 9.4 pg
TEQ.g-1 fat, PCDFs with 16.9, and PCBs with 69.2 pg.g-1 fat to the total TEQ value.
Compared with levels in human milk, these levels were distinctly higher (Černá et al, 2000).
Table 10.10-7: Dioxin toxic equivalents (TEQ) and percent
contribution to total TEQ
[pg.g-1 fat] in human adipose tissue
Group
PCDDs [%]
PCDFs [%]
PCBs [%]
Overall
9.8
17.7
69.2
Males
9.0
18.0
73.0
Females
10.4
19.2
70.5
In agreement with the results published by Schechter et al. (1994), 2,3,4,7,8-PeCDF was
the dominant congener among the PCDDs/Fs compounds also in our group. This compound
contributed more than 80 % to the dioxin toxic equivalents from PCDF congeners. OCDD,
which is the congener found in the largest amount (median concentration = 114 pg.g-1 fat),
provides about 53 % of the total PCDDs/Fs concentration but its contribution to the dioxin
toxicity is negligible. PCBs 156 and 126 accounted for 84 % (males) and 95 % (females) of
TEQ portion derived from the PCB congeners with dioxin toxic activity.
Regional differences were observed in concentrations of individual congeners as well as
in TEQ values. In samples from more industrialised districts (n = 35) slightly higher levels
were found in comparison to the results obtained in the fat tissue from rural districts (n =
26). However, the differences were not significant, probably because the mean age of
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persons in more industrialized area was significantly higher that that of the rural area. No
substantial local or gender differences were observed in the percentage contribution of
individual congeners to the total TEQ.
Among the indicator PCB congeners, PCB 138, 153, and 180 contributed substantially
to total PCB level in human adipose tissue. The results are summarised in Table 10.10-8 as
sum of above-mentioned congeners. The level of PCB correlated significantly with age (r =
0.3, p<0.01). Significantly higher values were obtained in the group of age 50 and more
(p<0.05) in comparison to the group younger than 50 years. No significant gender or local
differences in concentration levels were found.
Table 10.10-8: PCB levels expressed as sum of indicator congeners
138, 153, and 180 (median)
[pg.g-1 fat]
Group
Median
Ranges
Overall
1 753
786-8 167
Males
1 822
786-3 536
Females
1 695
836-8 167
Age >= 50
2 082 *
Age <50
1 611
1 147-8 178
786-3 362
* p<0.05
In conclusion, the presented values represent the first human data characterising the
background exposure of the Czech population. It is evident that the Czech population was at
a higher exposure risk in the past. PCBs contribute more dioxin like toxicity in human
tissues than do dioxins and dibenzofurans. However, the data concerning the level of
PCDDs/Fs are till now insufficient to characterise the time-related trends of the body
burden of the Czech population, therefore further monitoring activities are of high
importance.
The incidence of carcinogenic diseases in Slovakia is among the highest in the world. It
is possible that increasing environmental pollution by toxic chemicals, including persistent
chloroaromatic compounds may contribute to this undesirable trend (Kočan et al., 1994). The
potential exposure of human population in Slovakia is systematically studied many years.
The researchers from Institute of Preventive and Clinical Medicine in Bratislava have
published many research papers and reports during last ten years.
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The growing concern was done to the study of contamination of total diet, mother milk
and adapted cow´s milk, dairy products and other various food commodities (Prachar et al.,
1995). The contamination levels of organochlorine insecticides and indicator congeners of
PCBs in milk and butter from the markets in Bratislava were studied in 1994. From the
results obtained for organochlorine insecticides it can be seen that the highest levels were
measured for p,p´-DDE and p,p´-DDT. These findings could be ascribed to the use of nonstandard imported feed in the farms. This was especially true in the early spring months
characterised with a lack of inland feed for animals. In spite of measures taken in 1973,
lindane (gamma-HCH) preparations (e. g. Lindan, Hermal, Sanigran) were applied,
although in a restricted extent protection of feed supplies, for some following years. The
findings of total DDT in Slovakia (0.059 mg.kg-1 on fat basis) can be compared with those
found in butter in the Czech Republic for example by Strnad (1991), with mean of 0.053 mg.
kg-1 on fat basis and Bartonicek and Rob (1991) 0.033 mg.kg-1 on fat basis. In Poland, the
total DDT level in butter was reported at the mean of 0.096 mg.kg-1 on fat basis and a
maximum of 0.272 mg.kg-1 on fat basis (with comparison with Slovak maximum 0.208)
(Heinisch et al., 1994).
Although the mean levels of HCB were relatively low, the maximum levels found can
be influenced with the environmental contamination with this compound. In 90´s,
agriculture is not the main source of HCB environmental inputs in CEE countries. The
many HCB residues come from the deposits of chemical wastes. Especially, the vicinity of
Bratislava, the capitol of Slovakia was considered to be the "hot spots" of the HCB
contamination (Uhnák et al., 1996). The HCB levels found (mean value 0.004 mg.kg-1 on fat
basis), were in a good correlation with those in the samples of butter in the area of Schwerin
town (Germany) in 1990 with a mean content of 0.007 mg.kg-1 on fat basis (Heinisch et al.,
1994) and with the Czech Republic from 1991 year reported by Strnad (1991) with a mean
level of 0.014 mg.kg-1 on fat basis. Year before (1990), Bartonicek (1991) has found the
mean HCB level in butter at 0.044 mg.kg-1 on fat basis.
With regard to the conditions of CEE milk farming in this time, one sample of butter
represents a mean obtained from the milk coming from a number of farms. From this point
of view, the contamination levels measured in butter can be regarded as the measure of
environmental contamination with persistent organochlorine compounds (Heinisch et al.,
1994).
The results concerning to PCBs (Prachar et al., 1994) in fifty samples of mother milk and
20 samples of adapted cow´s milk produced for bottle feeding supplied from the lactarium
of the Pediatric Hospital in Bratislava, were examined for presence of 6 indicator congeners
of PCBs. In all samples, congeners Nos. 138, 153 and 180 were predominant (similarly to
Czech study by Schoula et al., 1996, 1998). The highest mean as well as the maximum level
was found for PCB 138 for both types of samples.
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The average daily intake based on the sum of indicator congeners was found to be
2.56 µg.kgbw-1.d-1 for mother milk, and 0.85 µg.kgbw-1.d-1 for adapted cow´s milk. The
calculated average daily intake from mother milk exceeded the value of Acceptable Daily
Intake which is 1 µg.kgbw-1.d-1, but this was observed also in other countries. From this
point of view bottle feeding would seem to be more advantageous, since the PCB levels are
significantly lower in adapted cow´s milk. In addition to this, the content of all congeners
found in adapted cow´s milk was deeply below the permissible level (0.04 mg.kg-1 for 28,
52, 101, 180 and 0.05 mg.kg-1 for 138 and 153 in fat).
Samples of subcutaneous abdominal adipose tissues were obtained from Slovak
population by autopsy and analysed for the level of PCBs (Petrik et al., 1991). The
concentrations found in Bratislava (males, n=32, females, n=14), were in the ranges 0.8 to
10.4 and 0.6 to 7.7 mg.kg-1 fat, in Trenčín (males, n=18, females, n=11) 2.1 to 5.5 and 0.4
to 6.1 and in Martin (males, n=17, females, n=13) 0.4 to 4.7 and 0.4 to 4.8 mg.kg-1,
respectively.
Fifty samples of human blood collected in 1992 from the general human population
living in five selected areas of the Slovak Republic (the Michalovce, Velký Krtiš and Nitra
Districts, Myjava area and Bratislava) were analysed for 18 PCB congeners and some
organochlorine pesticides (HCB, lindan, p,p´-DDE and p,p´-DDT). The levels of these
pollutants in serum lipids averaged for all the samples analysed are described in Table
10.10-9.
Table 10.109:
Levels in serum lipids averaged from five selected
areas in Slovakia, 1992 [µg.kg-1]
Pollutant
Mean
Median
Range
PCBs (18 congeners)
1.79
1.33
0.53 - 9.20
HCB
5.38
4.27
0.16 - 23.20
gamma-HCH
0.012
p,p´-DDE
6.05
4.39
1.30 - 34.80
p,p´-DDT
0.27
0.23
< 0.01 - 0.79
< 0.01 - 0.18
About three times higher levels of PCBs were found in the samples from the district
where PCB formulations had been produced (the Michalovce District). The PCB levels in
the Slovak population were in 1992 similar to previous findings, however, they were
substantially higher than PCB levels in humans from other countries. This difference was
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even more evident in the case of HCB, which levels were about hundred times higher than
levels in USA, Japan, Finland or Canada. Paper also described the arithmetic mean values
of PCBs, p,p´-DDE, p,p´-DDT and HCB found in the serum lipids of the male and female
populations. The mean levels of p,p´-DDT and PCBs were lower in females.
From data reviewed in these papers the levels of PCBs and related compounds in
humans from former Czecho-Slovakia are higher than observed in studies from other
countries. Higher exposure was found in the vicinity of PCB mixture manufacturing or
using. Since PCB production was banned in 1984, the total environmental PCB
contamination and consequent body burden in the general population of Czech and Slovak
Republics have decreased. However, the opportunity for human exposure still exists (Černá
and Bencko, 1999).
The other part of this project were focused on the investigation of levels of PCBs and
selected organochlorine pesticides in human milk in the same five model areas (Kočan et al.,
1995). Based on the WHO protocol, the human milk samples were collected from breastfeeding mothers (primiparae, milk sampling 2 weeks - 2 months after delivery, unchanged
residence at least 5 years before pregnancy).
HCB and p,p´-DDE were present in the human milk samples at higher concentrations
than individual PCB congeners and p,p´-DDT. HCB levels are noteworthy as they are one
or two orders of magnitude higher than reported from other countries (see Table 10.10-10).
Surprisingly high concentrations of HCB found in human samples from Slovakia are
probably caused by its use in agriculture and its formation during industrial manufacture of
some chlorinated solvents.
Levels of all the pollutants determined in the human milk lipids were substantially lower
than those in the blood and adipose tissue samples collected from the same areas. The
differences in PCBs levels in the milk samples from Michalovce District (location of former
PCBs producer) compared to the other districts were not as large as the adipose tissue and
blood serum differences. This could be caused by the lower age of breast-feeding mothers
in comparison with the mean ages of the adipose tissue and blood donors and by decreasing
OCPs and PCBs contamination of the environment after their use had been banned.
The average ratios of p,p´-DDE to p,p´-DDT in the milk samples from Bratislava,
Myjava, Nitra, Michalovce and Velký Krtiš were 14.7, 12.6, 17.5, 9.8 and 13.9,
respectively. This is also less than was observed in the adipose tissue and blood serum
samples (Kočan et al., 1994a, b). PCB congeners No. 153, 180 and 138 were the most
abundant congeners found in all of the samples.
Considering a 5 kg infant sucking daily 800 g of mother´s milk in the Michalovce
District, the average daily intake of the sum of the six PCB congeners was 7.5 µg.kg-1 bw.dhttp://www.recetox.muni.cz/old/index-old.php?language=en&id=4386 (11 of 27) [26.1.2007 8:27:21]
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1.
The range could be from 2.8 to 4.4 µg.kg-1 bw.d-1 in the other four model areas, which is
substantially higher than the acceptable or tolerable daily intake of 1 µg.kg-1 bw.d-1
(involves all PCB congeners) established in some countries. Concerning HCB and p,p´DDE + p,p´-DDT, the daily would range in all the 5 areas from 2.0 to 5.1 µg.kg-1 bw.d-1
and from 5.6 to 11.5 µg.kg-1 bw.d-1, respectively. In the case of DDE+DDT, these intake
were lower than the ADI value established by WHO (20 µg.kg-1 bw.d-1), but in the case of
HCB these intakes were two orders of magnitude higher than the provisional tolerable daily
intake of 0.08 µg.kg-1 bw.d-1 according to the Health Protection Branch of Health and
Welfare Canada.
This presented results from the pilot study involved a relatively small number of
specimens and it was questionable to evaluate any statistical parameters. But based on these
results was performed during period 1997-1998 very unique study which results are
described in the following text.
Kočan and co-workers also studied the PCDDs/Fs and coplanar PCBs levels in blood
serum samples collected from the Slovak human general population (5 district) and
occupationally exposed workers (Kočan et al., 1996). These pollutants were also determined
in blood samples taken from a limited number of workers employed for a long time at a
municipal waste incinerator or a PCBs production plant.
The summary results concerning the levels of the PCDDs/Fs and two of the most toxic
coplanar PCBs (PCB-126 and PCB-169) are given in Table 10.10-11. The mean total lipids
in the serum were 6.79 g.l-1. Mean TEQPCDDs, TEQPCDFs and TEQplanPCBs for each
sampling location were similar, including the MWI samples, whereas TEQPCDFs and
TEQplanPCBs values were several times higher in the case of samples from Chemko Strážské
(former producer of PCBs mixtures). Increased TEQ levels in the Chemko samples were
caused mainly by higher concentrations of 2,3,4,7,8-PeCDF and 3,3´,4,4´,5-pentaCB (126).
2,3,4,7,8-PeCDF has contributed 53 % to the total mean TEQ found in the Slovak general
population, 60 % in the case of the MWI workers, and 80 % in the case of the
occupationally exposed workers in PCB production. There were no substantial differences
between the PCDDs, PCDFs and planPCBs levels in the general population samples from
sampling districts.
In spite of long-term work at the old-type waste incinerator, PCDDs/Fs and coplanar
PCBs levels in workers blood, were found to be within the range of the levels reported for
the general population samples (Table 10.10-11). This in agreement with published data
although in some studies a slight increase in the concentrations of higher chlorinated
congeners was observed.
It is noteworthy that the ratio of I-TEQPCDDs to I-TEQPCDFs found in the Slovak
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general population was less than 1 (about 0.5), whereas according to published data from
other countries this ratio is expressively higher - from about 1 for Germany and Spain to 2.7
for the USA. This was due to relatively high levels of 2,3,4,7,8-PeCDF (I-TEQQ=0.5) in the
Slovak human samples in proportion to the total TEQ´s. On the other hand, the levels of
1,2,3,7,8-PeCDD (a congener with the same I-TEF) were found to be very low. Authors
assumed that the increased 2,3,4,7,8-PeCDF levels observed in the Slovak samples were
due to increased exposure to PCBs. This assumption was supported by findings of a high
2,3,4,7,8-PeCDF content in the blood lipids of the Chemko workers occupationally exposed
to PCBs. The ratio of the mean 2,3,4,7,8-PeCDF level in the Chemko to the mean level in
general population samples was 6 (121.2:21.1), which is also the ratio of total PCB levels
found in the same samples.
The goal of which was mentioned above study was the investigations of PCBs and
OCCs in samples of human population (from the District Michalovce, location of former
producer of PCBs and the District Stropkov). The basic topic of this project was to study the
environmental and human population load in the area contaminated with PCBs (Kočan et al.,
1999). The first summary of results from measurements of PCB contents in blood samples
of human population from these two studied regions is described in the Table 10.10-12.
The higher contents of PCBs, which were determined in various kinds of foods from the
District Michalovce must lead to higher levels of PCBs in human population from this
district. Fat samples from blood serum of general population of this region (107 males and
108 females) contained average concentration of PCBs 4.2 µg.g-1, in comparison with
District Stropkov (101 males + 104 females) where was observed the value of 1.2 µg.g-1.
The level 8.6 µg.g-1 of PCBs was found in the case of professionally exposed workers in
former producer Chemko Strážské (27 males and 11 females). It is important note that this
exposure was 20 - 30 years ago this measurements. Part of a general population was group
of 11 fishermen, which have consumed the fish from contaminated waters of Laborec River
and Zemplínská Šírava Dam. In this small not very representative group were observed very
high levels of contamination (58.7 ppm) but also relatively low (1.6 - 2.9 ppm). The higher
levels of PCB contamination were found in females in all evaluated groups of populations
from the both of Districts, but not statistically significantly. But the fact that the
consumption of contaminated kinds (eggs, chicken meat) of foods from home production
leads to higher level of contamination of human population was confirmed and was
statistically significant. The observed levels not only of PCBs, but also HCB and p,p´-DDE,
(including District Stropkov) are in Slovakia higher than in EU countries or in USA or
Canada.
Placental contamination with xenobiotics may act as a biological marker for the
exposure of the mother, or the foetus via transplacental transfer (Reichrtová et al., 1999). In
Slovakia, PCB congeners were detected in the human food chain including human breast
milk, where the PCB´s levels were found to be higher comparing to the cow´s milk. The
aim of this study was to compare the contamination of human placentas with organic
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xenobiotics (selected organochlorine compounds) in five environmentally different Slovak
regions.
Samples of placental tissue were taken from mothers in five environmentally different
regions in the Slovak Republic. The samples were analysed for the concentrations of 21
selected organochlorine compounds - polychlorinated biphenyls (PCBs - PCB-28, PCB-52,
PCB-101, PCB-118, PCB-138, PCB-153, PCB-180), chlorinated benzenes (1,4+1,3-DCBz,
1,2-DCBz, 1,3,5-TCBz, 1,2,4-TCBz, 1,2,3-TrCBz, TeCBz, PeCBz, HCB) and
organochlorine insecticides (alpha-HCH, beta-HCH, gamma-HCH, delta-HCH, p,p´-DDT,
p,p´-DDE) - see Table 10.10-13.
The statistical analysis of the placental organochlorine compounds concentrations
revealed that the mean contents of 12 (1,4+1,3-DCBz, 1,3,5-TrCBz, 1,2,3-TrCBz, TeCBz,
PeCBz, HCB, alpha-HCH, beta-HCH, gamma-HCH, delta-HCH, p,p´-DDT and PCB-101)
out of 21 organochlorine compounds analysed were significantly higher in the Region 1
polluted by chemical industry if compared to the other regions investigated. However,
concentrations of DDE and the PCB congeners 28, 52, 138, 153 and 180 were highest in the
agricultural region. Among the investigated regions, the lowest concentrations of 9 (1,2DCBz, 1,3,5-TrCBz, TeCBz, PeCBz, p.p´-DDT, PCB-28, PCB-52, PCB-138 and PCB-153)
organochlorine compounds were found in the both regions polluted by iron-ore mining /
iron-ore processing.
Exposure to organochlorine compounds can be determined in samples from various
tissues, encountered foetal and placental tissues. Experimental findings on animals revealed
that organochlorine compounds may induce oxidative stress in foetal and placental tissue
with subsequent tissue damage. Production of superoxide anion and lipid peroxidation, and
DNA-single strand breaks were found. In our previous work we have found the higher
proportion of pathological microstructural changes in the human placental samples collected
from the Region 1 polluted by chemical industry in comparison to the rural Region 5. The
period of intrauterine development of the embryo / foetus is highly susceptible to adverse
impacts of organochlorine compounds. Further research focused on the mechanisms of
these compounds in the reproductive pathology is needed. Our findings pointed to the
various contamination of human placentas with organochlorine compounds with respect to
predominant type of pollution in the selected regions.
Effect of organic xenobiotics in human placentas on allergic sensitization of newborns,
were studied by Reichrtová et al. (1999). Although we understand now more about the
genetics of atopy and the role of Th1 and Th2 cells in the control of immunoglobulin E
(IgE), there are puzzles regarding the environmental causes of atopy. The evidence linking
patterns of fetal growth to adult diseases has focused attention on the role of the placental
environment in the etiology of atopy and atopic diseases., In our study we gathered fresh
samples of full-term placentas and umbilical cord blood at the deliveries in the maternal
houses in environmentally different regions (industrial one polluted predominantly by
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organic xenobiotics and traffic, compared to a rural one). Questionnaires focused on
parameters of placentas and newborns were collected. Placental samples were analyzed for
21 compounds of persistent organic pollutants (POP) by capillary gas chromatography. In
umbilical blood samples the concentration of total IgE (as a biomarker of a sensitization of
newborns) using CAP system was determined. Laboratory analyses have shown the
statistically significantly higher concentrations of 17 compounds out of 21 POP investigated
in the placental samples collected from the industrialized region if compared to the rural
one. Paralelly, the increase in the total IgE level in the umbilical blood samples gathered
from industrial region was found, evoked possibly by organic xenobiotics. External
placental parameters differed too.
Allergic diseases are on the rise in both prevalence and severity, especially in
industrialised countries. Developing fetus and young children may be more susceptible to
effects of chemical agents in relation to allergic sensitisation, especially those with a genetic
propensity (Reichrtová et. al., 1999).
In general, the fetus is protected against external influences by the placental barrier, but
this barrier is selective, especially for maternal immunoglobulin G (IgG) antibodies, various
antigens, and chemical substances. Contrary to the transplacental IgG transport, only a low
amount of immunoglobulin E (IgE) antibodies are present in newborns, and it seems that
these IgE antibodies have a fetal origin. There are environmental chemicals and drugs (e.g.
xenobiotics) that may enhance the sensitisation to allergens of various origins in susceptible
persons (due to their modulative effect on T cells). Therefore it is of great importance to
understand the pathogenic mechanisms (neoantigen formation, metabolism of xenobiotics
into reactive - haptenic metabolites, induction of costimulatory enzymes, and sensitisation
of T cells) involved in the xenobiotics action. Assuming that the infants undergo antigen/
allergen priming in utero, xenobiotics may influence the response to antigen exposure and
bring about allergic diseases in early childhood.
Demonstration of benzo(a)pyrene-DNA (BaP) adducts in human placenta and cord
blood approved the metabolic capacity of the placenta, the transfer of BaP from mother to
the fetus, and the genotoxicity of BaP as well. Organochlorine compounds are accumulated
in the body during the life, therefore individual body burden increases to levels that are
toxic to organism and the offspring is exposed in utero by maternal transfer of them.
Organochlorine compounds exert estrogenic effects (endocrine disruption) and a variety of
associated effects such as reproductive and immune system dysfunction. Neonatal exposure
to polychlorinated biphenyls (PCBs), especially to their congeners 28 and 52, were found to
have persistent neurotoxic effect in adult animals. In Slovakia, these PCB congeners were
detected in human breast milk as well as in the cow´s milk and dairy products.
Placental contamination with chemicals may act as a biological marker for the exposure
of the mother, or the fetus via transplacental transfer. Placentas were collected from term
deliveries in two Slovak regions. The samples were then analysed for 21 selected
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organochlorine compounds. The study was based on 2 050 full-term deliveries, randomly
selected in two Slovak regions, principally differing from each other in the industry-related
environmental pollution. The industrial region was represented by a city (Bratislava)
polluted mainly by the organic chemical industry (petrol, pesticides and rubber industry),
and by the traffic. The rural region was situated in the mountains (Stará Lubovna) devoid of
any industrial source of environmental pollution, but with traffic linked to tourism and a
border check-point. Women were selected according to the following criteria: residence in
the investigated areas (at least 3 years before the conception), normal term of deliveries
(40 ± 2 weeks of gestation), and non-occupational exposure to organochlorine compounds.
The data from questionnaires focused on mothers (e.g. residence, smoking habit,
occupation) were monitored. Also monitored were external parameters of placentas
(placental longest and transverse diameters and thickness), and newborns (birth weight and
height). The average age of the mothers investigated in the industrial region was 24.2,
whereas in the rural region 22.6 years of age. Cigarette consumption in the industrial region
was 26 %, and in the rural region 27 % of mothers. The incidence rate of atopic eczema
cases (per 10 000 children) in 1995 was 30.82 at Bratislava city, and 12.78 in Stará
Lubovna region. In the maternity clinics of the selected regions, samples of cord blood of
newborns (N=2 050) were collected, and sera prepared by the centrifugation.
Simultaneously, randomly selected samples (N=120) of full-term placentas were taken.
Specimens of cord blood from 2 050 neonates were gathered for the determination of levels
of total immunoglobulin E (IgE).
The contents of 21 substances of organochlorine compounds in the human placental
samples collected from the industrial and the rural region are presented in Table 10.10-14.
Comparisons between regions revealed that both the placental contamination with 16 (out of
21) organochlorine compounds and the cord serum IgE levels were significantly higher in
the industrial region. Furthermore, the percentage of non-contaminated placental samples
was significantly higher in the rural region if compared to the industrial one. The contents
of the all congeners of polychlorinated biphenyls (mainly PCB congeners 101 and 153), and
organochlorine insecticides analyzed in the placental samples were found to be higher in the
industrial region. The neonates were divided according to their cord serum IgE
concentration into 3 groups as follows: < 0.7 (e.g. negative newborns), 0.7-3.5, and
> 3.5 kU.l-1. A higher number (expressed in per cent) of IgE positive neonates in the 2nd
and 3rd group were found to be in the industrial region as compared to the rural region
(p<0.001). A lower number of IgE negative newborns were shown to be in the industrial
region (68.7 %) as compared to the rural region (82.4 %). The findings pointed to an
association between organochlorine compounds and the higher levels of total IgE in
newborns, signaling a higher allergic sensitization in the industrial region. This association
was supported by the higher incidence rate of atopic eczema cases in the population
registered in the industrial region. The positive Spearman correlations for p,p´-DDE
(r=0.3294, p=0.01), and for PCB 118 (r=0.3482, p=0.006) and cord serum total IgE level
were found.
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External parameters of human term placentas and birth parameters of neonates between
the rural and the industrial region are compared in Table 10.10-15. In spite of non-differing
average weights of placentas in both regions, other parameters (e.g. longest diameter,
transverse diameter and thickness) were found to be significantly higher in the rural region.
Comparison of birth parameters (weight and height) revealed that there was not significant
difference between the investigated regions. A higher percentage of microstructural lesions
diagnosed in human placentas from the industrial region (Bratislava city) in comparison to
the rural region (Stará Lubovna) was shown. These microstructural lesions may be
responsible for the different external parameters of human placentas (e.g. higher longest
diameter, transverse diameter and thickness) found in the industrial region.
Comparing the biomarkers of mother´s chemical exposure in studied cohorts (e.g.
different placental metal and organochlorine contents in the placental samples) to cord sera
IgE levels between two environmentally different regions has lead to a hypothesis of the
possible fetal allergic sensitization evoked by organochlorine compounds in the placenta.
Most of the persistent organochlorine pesticides, excluding lindane, were banned in
Poland in 1975/76. The first restrictions concerning the use and marketing of lindane
became effective in 1980 and were gradually extended until it´s agricultural use was
ultimately banned in 1989. Unfortunately, there are no detailed data on the use and release
of PCBs to the environment in Poland. OCCs and PCBs in human adipose tissues were
studied in Warsaw (Ludwicki and Góralczyk, 1994) and chemically more detailed in Gdaňsk
and one province of inland Poland (Falandysz et al., 1994).
Subcutaneous adipose tissues were taken from surgically treated patients in the Warsaw
´s hospitals (Ludwicki and Góralczyk, 1994). Samples were collected between year 1989 and
1992 from men and women, aged between 10 and 80. The total number of analysed samples
was 277 (142 from men, and 135 from women) (Table 10.10-16).
Table 10.10-16: Levels in human adipose tissues serum lipids
averaged from 277 patient from Warsaw´s hospital,
Poland, 1989-1992 [mg.kg-1 of fat]
Pollutant
Mean
Median
Maximum
PCBs
0.856
0.500
36.000
HCB
0.310
0.120
9.020
alpha-HCH
0.016
beta-HCH
0.228
0.120
5.097
gamma-HCH
0.074
0.030
2.727
0.160
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p,p´-DDE
5.745
4.382
35.850
p,p´-DDT
0.537
0.478
9.600
This study has been shown that the age may considerably contribute in organochlorine
concentrations in human adipose tissue. The same authors studied the excretion of these
pollutants from the man´s body by lactation (Czaja et al., 1997). Lactation is an important
factor in disposing organochlorine compounds from the woman´s body. From these reason
the authors studied the role of number of deliveries and the following lactations and their
effects on OCCS levels excreted in the mother´s milk. The relationship between age,
number of deliveries and the concentrations of OCCs in mother´s milk was to be identified
by examining the findings from the analysis of 253 samples of human breast milk.
Subjected to analysis were 108 milk samples from primaras and 145 samples from
multiparous females who had from 2 to 7 deliveries.
No decline was found in the mean concentrations of OCCs in multiparous females as
compared to primaras. This may stem from the age of the woman studied. Mean HCB and
Sum of HCHs concentrations were similar for both groups of donors, and mean p,p´-DDT
and PCBs concentrations were even higher for multiparous females (statistically significant
only for PCBs; p < 0.05).
Women with the highest number of deliveries (over four) were reported to the highest
DDT, its metabolites, and PCB levels. Also, it must be noticed that the average age of those
donors was also highest and amounted to 33 years.
The concentrations of chlorinated hydrocarbons identified in human milk are the result
of two processes: bioaccumulation of such compounds in the adipose tissue and excretion of
the compounds to human milk in the course of lactation. Older women may be expected to
have higher concentrations of OCCs due to longer exposure thereto. On the other hand,
lactation is an important means of disposing of such compounds from the woman´s body.
Daily disposal during lactation is much greater than daily intake. Thus, the concentrations
of chlorinated hydrocarbons in human milk may be expected to fall as the number of
deliveries increases (Czaja et al., 1997a, b; Jensen and Slorach, 1991).
My becomes chronically exposed to organochlorine compounds mainly through food
(Czaja et al., 1997a, b). Bioavailability of these compounds in breast-fed infants is higher
than that in formula-fed infants. It is therefore critical that one determines whether these
compounds are hazardous to the health of infants and small children in the high risk
category and identifies the safety margin between the current concentrations of the OCPs in
human milk and the limit beyond which health hazard is no longer acceptable.
On this base, the exposure of infants to PCBs and OCPs (HCB, HCHs, DDTs) from
mother´s milk were studied (Czaja et al., 1997c). Samples of human milk were collected in
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lactarium and maternity clinic in Warsaw and from donors in different regions in Poland.
462 human milk samples were analysed. To assess the exposure of breast-fed children to the
above mentioned compounds, data was gathered on the Acceptable Daily Intake (ADI) and
FAO Guidelines used to calculate the Theoretical Maximum daily Intake (TMDI) and
Estimated Daily Intake (EDI) for the tested compounds. Average concentrations of the
observed compounds are shown in Table 10.10-17.
It is worth noting that higher concentrations of PCBs and beta-HCH were reported for
mature milk than for that collected on the 4th day (statistically significant, p < 0.05). In
Poland Sum of DDTs and PCBs had the highest share in the Estimated Daily Intake by
breast-fed infants. The relation among ADI, TMDI and EDI was calculated only for Sum of
DDTs and Sum of HCHs as these were the only compounds for which ADI was identified.
The above mentioned calculations were then used to estimate the safety margins for Sum of
DDTs and Sum of HCHs. These amounted to 4.2 (ADI for Sum of DDTs = 20 µg.kg-1 bw.d1) and 13.3 (ADI for gamma-HCH = 8 µg.kg-1 bw.d-1), respectively. The estimated EDIs
for Sum of DDTs and Sum of HCHs did not exceed the values assumed to be safe, i.e. ADI
and TMDI.
While the PCBs intake in the initial period of lactation (4th day) was relatively low and
did not exceed the TMDI calculate during FAO/WAO guidelines, the EDI for PCBs in the
mature milk exceeded the relevant TMDI in some regions of Poland. Nevertheless, the
concentration of PCBs inhuman milk in Poland was lower than that found in highly
developed countries and amounting to, on average, 1 mg PCBs.kg-1 of fat. According to the
literature sources, the infant´s average PCBs intake from human milk was 4.4 µg.kg-1 bw.d1. The EDI for PCBs estimated in this study averages 2.8 µg.kg-1 bw.d-1.
These values of IDE for PCBs exceed the reference values of 1 µg.kg-1 bw.d-1 (FDA
US) or 0.6 µg.kg-1 bw.d-1 as proposed National Food Agency of Denmark. However, in the
light of the recent toxicological research, there is no reason why the levels of
organochlorines detected in human milk should be grounds for altering the children breastfeeding recommendations. The benefits of breast feeding for the child far outweigh the
possible negative impact of compounds found in mother´s milk (Czaja et al., 1997a, b, c).
The authors also have studied the differences between more and less industrialised areas
of Poland (Czaja et al., 1997b). Higher concentrations of HCB and DDT were reported for
the milk of women from more industrialised areas (Table 10.10-18). Among eight
chlorinated hydrocarbons examined, the concentrations of PCBs and p,p´-DDE were always
the highest. Statistically significant differences were found between the mean
concentrations beta-HCH, HCB, p,p´-DDT and PCBs examined in the milk samples of
women from more and less industrialised areas (p<0.05). In general, the concentrations of p,
p´-DDT (recalled from usage in Poland 20 years ago) were consistently lower than those of
its metabolite p,p´-DDE. The DDT/DDE ratio in the biological material falls with the
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passage of time since the DDT introduction to the environment.
The beta-HCH isomer showed highest concentrations although its fraction in
commercial lindane-containing pesticide products usually does not exceed 2 to 3 %. The
reason is that the excretion of beta isomer from human body takes five times longer than for
the other HCH isomers, and the beta-HCH ability to accumulate in tissue fat is from 10 to
30 times stronger than it is in other isomers. The alpha- and gamma-HCH levels
approximated the detection limit of the method.
Mean hexachlorbenzene concentrations were reported to be relatively low in human
breast milk, there are comparable to those found in other European countries. The PCBs
mean concentrations were lower than those found in other countries that amounted to the
mean 1 mg PCBs.kg-1 of fat.
Persistent organochlorine compounds found in human breast milk all over the world
have very high bioavailibility and can be almost fully absorbed from the infants´ alimentary
canal (Czaja et al., 1999a). In the course of lactation, persistent organochlorine compounds
dissolved in milk fat are removed from a woman´s body. The infant is exposed to the
compounds in question throughout the breast-feeding period.
This study was an attempt to identify if there are any trends in excretion of HCH
isomers alpha-, beta-, gamma-, HCB, p,p´-DDT, p,p´-DDD, p,p´-DDE, and polychlorinated
biphenyls with human milk during lactation. The human milk was sampled from eight
women from Warsaw region during lactation (Table 10.10-19). Results showed individual
differences in the excretion of the compounds. On occasion also subsequent milk samples
collected once a week from the same woman differed markedly. The levels of compounds
excreted with milk are reported to exceed significantly the daily intakes of those compounds
by breast-feeding women. The findings of this study are not conclusive enough to claim that
the infants´ exposure to those compounds decreases or increases as breast-feeding
continues. In light of current knowledge, the advantages of natural breast-feeding outweigh
the potential risk of negative implications for a child, resulting from toxic compounds in
human breast milk.
Table 10.1019:
Lowest
conc.
The range of average concentrations for the eight
donors [mg.l-1 of milk ± SD]
HCB
beta-HCH
p,p´-DDT
p,p´-DDE
PCBs
0.0003
±0.0002
< 0.0002
0.0033
±0.0019
0.0075
±0.003
0.0039
±0.0033
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Highest
conc.
0.0025
±0.0008
0.005
±0.0076
0.0129
±0.0098
0.1387
±0.1916
0.0384
±0.0854
The concentrations of organochlorine compounds in breast milk depend on two
processes: their life spanning bioaccumulation in the adipose tissue and excretion with milk
during lactation (Czaja et al., 1999b). Assuming that lactation can be an important process for
eliminating organochlorine compounds from the human organism, an attempt was made to
understand how consecutive deliveries and the following lactations impact the
organochlorine compound levels detected in human milk. The excretion of the examined
compounds during lactation is much higher than the intake of these compounds with the
diet, which may imply that the tissue deposits of the organochlorine compounds in women
decrease with consecutive lactation.
Literature provides different perspectives on the impact of consecutive lactation on the
organochlorine compound levels in breast milk. Some decrease in DDE, HCHs and PCBs
levels in the donors´ milk following consecutive deliveries was reported. The basic factors
affecting the concentrations of these compounds include the donors´ age, number of
children, and duration of breast-feeding after each delivery.
The material examined in the other study was breast milk from 2 donors´ two
consecutive lactation (Czaja et al., 1999b). The interval between the lactation was 8 months
for one donor and 2 years for the other donor. Milk samples were analyzed for the presence
of p,p´-DDT, p,p´-DDE, p,p´-DDD, alpha-, beta-, gamma-HCH and Sum of PCBs, using
the gas chromatography method with an electron capture detector.
This study has indicated that, for the mother with a shorter interval between lactation,
mean concentrations of the examined compounds were higher in the milk of the first
lactation than that of the second (Fig. 10.10-1). These variances were statistically significant
for each compound examined.
For the other donor whose second lactation began after 2 years, the differences in the
concentrations of compounds followed a different pattern. Mean levels of HCB, beta-HCH,
DDD, and PCBs in her milk were higher during the first lactation (Fig. 10.10-2), just like it
was the case for the first donor. However, these differences were not statistically significant.
At the same time, the concentrations of DDT and DDE after the second delivery were
slightly higher, with the variance being statistically significant. Also noted was the lack of
decreasing DDT and DDE levels in the other donor´s milk during the second lactation. This
may be related to a relatively fast complement of tissue deposits of these compounds during
a longer (2 years) interval between the lactation.
The woman´s organism ability to quickly complement tissue deposits of the
organochlorine compounds has been confirmed in earlier studies (Czaja et al., 1997a), where
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the mean concentrations of these compounds in primaras and multiparous females were
compared, also for the donors´ age. No decrease in mean concentrations of the studied
compounds was reported for multiparous females versus primaras. Mean concentrations of
HCB and Sum of HCHs were similar in both donor groups, with DDT and PCBs being even
higher for multiparous females. Such results may stem from the age of the women under
examination. The number of deliveries did not affect the mean concentrations of HCB and
Sum of HCHs. For women with the same number of children, DDT, its metabolites, and
PCBs increased with age. Other authors have reported similar results showing that
organochlorine compound concentrations in breast milk increase with donors´ age.
Age, more than the number of deliveries seems to affect the concentrations of
organochlorine compounds in breast milk. This phenomenon may imply that the deposits of
these compounds complement in women´s tissues after lactation quickly. This is confirmed
by the results of this study, where higher concentrations of DDT and DDE were detected in
the second lactation milk of a woman with a longer interval between deliveries.
Adipose tissue of inhabitants of the Gdaňsk city located at the southern coast of the
Baltic Sea and of the province of Skierniewice of inland Poland have been investigated for
congeners of PCBs by the HRGC-HRMS technique and of OCCs by HRGC-ECD
techniques. The samples were collected during autopsies from randomly selected donors in
Gdaňsk city in 1990 and the province of Skierniewice in 1979. Earlier data indicated high
concentrations of DDTs and total PCBs in these samples, and much lower of isomers of
HCHs, HCB and chlordanes (Falandysz et al., 1994a; Tanabe et al., 1993).
PCB-153 was a high contributor of the congener occupying 23 % of the total PCB
content, and together with PCB-138 (18 %) and PCB-180 (13 %) were the most prevalent
members. Samples taken in Gdaňsk in 1990 contained 1.5 ± 1.3 µg.g-1 of total PCBs on a
fat basis while the citizens from inland province, sampled in 1979, contained 1.2 ± 0.4 µg.g1, which seemed to indicate a persistent PCB exposure in Poland.
Among Gdaňsk citizens, randomly selected autopsy samples of liver cancer from dead
persons contained 4.7 µg.g-1 of PCBs, while in all other samples the level was between 0.75
and 1.9 µg.g-1 of PCBs. TCDD toxic equivalent of 13 detectable coplanar members of
PCBs in adipose tissues of Gdaňsk, and Skierniewice inhabitants, was 210 and 190 pg.g-1
on a lipid weight basis, respectively, including 45 and 59 pg.g-1 of non-ortho, 142 and
110 pg.g-1 of mono-ortho and 24 and 16 pg.g-1 of di-ortho chlorobiphenyls. A fingerprint of
chlorobiphenyl composition in the samples examined was virtually the same for human
adipose tissue taken in 1990 from the coastal city of Gdaňsk and in 1979 from the inland
province of Skierniewice, in spite of geographic variations and sampling interval.
Baseline data on the non-ortho coplanar PCBs concentrations in human adipose tissue
from Poland from the same two localities (Gdaňsk and Skierniewice), were published too
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(see Table 10.10-20).
Table 10.1020:
Range of levels of non-ortho coplanar PCBs and
range of their 2378-TCDD TEQ in human tissues
from two localities in Poland (Gdaňsk 1990,
Skierniewice 1979)
PCBs
Range of
concentration
[pg.g-1 fat wt]
TEF
Range of TEQ
[pg.g-1 fat wt]
Mean of TEQ
77
54 - 500
0.01
0.54 - 5.0
2.3
126
41 - 850
0.10
4.1 - 85
34
169
50 - 390
0.05
2.5 - 27
13
Total
145 - 1 740
7.1 - 107.3
49.3
The recorded concentrations were comparable to higher than those reported for other
countries including Czech and Slovak Republics (see Chapter 10.10.2). The levels were
comparable from the both sites. This suggested a slower elimination rate of coplanar
congeners and/or a continuing exposure of Polish population to PCBs.
Tanabe and Falandysz (Tanabe et al., 1993) also compared the previous data on
organochlorine contamination in human adipose fat of Polish cadavers reported by various
researchers so far. Concentrations of PCBs as determined in this study were found to be
somewhat higher than those reported formerly in other regions of Poland (Table 10.10-21).
This was probably due to the identification and determination of large numbers of PCB
components by using capillary GC in this investigation. Other organochlorine insecticide
levels were rather comparable among various study periods reported for various regions in
Poland. The results have shown that DDT levels in the Polish environment and biota were
likely to be declining at a slower rate after withdrawal from use, but the existing levels in
Polish human fat were still higher on the international comparative basis. PCB
contamination in Poles corresponds to that in other industrialised nations.
Organochlorine pesticide residues and PCBs were also determined in human milk in
Croatia (Frkovič et al., 1996). The first evaluation of OCC in breast milk from nursing woman
living in Croatia was done in mid-seventies. During the last two decades a decrease of
OCCs and PCBs is observed in human milk samples collected in the city area of Zagreb.
The first determination of these pollutants in breast milk from two small towns in the
Northern Adriatic area were carried out in 1986/87 and 1989 year. Both locations are
approximately 50 km away from the city of Rijeka, one situated in the nearby Istrian
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peninsula, while the other is on the island of Krk. Frkovič et al. (1996) described the OCCs
and PCBs levels in 31 breast milk samples collected in the Rijeka Clinical Hospital.
The results of the organochlorine pesticide determination in human milk from nursing
women living in the Northern Adriatic region indicate that the observed levels were the
lowest determined in Croatia since the beginning of their survey in mid-seventies. Such a
decline could be a part of an overall tendency that is observed in other countries, as well.
Contrary to the OCCs, PCB level in breast milk was the highest ever observed in Croatia, a
fact that was presently hard to explain. Although PCB use has been restricted, there are still
some sources of PCBs in the environment. No statistically significant difference was
obtained in OCC and PCB levels in human milk regarding mothers´ age, parity, residence,
smoking habitats, weight during pregnancy and milk fat content. Good correlation between
OCCs and PCBs was obtained (r=0.527, p=0.05) indicating the similar fate of this lipophilic
compounds in human body.
Generally, the levels of organochlorine pesticide residues in the breast milk from
women living in this area were by 10 to 50 times lower compared to the previous reported
results and were comparable to the lowest levels observed in Italy and Canada. This could
be the results of constantly decreasing levels observed in Croatia over 20 years, with the last
results regarding the city of Zagreb in 1990/1991.
PCBs are widely distributed in human milk from industrialised countries, while they are
mostly below detection limit in milk from developing countries. The average concentrations
of PCBs in human milk are typically between 500 and 2 000 µg.kg-1 milk fat (Sonawane,
1995). The mean level of PCBs (as Arochlor 1260) in Frkovič study (Frkovič et al., 1996) was
equal to 898 µg.kg-1 milk fat and is the highest reported in Croatia. Regerding the previous
results from the Nothern Adriatic Area, the median value (778 µg.kg-1 milk fat) is by 56 %
higher compared to the content from Istrian location, and three times higher than the median
value from the islands of Krk.
OCCs in human milk were analysed in samples collected over the nine-year period
(1987-1995) from 139 nursing mothers whose children were hospitalised for various
disorders at the Department of Pediatrics, Clinical Hospital Center in Zagreb, Croatia
(Krauthacker et al., 1998). Mothers were not occupationally or accidentally exposed to
organochlorine pesticides or PCBs.
All samples contained p,p´-DDE and PCBs; the median concentrations were 318 µg.kg1 milk fat and 220 µg.kg-1 milk fat, respectively. Higher levels were found in mothers
(N=12) nursing neonates with impaired neurodevelopmental competencies or an
inappropriate arousal reaction. No difference was observed between mothers nursing
children with respiratory or gastrointestinal diseases, urinary tract infections or other
infectious diseases, anemias, prolonged neonatal hyperbilirubinaemias or when children
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were with dermatological findings, congenital malformations or healthy.
Levels of OCPs in human serum samples collected in Croatia are being monitored since
1975 and levels of total PCBs since 1985. No results were however available as far on the
content of individual PCB congeners (Krauthacker et al., 1996). From this reason, samples of
human blood serum were collected from one group from the general donors from the
general population and one group of occupationally exposed workers. From the general
population samples were collected from 14 donors (3 males and 11 females; between1 4 and
83 years old). Fifteen samples were collected from donors who were workers employed
between 3 months and 28 years repairing transformers and capacitors. All donors were
residents of Zagreb, capitol of Croatia. Six indicator PCB congeners (28, 52, 101, 138, 153,
180) and some OCPs (HCB, HCHs, DDTs) were determined.
The median concentrations of the analysed organochlorines are given in Table 10.10-22.
All serum samples contained PCB-138 and PCB-153 and also HCB and p,p´-DDE. The six
PCB congeners were present at higher levels in the exposed workers than in the general
population, but there was no difference between the two groups concerning the
concentration of OCPs. All levels of OCPs and PCBs were fully within the concentration
range found for the same compounds in the general population over the past ten years. The
distribution pattern of PCB congeners in human serum and human milk was shown to
correlate well with Aroclor 1260 (Krauthacker and Reiner, 1994). The sum of the six PCB
congeners found in the analysed serum samples was lower than the total PCB content
determined with Aroclor 1260. The same was found for human milk samples collected in
Zagreb during the same year (Zubčič et al., 1996). This indicates that more than six analysed
PCB congeners should be determined in order to assess the total PCB body burden.
Studies concerning the concentration of OCPs in human breast milk were started in
Estonia in 1971, but data about the content of PCBs in human breast milk were missing.
The determination of PCBs in the breast milk of Estonian women was performed in 1980ies
and the results were compared with the results obtained in other Baltic Sea countries (Roots,
1996). The levels of OCPs and PCBs in Estonian human milk are given in Table 10.10-23.
Table 10.10-23: Concentrations of OCPs and PCBs in Estonian
human milk
[µg.g-1 wet weight]
Year
DDT
1971
DDE
0.026
0.099
0.004-0.050 0.021-0.230
Sum of
DDTs
PCBs
DDE * 100 /
Sum of DDTs [%]
0.125
-
79
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1974
1984
0.021
0.063
0.002-0.080 0.008-0.180
0.084
-
0.006
0.012
0.003-0.011 0.006-0.017
75
95
During the years 1974-1984, decomposition of DDT onto its main metabolite DDE was
increased in the human breast milk from 79 % up to 95 %. As DDE is less toxic to a human
organism than DDT, in 1984 much less OCPs and less toxic compounds got into the
organism of a newborn child than during the years 1971-1974 (Roots, 1996).
A newborn child, weighting 5 kg and drinking 1 kg of a milk a day, intakes the average
of 0.001 mg.kg-1 of summary DDT and 0.002 mg.kg-1 of PCBs a day - that is 5-20 times
less of DDT than in the beginning of seventies. Six years after the total ban of DDT in
Estonia in 1968, the content of its metabolite DDE in human milk rose up to 75-79 %. The
amounts of DDT and DDE consumed by newborn children on the first week after birth were
5.6 µg of DDT and 15.9 µg of DDE a day. During the period of II-IV weeks after birth, the
amounts were respectively 11.2 µg of DDT and 35.4 µg of DDE a day.
It was found, that in the mid-1980ies, the average daily intake of total DDTs and PCBs
by newborn children did not exceed the ADI proposed by the WHO (for DDTs 0.05 mg.kg1 and for PCBs concentration 0.07 mg.kg-1.d-1, exceeding of which caused "Yusho" disease
in Japan in 1968 and in Taiwan in 1979).
The potential human exposure of DDTs and PCBs by daily nutrition, were also studied
(Roots, 1996). Some of the authors claimed, that in the Baltic Sea countries human organism
gets 90 % of toxic compounds from fish. In the end of the 1960ies, the content of DDTs in
daily nutrition of the residents of Estonia was 0.036 mg on the average. According to
certain data, the concentration of DDT in fish was highest 10-11 years after maximum
usage of DDT (in Estonia 1965).
If man eats 30-50 g of fish a day and if the average concentration of biphenyls and DDT
in fish is not higher than it was in mid-1980ies (0.2 mg.kg-1 and 0.1 mg.kg-1), then the
concentration of DDTs and PCBs in the daily nutrition of Estonian residents was 3-5 µg.day1 and 6-10 µg.day-1 respectively (if herring forms the main part of the consumed fish), that
is 0.05-0.08 µg.kg-1 of DDT a day and 0.10-0.17 µg.kg-1 of PCBs a day (if a man weights
60 kg). Similar results have been obtained in Finland and Sweden (Roots, 1996).
In the beginning of 1980ies, the content of DDT in the daily nutrition was as follows - in
former Soviet Union - 10-75 µg, in USA - 2-145 µg, in Great Britain - 27-44 µg, in
Canada - 18 µg, in Italy - 52 µg, in the Netherlands - 60 µg and in Bulgaria - 60 µg. At the
same time, the content of summary DDTs and PCBs in the Baltic fish ranged from 0.017http://www.recetox.muni.cz/old/index-old.php?language=en&id=4386 (26 of 27) [26.1.2007 8:27:21]
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0.030 mg.kg-1 and from 0.035-0.060 mg.kg-1. Daily concentration of DDTs and PCBs in
nutrition (fish) decreased down to 0.5-1.5 µg.day-1 and 1.1-3.0 µg.day-1 respectively, that
was 0.008-0.025 µg.kg-1 of DDTs a day and 0.018-0.050 µg.kg-1 of PCBs a day.
On the basis of these data and an overall no-effect level for toxicity of DDT of 0.25 mg.
kg-1 body weight.day-1 in humans, a daily intake of this scale would not involve any human
cancer risk. Thus, if a 60 kg person consumed 30-50 g.day-1 of fish containing 17-30 µg.kg1 of DDT and its metabolites, the daily intake would be maximal of 0.025 µg.kg-1 body
weight. This would constitute 1/800 of the ADI and 1/12 000 of the lowest dose of
unmetabolized DDT, which caused liver tumours in male mice of the most sensitive strain
tested (Roots, 1996).
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Persistent, Bioaccumulative and Toxic Chemicals in Central
and Eastern European Countries - State-of-the-art Report
Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
10.10.2 Polychlorinated dibenzo-p-dioxins and dibenzofurans
Although the world was engaged in professional discussion about the sources of PCDDs/
Fs, their fate in the environment and their influences and risk to various organisms, in the
CEE countries concrete information about contamination of human tissues practically does
not exist (Holoubek et al., 1995). During 1965 to 1968, 80 workers who had been engaged of
2,4,5-sodium trichlorophenoxyacetate and butylester of trichlorophenoxy-acetate acid
became ill (Pazderová-Vejlupková et al., 1981). The cause of the illness was 2,3,7,8tetrachlorodibenzo-p-dioxin. This incidence of mass intoxication occurred during a time
when alkaline hydrolysis of tretrachlorobenzene at atmospheric pressure was used to
increase and shorten reaction time, and probably during the same time the mother liquor,
which was originally disposed of, was put back into production. The concentration of
TCDD in the work atmosphere was never measured; however, TCDD was found in final
product - Arboricide E - and several years later, was also found in the building and on wall
paintings. This contamination is still measurable. It was something as small "Seveso" in the
former Czechoslovakia. A 10-year study has been conducted for 55 exposed individuals.
The majority of the patients developed chloracne, and 11 manifested porphyria cutanea
tarda. Approximately one-half of the patients suffered from metabolic disturbances, i.e.
pathologically elevated lipids with abnormalities in the lipoprotein spectrum, and two-fifths
of the patients had pathological changes in the glucose tolerance test. One third of the
patients had biochemical deviations indicative of a mild liver lesion. Histological
examination revealed light steatosis, or periportal fibrosis, or activation of Kupffer cells. In
17 persons symptoms of nervous system focal damage existed, with predominance of
peripheral neuron lesion of the lower extremities. The majority of patients suffered from
various psychological disorders. To the 1981, if this results were published, two patients
have died of bronchogenic lung carcinoma; one of liver cirrhosis; one of a rapidly
developed, extremely unusual type of atherosclerosis precipu cerebri, and some patients
have died in traffic accidents. The conditions of most other patients have improved. The
measurements of air in working hall and contents of PCDDs/Fs in wall and soil, were
performed few years ago, but results never been published.
Informative measurements for the obtaining the first information concerning the
contamination of human tissues by PCDDs/Fs and PCBs-dioxin like were done in cooperation of Czech and Slovak scientist with people from CDC Atlanta, USA (Holoubek et
al., 1995). Samples of human adipose tissues from two different sites of the former
Czechoslovakia were used. Seven samples (from Prague and Michalovce) were used for
determination of PCDDs/Fs, PCBs and HCB, HCHs and DDTs. The results of PCBs and
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OCCs determination confirm trends describe by Schoula (Schoula et al., 1996, 1998)
concerning the higher level of contamination in Michalovce region. The level of planar
PCBs were lower than in Poland (Falandysz et al., 1994b)
Only 2,3,7,8-substituted congeners of PCDDs and PCDFs, especially hepta- and
octachlorinated in adipose tissue, were found. This was in agreement with previous studies
(Ahlborg et al., 1992). While there were some differences in congeners patterns from some
countries (Jensen, 1989), in general the pattern and levels were similar to previous CDC
studies (Patterson et al., 1994). The I-TEQ values for the coplanar PCBs made a major
contribution to the total TEQs in these samples which were similar to reports from Japan
and Sweden (Patterson et al., 1994). The percent of contribution of the PCDFs to the total
TEQ in these samples was 2 to 3 times higher than the PCDDs, which was very different
from data from other countries. The high I-TEQ values for the PCDFs in these samples
from Czech and Slovak Republics were due to the relatively high levels of 2,3,4,7,8pentaCDF (range of 21 to 44 ppt). The average concentration of 2,3,7,8-TCDD was 1.9 pg.g1, which is low compared to other industrialised countries. Relatively high concentrations of
octa-CDD (100 to 460 ppt) were found in the human tissues considering that this isomer
was found in low concentration in pork and beef. This suggests another source on
contamination for this congener (Table 10.10-24).
Table 10.10-24: The range of concentrations of PCDDs/Fs, PCBs and
OCCs in human adipose tissue from Czech and
Slovak Republics (n=7) (Holoubek et al., 1995a)
I-TEQ [pg.g-1]
PCDDs
PCDFs
Planar
PCBs
Total ITEQ
[pg.g-1]
6.4-10.7 12.0-25.2 6.0-32.6 31.3-59.4
Sum of
Sum of Sum of
HCB
HCHs
DDTs PCBs
-1]
[µg.g
[µg.g-1]
[µg.g-1] [µg.g-1]
0.0390.251
0.2533.395
0.5659.966
1.1573.525
Sum of HCHs - sum of isomers alpha-HCH, beta-HCH, gamma-HCH
Sum of DDTs - sum of isomers and metabolites of DDT (o,p´-DDT, p,p´-DDE,
o,p´-DDD, p,p´-DDD, p,p´-DDT)
WHO/EURO measured the levels of PCBs and PCDDs/Fs in human milk in various
European countries including the countries of CEE region. The values of TEQ in pg.g-1 fat
for PCDDs/Fs were 18.4 pg TEQ.g-1 fat in Uherské Hradiště and 12.1 pg TEQ.g-1 fat in
sample from Kladno. In Slovakia, the values of TEQ were 15.1 pg TEQ.g-1 fat in district
Michalovce and 12.6 pg TEQ.g-1 fat in Nitra.
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Persistent, Bioaccumulative and Toxic Chemicals in Central
and Eastern European Countries - State-of-the-art Report
Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
10.10.3 References
Ahlborg U. G., Brouwer A., Fingerhut M. A., et al. (1992): Impact of polychlorinated
dibenzo-p-dioxins, dibenzofurans, and biphenyls on human and environmental health, with
special emphasis on application of the toxic equivalency factor concept. Eur. J. Pharmacol.
228, 179-199.
Bartoniček F., Rob O. (1991): Residues of selected organochlorine compounds in the food
chain and the exposition of human organisms. Proceedings from the XV. Symposium on the
Food Chain Contamination, Košice, Slovakia. 35-38.
Bencko V., Skulová Z., Krečmerová M., Djien Lie, A. K. (1998): Selected
polyhalogenated hydrocarbons in breast milk. The Czech Republic data from the 2nd round
of WHO-co-ordinated exposure study. Toxicol. Lett. 96, 341-345.
Czaja K., Ludwicki J. K., Góralczyk K., Strucinski P. (1997a): Effect of age and number
of deliveries on mean concentration of organochlorine compounds in human breast milk in
Poland. Bull. Environ. Contam. Toxicol. 59, 407-413.
Czaja K., Ludwicki J. K., Goralczyk K., Strucinski P. (1997b): Organochlorine
pesticides, HCB and PCBs in human milk in Poland. Bull. Environ. Contam. Toxicol. 58,
769-775.
Czaja K., Ludwicki J. K., Góralczyk K., Strucinski P. (1997c): Exposure of infants to
polychlorinated biphenyls and organochlorine pesticides from mother´s milk.
Organohalogen Compounds 38, 109-112.
Czaja K., Ludwicki J. K., Goralczyk K., Strucinski P. (1999a): Effect of changes in
excretion of persistent organochlorine compounds with human breast milk on related
exposure of breast-fed infants. Arch. Environ. Contam. Toxicol. 36, 498-503.
Czaja K., Ludwicki J. K., Goralczyk K., Strucinski P. (1999b): Persistent
organochlorine compounds in breast milk from two consecutive lactation of the same
donors. Organohalogen Compounds 44, 89-92.
Černá M., Bencko V. (1999): Polyhalogenated hydrocarbons: body burden of the Czech
http://www.recetox.muni.cz/old/index-old.php?language=en&id=4388 (1 of 6) [26.1.2007 8:27:29]
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and Slovak populations. I. Polychlorinated biphenyls. Centr. Eur. J. Publ. Hlth. 7, 67-71.
Černá M., Svobodník J., Čížková M., Krýsl S., Šmíd J. (2000): Levels of PCBs, PCDDs
and PCDFs in human milk of mothers living in four districts of the Czech Republic. Centr.
Eur. J. Publ. Hlth., 8, in press.
Černá M., Balasová V., Čížková M., Grabic R., Šmíd J. (2000): PCB congeners,
PCDDs, and PCDFs in the adipose tissue of the Czech population. PCB Workshop. Recent
Advances in the Environmental Toxicology and Health Effects of PCBs. Lexington,
Kentucky, USA, 09-12/04/2000 (poster).
Duarte-Davidson R., Burnett V., Waterhouse K. S., Jones K. C. (1991): A congenerspecific method for the analysis of PCBs in human milk. Chemosphere 23, 119-131.
Falandysz J., Yamashita A., Tanabe S., Tatsukawa R. (1994a): Congener-specific data
of polychlorinated biphenyl residues in human adipose tissue in Poland. Sci. Total Environ.
149, 113-119.
Falandysz J., Kannan K., Tanabe S., Tatskukawa R. (1994b): Concentrations and
2,3,7,8-tetrachlorodibenzo-p-dioxin toxic equivalents of non-ortho coplanar PCBs in
adipose fat of Poles. Bull. Environ. Contam. Toxicol. 53, 267-273.
FAO (1993): Fishery Statistics, Commodities, Food Balance Sheets 77, 337.
Frkovič A., Živkovič A., Alebič-Juretič A. (1996): Organochlorine pesticide residues and
polychlorinated biphenyls in human milk from Northern Adriatic region (Croatia).
Fresenius Environ. Bull. 5, 474-481.
Georgii S., Bachour G., Elmadfa J., Brunn H. (1995): PCB congeners in human milk in
Germany from 1984/85 and 1990/91. Bull. Environ. Contam. Toxicol. 54, 541-545.
Hajšlová J., Holadová K., Kocourek V., Poustka J., Cuhra P., Ravrdino V. (1993):
Determination of PCBs in fatty tissues by means of several detection techniques. Z.
Lebensm. Unters. Forsch. 197, 562-569.
Heinisch E., Wenzel-Klein S., Stechert J., Uhnák J., Ludwicki J. K., Bartonicek F.,
Rob O. (1994): Butter as a matrix for indication of low volatile organochlorine compounds.
In: Schadstoffatlas Osteuropa (Heinisch E, Wenzel-Klein S, Kettrup A, Eds.).
Verlagsgesellschaft AG & Co. Kg. Landsberg, Germany. 69-74.
Holoubek I., Dušek L., Mátlová L., Čáslavský J., Patterson D. G., Turner W. E.,
Pokorný B., Bencko V., Hajšlová J., Kocourek V., Schoula R., Kočan A., Chovancová
J., Petrik J., Drobná B. (1995): The fate of selected organic compounds in the
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environment Part XXVI. The contents of PCBs and PCDDs/Fs in human fat in Czech and
Slovak Republics. Organohalogen compounds, 26,257 - 260.
Jensen A. A. (1989): Background levels in human milk. In: Gunter F. A., (Ed.): Residue
Reviews. Springer-Verlag, New York, 104-107.
Jensen A. A., Slorach S. A. (1991): Chemical contaminants in human milk. CRC Press
Inc., Boca Raton.
Johansen H. R., Becher G., Polder A., Skaare U. J. (1994): Congener-specific
determination of polychlorinated biphenyls and organochlorine pesticides in human milk
from Norwegian mothers living in Oslo. J. Toxicol. Environ. Hlth. 42, 157-171.
Kočan A., Petrik J., Drobná B., Chovancová J. (1994a): Levels of PCBs and some
organochlorine pesticides in the human population of selected areas of the Slovak Republic.
I. Blood. Chemopshere 29, 2315-2325.
Kočan A., Petri J., Drobná B., Chovancová J. (1994b): Levels of PCBs and some
organochlorine pesticides in the human population of selected areas of the Slovak Republic.
II. Adipose tissue. Organohalogen Compounds 21, 147-151.
Kočan A., Drobná B., Petrik J., Chovancová J., Patterson Jr. D. G., Needham L. L
(1995): Levels of PCBs and selected areas of the Slovak Republic. Part III. Milk.
Organohalogen Compounds 26, 187-192.
Kočan A., Patterson Jr., D. G., Petrik J., Turner W. E., Chovancová J., Drobná B.
(1996): PCDD, PCDF and coplanar PCB levels in blood from the human population of the
Slovak Republic. Organohalogen Compounds 30,137-142.
Kočan A., Petrik J., Drobná B., Chovancová J., Jursa S., Pavúk M., Kovrižnych J.,
Langer P., Bohov P., Tajtaková M., Suchánek P. (1999): The environmental and human
load in the area contaminated with polychlorinated biphenyls. Prepared by Institute of
Preventive and Clinical Medicine, Bratislava, Slovakia for Ministry of the Environment,
Slovakia, February, 240 pp.
Koopman-Esseboom C., Huisman M., Weisglas-Kuperus N., van der Paauw, C. G.,
Tuinstra L. G. M. T., Boersma E. R., Sauer P. J. J. (1994): PCB and dioxin levels in
plasma and human milk of 418 Dutch woman and their infants. Predictive value of PCB
congener levels in maternal plasma for fetal and infant´s exposure to PCB and dioxins.
Chemopshere 28, 1721-1732.
Kliment V., Kubínová R., Kazmarová H., Havlík B., Šišma P., Ruprich J., Černá M.,
Kódl M. (1997): System of monitoring the environmental impact on population health of
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the Czech Republic. Centr. Eur. J. Publ. Hlth. 5, 107-116.
Krauthacker B., Reiner E. (1994): Intake of organochlorine compounds and levels in
population groups. In: Richardson M. (Ed.): Chemical Safety, International Reference
Manual, VCH Verlagsgesellschaft mbH, Weinheim, 157-170.
Krauthacker B., Kralj M., Reiner E. (1996): PCB congeners and organochlorine
pesticides inhuman serum samples collected in Zagreb, Croatia, during 1994/1995.
Organohalogen Compounds 30, 143-145.
Krauthacker B., Reiner E., Votava-Raič A., Tješič-Drinkovič D., Batinič D. (1998):
Organochlorine pesticides and PCBs in human milk collected from mothers nursing
hospitalized children. Chemopshere 37, 27-32.
Ludwicki J. K., Góralczyk K. (1994): Organochlorine pesticides and PCBs in human
adipose tissues in Poland. Bull. Environ. Contam. Toxicol. 52, 400-403.
Patterson Jr. D. G., Todd G. D., Turner W. E. et al. (1994): Levels of non-ortho
substituted (copalnar), mono- and do-ortho-substituted polychlorinated biphenyls, dibenzop-dioxins and dibenzofurans in human serum and adipose tissues. Environ. Hlth. Perspect.
Suppl. 102, 195-204.
Pazderová-Vejlupková J., Němcová M., Pícková J., Jirásek L., Lukáš E. (1981): The
development and prognosis of chronic intoxication by teatrachlorodibenzo-p-dioxin in men.
Arch. Environ. Hlth. 36, 5-11.
Petrik J., Chovancová J., Kočan A., Holoubek I. (1991): Project TOCOEN: The fate of
selected organic pollutants in the environment. Part VIII. PCBs in human adipose tissues
from different regions of Slovakia. Toxicol. Environ. Chem. 34, 13-18.
Prachar V., Veningerová M., Uhnák J., Kovačičová J. (1994): Polychlorinated biphenyls
in mother milk and adapted cow´s milk. Chemopshere 29, 13-21.
Prachar V., Veningerová M., Uhnák J., Pribela A. (1996): Persistent organochlorine
compounds in cow´s milk and butter. Fresenius Environ. Bull. 4, 413-417.
Reichrtová E., Ciznár P., Prachar V., Palkovicová L., Veningerová M. (1999): Cord
Serum Immunoglobulin E Related to the Environmental Contamination of Human Placentas
with Organochlorine Compounds.
Reichrtová E., Prachar V., Palkovicová L. (1999): Contamination of human placentas
with selected organochlorine compounds in five Slovak regions related to different
environmental characteristics.
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Reichrtová E., Prachar V., Palkovicová L., Ciznár P. (1999): Effect of organic
xenobiotics in human placentas on allergic sensitization of newborns. Toxicol. Lett.
Roots O. (1996): Toxic chloroorganic compounds in the ecosystem of the Baltic Sea.
Ministry of the Environment of Estonia. Environment Information Centre (EEIC). Tallinn,
Estonia, 144 pp.
Ruprich J. (1997 - 1999): System of monitoring the environmental impact on population
health of the Czech Republic. Health risk assessment of dietary exposures to the selected
chemical substances in the Czech Republic. Annual Reports for the years 1996 - 1998.
National Institute of Public Health, Prague.
Schechter E., Fürst P., Fürst C., Päpke O., Ball M., Ryan J. J., Cau H. D., Dai L. C.,
Quynh H. T., Cuong H. Q., Phuong N. T. N., Phiet P. H., Beim A., Constable J., Startin
J., Samedi M., Seng Y. K. (1994): Chlorinated dioxins and dibenzofurans in human tissue
from general populations: A selective review. Environ. Health Perspect., 102, Suppl. 1, 159171.
Schoula R., Hajšlová J., Bencko V., Poustka J., Holadová K., Vízek V. (1996):
Occurrence of persistent organochlorine contaminants in human milk collected in several
regions of Czech Republic. Chemosphere 33, 1485-1494.
Schoula R., Hajšlová J., Gregor P., Kocourek V., Bencko V. (1998): Persistent
organochlorine contaminants in human tissues of the Czech and Slovak populations.
Toxicol. Environ. Chem. 67, 263-274.
Sonawane B. R. (1995): Chemical contaminants in human milk: an overview. Environ.
Hlth. Perspect. 103, 197-205.
Strnad Z. (1991): The contaminants in the food- and feedstocks as well as in products of
animal origin and water. State in 1991. The Informative Bulletin of the Veterinary Service,
Czech Republic. A1/1992.
Ševčík J., Leníček J., Čítková M., Sekyra M., Rychlíková E. (1985): Some knowledge
from observing of polychlorinated biphenyls. Cs. Hyg. 30, 499-504 (in Czech).
Tanabe S., Falandysz J., Higaki T., Kannan K., Tatsukawa R. (1993): Polychlorinated
biphenyl and organochlorine insecticide residues in human adipose tissue in Poland.
Environ. Pollut. 79, 45-49.
Uhnák J., Veningerová, M., Prachar V., Kovačičová J. (1995): Organochlorine
pollutants in a heavily contaminated locality in the vicinity of a chemical plant. Arch. Ochr.
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Srod.
Van den Berg M., Birnbaum L., Bosveld A. T. C., Brunström B., Cook P., Feeley P.,
Giesy J. P., Hanberg A., Hasegawa R., Kennedy S. W., Kubiak T., Larse J. C., van
Leeuwen F. X. R., Djien Liem A. K., Nolt C., Peterson R. E., Poellinger L., Safe S.,
Schrenk D., Tillitt D., Tysklind M., Younes M., Waern F., Zacharewski T. (1998):
Toxic equivalency factors (TWFs) for PCBs, PCDDs, PCDFs for humans and wildlife.
Environ. Health Perspect., 106, 775-792.
WHO/EURO (1996): Levels of PCBs, PCDDs and PCDFs in human milk. Second round
of WHO-co-ordinated exposure study. Environmental Health in Europe, 3.
Zubčič S., Krauthacker B., Kralj M. (1996): Distribution of PCB congeners inhuman
milk. In: Abstracts of Lectures and Poster Contributions, 1st Croatian Congress of
Toxicology, Zagreb, p. 20.
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Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
11.5 Polychlorinated naphthalenes
have summarised some data on the concentration of the total PCNs in
the environment, recently. The environmental contamination with PCNs, were recorded in
many parts of the world and these compounds are, in present time, ubiquitous global
pollutants.
Falandysz (1998)
The concentration of PCNs in some environmental matrices
Site
Concentration
Reference
Ambient air [pg.m-3]
150 000 - 1 400 000 Erickson et al., 1978
USA - manufacturing site
Germany - urban area
60
- rural area
Dörr et al., 1996
24
Canada - urban area, winter 1996
USA - urban area, winter 1995
17 (12 - 22)
68 ± 42 (24 - 180)
Harner and Bidleman,
1997
Harner et al., 1997
Arctic - summer 1996
Sediments [ng.g-1 dry wt]
7.3 - 100
Japan
Poland - Visla River
Saginaw Bay and Saginaw River
Basin, USA
7.7
Imagawa and
Yamashita, 1996
Falandysz et al., 1996
Giesy et al., 1997
< 500 - 1 000
pg.g-1 (wet weight)
Baltic Sea - Gotland
7.6
Sweden - Background site
0.23
- Polluted site
6.4 - 270
- Various rivers
0.62 - 3.1
Water [ng.l-1]
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Fresh water (PCB polluted)
0.89
Percolating water, city dump site
(Stockholm, Sweden)
2.6
Järnberg et al., 1997
There is a similarity in fingerprint of tetra- to hepta-CNs in such abiotic environmental
matrices as gas phase ambient air and fresh water collected in Sweden (Järnberg et al., 1997)
to river sediments in Poland and also to subsurface marine plankton (Falandysz et al., 1996;
Falandysz and Rappe, 1996).
Polychlorinated naphthalenes (PCNs) can accumulate in wildlife and they were detected
in biotic samples from many regions. Some examples are shown in the following table.
The concentrations of PCNs in biota [ng.g-1] (tetra- to hepta-CNs)
Site
Concentration
Reference
Fish (flesh and liver), lakes and rivers,
Sweden
2.6 - 360
Herring, Baltic Sea
0.98 - 26
Fish (whole), Baltic Sea, Gulf of
Gdaňsk
8.9 - 290
Falandysz et al., 1996
Fish (flesh), Saginaw Bay, USA
0.16 - 33
Giesy et al., 1997
Guillemot, Uria aalgae, Baltic Sea
84 - 220
Järnberg et al., 1997
Järnberg et al., 1997
Piscivorous bird eggs, Saginaw Bay,
USA
20 - 1 000
Giesy et al., 1997
White-tailed sea eagle, Haliaeetus
albicilla, Sweden
120 - 130
Järnberg et al., 1997
Otter, Lutra lutra, Sweden
2.6 - 7.0
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Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
11.6 References
Dörr G., Hippelein M., Hutzinger O.(1996): Baseline contamination assessment for a new
resource recovery facility in Germany. Part V: Analysis and seasonal/regional variability of
ambient air concentrations of PCN. Chemosphere 33, 1563-1568.
Falandysz J. (1997): Bioaccumulation and biomagnification features of polychlorinated
naphthalenes. Organohalogen Compounds 32, 374-379.
Falandysz J. (1998): Polychlorinated naphthalenes: an environmental update. Environ.
Pollut. 101, 77-90.
Falandysz J., Rappe C. (1996): Spatial distribution in plankton and bioaccumulation
features of PCNs in a pelagic food chain in the southern part of the Baltic proper. Environ.
Sci. Technol. 30, 3362-3370.
Falandysz J., Strandbers L., Berqvist P.-A., Kulp S. E., Strandberg B., Rappe C.
(1996): Polychlorinated naphthalenes in sediment and biota from the Gdaňsk Basin. Baltic
Sea. Environ. Sci. Technol. 30, 3266-3274.
Giesy J. P., Jude D. J., Tillitt D. E., Gale R. W., Meadows J. C., Zajicek J. L.,
Peterman P. H., Verbrugge D. A., Sanderson J. T., Schwartz T. R., Tuchman M.
(1997): PCDDs/Fs, PCBs and 2,3,7,8-TCDD equivalents in fishes from Saginaw Bay.
Michigan. Environ. Toxicol. Chem. 16, 713-724.
Harner T., Bidleman T. F..(1997): Polychlorinated naphthalenes in urban air. Atmos.
Environ. 31/32, 4009-4016.
Harner T., Bidleman T. F., Kylin H., Strachan W., Halsall C. (1997): Polychlorinated
naphthalenes in urban and Arctic air. Organohalogen Compounds 33, 134-139.
Imagawa T., Yamashita N. (1996): Estimation of emission sources of polychlorinated
naphthalenes using fingerprint method for isomer composition. J. Environ. Chem. 6, 495501.
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Järnberg U., Asplund L., de Wit C., Egeback, A.-I., Widequist U., Jakobsson E.
(1997): Distribution of polychlorinated naphthalene congeners in environmental and sourcerelated samples. Arch. Environ. Contam. Toxicol. 32, 232-245.
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and Eastern European Countries - State-of-the-art Report
Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
12.2 Study of effects of PBT compounds
12.2.1 Biochemical monitoring
The objective of biochemical monitoring is to assess actual toxic effects of
contamination by measuring responses of specific biochemical parameters (biomarkers) to
the most important modes of toxic action. Along with chemical analyses of some major
groups of contaminants, this approach to the monitoring of aquatic pollution is becoming a
part of ecotoxicological risk assessment.
Candidate biochemical in vivo markers should indicate exposure to or specific noxious
effects of aquatic contaminants. Only such biochemical parameters are considered suitable
whose modulation due to chemical contamination is sensitive enough. In view of a variety
of mechanisms of adverse effects of xenobiotics, one biomarker is insufficient and it will be
necessary in the near future to develop a battery of sensitive biomarkers responding to
major modes of action of contaminants including dioxin-like toxicity and oxidative stress.
Biochemical markers of dioxin-like toxicity and oxidative stress were investigated in
hepatic microsomal fractions of bream (Abramis brama) and perch (Perca fluviatilis)
collected in August 1996 at six sites of the Elbe river (Czech Republic) (Machala et al.,
2000). Concentrations of polychlorinated biphenyls (PCBs) and the organochlorinated
pesticides DDT, hexachlorobenzene (HCB) and hexachlorohexane (HCH) and their
metabolites were determined in fish muscles to screen contamination rates of the sampling
sites (Table 12.2-1). The results of chemical analyses indicate that fish were contaminated
by PCBs already at site 1 situated upstream from the Pardubice industrial area. Significantly
higher PCB contamination rates were found at sites 5 and 6, but even here the
concentrations in muscle tissue were below maximum value tolerated in the Czech
Republic. The concentrations of DDT, its metabolites, and HCB at sites 5 and 6 were also
rather high. On the other hand, lindane and other HCH isomers were present at very low
concentrations only (maximum of 0.002 µg.kg-1 fresh weight). The bioaccummulation of
chlorinated aquatic contaminants was apparently higher in bream than in perch muscle
tissues.
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Table 12.2-1:
Sampling sites, number of samples and
concentration of contaminants in fish muscle [mg.kg1 fresh weight]
Sampling site Species (n) Age [years] Sum of PCB
1 Opatovice bream (5)
perch (8)
2 Valy
perch (7)
3 Lysá n.L. bream (4)
perch (3)
4 Obříství
bream (5)
perch (10)
5 Děčín
bream (4)
6 Hřensko
bream (4)
5-6
2-5
3-4
3-7
4-7
4-8
5-8
6-9
5-7
0.111
0.038
0.096
0.174
0.069
0.187
0.050
0.307
0.251
Sum of DDT
+DDE
0.030
0.010
0.008
0.018
0.008
0.026
0.007
0.093
0.087
HCB
0.001
0.001
0.002
0.003
0.002
0.002
0.001
0.023
0.028
The dioxin-like toxicity includes effects, whose activation is connected with the
interaction of the toxicant with a certain cellular receptor (Ah-receptor). This interaction
results in increased metabolic activation of promutagens and procarcinogens, increased
cellular proliferation, neurotoxicity, endocrine dysbalance, etc. Oxidative stress is one of the
important manifestations of general stress caused by pollutants. It is defined as a dysbalance
between the natural production of prooxidants and the levels of antioxidant defence
systems. Exposures to xenobiotics are followed by changes in the levels of certain enzymes
involved in prooxidative processes. Such changes can result in increased susceptibility of
membrane lipids to oxidative damage as indicated by the level of Fe(II)/NADPH-induced
lipid peroxidation in vitro in the hepatic microsomal fraction.
In this study, induction of the cytochrome P4501A-dependent 7-ethoxyresorufin Odeethylase (EROD) activity was used as the biomarker of dioxin-like toxicity, and the
activation of microsomal glutathione S-transferase (mGST) and in vitro susceptibility to
lipid peroxidation were chosen as the biochemical markers of oxidative stress in fish.
Biochemical markers in hepatic tissue of bream and perch from the same sampling sites
were induced in a very similar way (Figs. 12.2-1 - 12.2-3). Sampling site 1 was taken as a
reference site with a low contamination rate. The EROD activity, as the specific biomarker
of exposure to planar organic contaminants with dioxin-type toxic potencies, was
significantly increased at sites heavily contaminated by persistent chlorinated chemicals.
Although the concentrations of PCBs and DDT metabolites were higher in bream than
perch tissues; the EROD activity was higher in perch, which were also found to be more
susceptible to oxidative damage to cellular membranes measured as Fe/NADPH-enhanced
in vitro lipid peroxidation. Both oxidative stress parameters under study were significantly
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increased at sampling sites 2 and 6 (Fig. 12.2-3). A comparison of analytical data with
increased values of biomarkers at the two sampling sites let us assume that oxidative stress
found at site 2 was probably caused by other than the monitored contaminants. The
activation of mGST directly correlates with the increase of prooxidative processes. On the
other hand, lipid peroxidation in vitro is not an unambiguous parameter as shown in a recent
field study in roach. Increased or decreased lipid peroxidation in vitro can be found in
hepatic microsomal samples of fish collected at contaminated sites. This difference in the
modulation between the two oxidative stress parameters can be explained as a result of
increased capacity of antioxidant systems accompanied by a less severe damage to
membrane phospholipids.
In conclusion, the hepatic microsomal EROD activity was shown to be a suitable
biomarker responding to the dioxin-like toxicity in both bream and perch. The activation of
mGST was found to be a sensitive biochemical marker of oxidative stress in these fish
species. Practical application of Fe(II)/NADPH-enhanced in vitro lipid peroxidation as
another candidate of oxidative stress indicator will require a more detailed explanation of its
modulation mechanisms.
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12.2.2 The study of PAH phytotoxicity
Polycyclic aromatic hydrocarbons (PAHs) participate to a considerable extent in the
increasing antropogenic pollution of environment. These persistent organic compounds
penetrate into the food-chain and can operate as potential carcinogens, mutagens and
teratogens. In this connection it is necessary to study the effect of selected PAHs on higher
plants, which are a dominant component of terrestrial ecosystems, having the ability of
taking up those compounds from the environment. These compounds can, depending on the
time and intensity of influence, evoke acute, chronic and latent injury of plants, above all in
an interaction with further environmental factors. Long-term influence of toxicants can
affect the structure and function of ecosystems (diversity of plant species, reduction of
biomass production, reduction of O2 production and/or the degradation of the natural
environment).
Plants growing in soil can accept PAHs in several ways: a) uptake of PAHs from the
soil solution via the root tissue, b) absorption across the root surface, c) foliar uptake of
PAHs volatilising from the soil surface, d) absorption from the atmosphere by the leaf
surface, e) some PAHs can be synthetised by some plant cells. Probably the most important
source of PAHs for plants is the atmospheric deposition causing soil contamination.
The rate of uptake is affected by a number of factors (concentration and physicochemical properties of the compound, soil type, the content of organic soil mass, pH,
humidity, temperature, plant species, etc.).
To our best knowledge, there is no comprehensive work dealing with uptake,
translocation and metabolic transformations of PAHs in plants. It is generally accepted, that
the pollutants are able to penetrate to all plant organs, but the mechanisms involved may be
different. Transport through cuticula and biological membranes is probably facilitated by
lipophilic nature of PAHs. This idea was supported by findings of high amount of
accumulated PAHs in leaves with thick layer of cuticular waxes, like conifer needles.
A little bit more complicated situation is in the soil compartment, where affinity of
organic molecules to soil particles may influence the uptake rate by roots. The more
hydrophobic species of PAHs (with higher value of octanol-water separation coefficient,
Kow) are more firmly bound to organic particles, which contribute to preferential uptake of
lower-molecular compounds by the roots. Several other soil factors (temperature, moisture,
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acidity, organic matter content, etc.) may change the mobility of PAHs molecules in the
soil.
The radial and longitudial transport within a plant should be, at least theoretically, not
very easy, because of large dimensions and lipophilic nature of PAHs molecules
(particularly of compounds with higher Kow) but quantitative experimental data are still
lacking. Nevertheless, translocation of PAHs from one (exposed) organ to other, was
observed by several authors. Both xylem and phloem transport systems may be involved.
Plants can metabolise a great number of xenobiotics ranging from highly polar to
nonpolar xenobiotics. Plant metabolism of PAHs is species specific, and in a given plant
may be restricted at a specific tissue or organ, and temporally isolated to a certain
developmental stage. Extent of transformation also depends on the PAH compound. In
general, lower molecular weight two- and three ringed PAHs (naphtalene, anthracene,
phenanthrene) should be biodegraded more rapidly than higher molecular weight fiveringed compounds (e.g. perylen, benzo(a)pyrene, dibenzo(a,h)anthracene); angular may be
considered more stable than linear species.
Plant metabolism can be divided into three phases. Phase I consist of transformation
reactions, which introduce functional groups (-OH, -NH2, -SH) into various xenobiotic
compounds. Oxidation is the most frequently observed reaction type. Aromatic or alkyl
hydroxylation, nitrogen or sulphur oxidation, epoxidation, as well as N- or O-dealkylation
are the major oxidative processes. In the plant metabolism of exogenous compounds,
hydroxylations of aromatic rings may be catalysed by cytochrome P-450 dependent
systems, peroxidases, or hydroperoxidases. The well-know PAHs such as benzo(a)pyrene
are innocuous by themselves, but can be biologically activated by enzymes to form
epoxides (e.g. cytochrome P-450 catalysed the formation of benzo(a)pyrene-9,10-epoxide)
that are carcinogenic and mutagenic.
Phase II can be subdivided according to the "soluble" or "insoluble" ("bound") nature of
the formed conjugates. The main rection types for soluble conjugates include glucoside,
glutathion, aminoacid, and malonyl conjugation. The substituents are attached to functional
groups existing in the xenobiotics or introduced in Phase I. Xenobiotics can be further
incorporated into biopolymers of the plant cell which are not soluble in the commonly used
solvents ("insoluble" or "bound" residues). Many aromatic or heteroaromatic compounds
with existing or introduced hydroxyl, carboxyl, amino, or sulphydryl groups, are known to
be deposited into lignin or the other cell wall components.
Phase III of plant xenobiotic metabolism involves storage and compartmentation of
soluble conjugates in the vacuole and of insoluble conjugates in the cell wall. It is usually
unclear whether the reactions of phase II and III occur simultaneously or sequentially.
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Polycyclic aromatic hydrocarbons can affect all stages of plant growth from germination
to reproduction. A sensitive response to PAHs loading can be assumed above all in the first
stages of ontogenesis, the germination of seeds and the root elongation. The germination of
the seed is the existential condition of the further development of the plant. In this relatively
short period the plant has not yet sufficient detoxicative ability. The affection of
germination due to the contamination of soils with polyaromatic compounds can be one of
the factors of natural selection and even also of the plant evolution. It can be assumed that
in plants there exists and is further developed the adaptation of germination to those
selection conditions.
The phytotoxic effects of PAHs were studied very intensively (Kummerová et al., 1994,
1997a,b, 1998; Slovák et al., 1995; Kmentová and Kummerová, 1998). The effect was studied of
increasing concentration (10, 100 and 500 mg.l-1) of fluoranthene (FLU) in solution on the
energy of germination and the germination rate seeds of Allium cepa L., Helianthus annuus
L., Lactuca sativa L., Picea abies (L.) Karst., Sinapis alba L., Solanum lycopersicum L.,
Triticum aestivum L., Zea mays L. The content of lipids in the seeds was determined and the
effect of FLU on the uptake of water by the seeds evaluated.
The obtained results demonstrated that the increasing FLU concentration inhibited the
energy of germination and the germination rate of seeds of all plant species. The species
studied showed different sensitivity to the content of FLU. The effect of increasing FLU
concentration was reflected more conspicuously in plant species with a higher content of
lipids in the seed (Helianthus annuus L., Lactuca sativa L., Picea abies (L.) Karst.,
Solanum lycopersicum L.). The inhibition of germination maked deeper significantly by the
application of FLU from the beginning of inhibiton. In none of the plant species FLU did
not affected the uptake of water by the seeds.
The influence of interaction of increasing concentration of fluoranthene (FLU - 1, 10,
100, 500 and 1 000 mg.l-1) and higher temperature (15, 20, 25 and 30 °C) and influence of
interaction of increasing concentration of fluoranthene and environmental acidity (pH 4.5,
6.5 and 7.5) on the germination of lettuce (Lactuca sativa L.) was studied.
The obtained results demonstrate the fact that interaction of increasing concentration of
fluoranthene and higher temperature inhibited the germination rate of seeds of lettuce. In
acid, neutral and alkaline environments no significant effect of pH was found on the action
of FLU.
On the basis of our long-term experience lettuce plants (Lactuca sativa) were used for
judging the effect of BaP (benzo(a)pyrene) and FLU (fluoranthene) on the growth of the
plant. The criterion for judging the effect of increasing concentration of BaP and FLU in the
environment and factors affecting BaP and FLU uptake were the lengths of the root and of
the hypocotyl of the tested plants.
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The effect of increasing concentration of benzo(a)pyrene (0.1, 1, 5, 10, 50 and 100 mg.l1), the interaction of sodium humate (10, 100 and 500 mg.l-1) and BaP (0.1 - 10 mg.l-1) and
the effect of environmental acidity (pH 4.5, 6.5 and 8.5) on the growth of the root and the
hypocotyl of lettuce in the dark and in the light was studied.
The results obtained document the fact that increasing BaP concentration (0.1 - 10 mg.l1) stimulated the length of both root and hypocotyl of plant growing in the dark as well as in
the light. Significant inhibition of growth was demonstrated in plants cultivated in BaP of
100 mg.l-1 concentration.
Significantly lower lettuce root and hypocotyl growth in comparison with stimulating
effects of BaP was recorded in the application of all combinations of BaP with sodium
humate.
In neutral and alkaline environments (pH 6.5 and 8.5) no significant effect of pH was
found on the action of BaP. In an acid environment (pH 4.5) a synergic effect of
environmental acidity and BaP toxicity was observed on the inhibition of root elongation.
Different plant organs do not exhibit the same sensitivity to the concurrent concentration
of BaP in the environment.
The plants exhibited a response to toxic compounds only when reached a certain, socalled "threshold concentration". The first part of the experimental study was oriented at the
evaluation of the effects of increasing concentration of FLU in the solution to the elongation
of the root of lettuce plants. The concentration series of FLU was chosen in such a way as to
reflect the possible positive as well as inhibitory action of this compound. The results
obtained documented the fact that increasing FLU concentration (0.1 - 5 mg.l-1) stimulated
the length of root. A drop in stimulation was registered in the highest concentration of FLU
10 mg.l-1. Significantly lower lettuce root growth in comparison with stimulating effects of
FLU was recorded in the application of all combinations of FLU with sodium humate. In an
acid, neutral and alkaline environments (pH 4.5, 6.5 and 8.5) no significant effect of pH was
found on the action of fluoranthene.
In the second part of this study the influence of increasing concentration of fluoranthene
(FLU - 1, 10, 100, 500 and 1 000 mg.l-1) and higher temperature (15, 20, 25 and 30 °C) on
the root elongation of lettuce was studied. The obtained results demonstrate the fact that
interaction of increasing concentration of fluoranthene and higher temperature (15, 20, 25
and 30 °C) significantly stimulated length of root. The interaction of the highest temperature
(30 °C) and increasing concentration of FLU inhibited root growth.
The goal of next study was to compare and to evaluate sensitiveness of two
phytotoxicity tests: the seed germination and the root elongation tests, on the increasing
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loading of environment by polycyclic aromatic hydrocarbons (PAHs) with interaction
factors of external environment, which influenced early stages of plant growth. The
influence of interaction of concentration of fluoranthene (FLU - 1, 10, 100, 500 and
1 000 mg.l-1), higher temperature (15, 20, 25 and 30 °C) and environmental acidity (pH 4.5,
6.5 and 7.5) on the seed germination and the root elongation of lettuce (Lactuca sativa L.)
was studied.
The obtained results demonstrated the sensitive response of the seed germination test
and the root elongation test to increasing loading environment by PAHs and factors
influenced early stages of plant growth. The seed germination test appeared to be more
sensitive to increasing loading of environment by FLU (1, 10, 100, 500 and 1 000 mg.l-1)
and to higher temperature (15, 20, 25 and 30 °C). In acid, neutral and alkaline environments
(pH 4.5, 6.5 and 7.5) no significant difference in sensitiveness of the seed germination test
and the root elongation test was found. A different responsibility of root and hypocotyl
growth of lettuce to the increasing concentration of FLU, higher temperature and change of
environmental acidity was observed.
Relatively few papers deal with the fate of PAHs in plants - i.e., with the accumulation,
translocation and metabolisation. The ability of accumulation is specific of the plant species
and the individual plant organs, depending above all on the value of the octanol-water
coefficient (Kow) of the given compound and on the share of the lipidic fraction in the plant.
These factors also limit the translocation of polyaromates in plants. Some authors describe
the acropetal and basipetal transport, but other sources quote zero or negligible translocation
between the roots and shoot. The phytotoxicity of PAHs is to a considerable extent given by
the ability of the plant organism to metabolise those substances.
The study of the uptake of organic xenobiotic compounds by the plants is of
fundamental importance for evaluating of their role in food chain (bioaccumulation,
transformation, toxicity). Organic pollutants taken up by a plant can affect a number of its
biochemical and physiological processes, which are integrated in the overall growth rate.
Measurement of the growth rate from dry mass increments is thus a suitable measure for
assessing of the effect of FLU on plants.
The influence of increasing concentration of fluoranthene (FLU) in the nutrient solution
(10, 100 and 1 000 mg.l-1) on the growth, the content of assimilation pigments and the rate
of photosynthesis of maize plants was studied. Accumulation of FLU in individual leaves
and other organs was also measured.
As early as after 10 days of cultivation a significant inhibition of the root and shoot
growth was found in plants at FLU concentrations of 100 and 1 000 mg.l-1 significant drop
of the content of the chlorophyll a was registered. After 24 days of cultivation, in plants
from all treatments a significant inhibition of root and shoot growth was observed and the
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concentration of photosynthetic pigments was also much lowered. Net photosynthetic rate
was significantly inhibited in plants from FLU 100 and FLU 1 000 treatments.
The highest concentration of FLU was found in roots of the experimental plants from all
treatments during the whole period of cultivation. Translocation of some amount of FLU
into the aboveground parts was also confirmed. The accumulation of FLU in all plant parts
increased significantly with the length of cultivation.
From the results it is evident, that the content of photosynthetic pigments, particularly
chlorophyll a, was primarily affected, and subsequently the uptake of CO2. A significant
lowering of the content of chlorophyll a in leaves of the FLU 1 000 plants was registered
already after 10 days of cultivation, but the reduction of the CO2 uptake was observed in
plants of this treatment only after 17 days. Also in plants of FLU 100 the lowering of the
content of chlorophyll a preceded in time the inhibition of the rate of photosynthesis. The
effect of fluoranthene on photosynthetic characteristics of leaves was best observable after
24 days of cultivation. In plants of the variants FLU 100 and FLU 1 000 the rate of net
photosynthesis was significantly inhibited not only under light saturation, over the whole
range of the irradiances tested. The values of the quantum yield were even reduced in the
variant FLU 10. It is thus evident that due to FLU both photochemical and biochemical
processes of photosynthesis were inhibited. The negative effect of FLU on the
photosynthetic apparatus may explain the decrease of biomass production and leaf area
expansion. Besides the direct effects of FLU on photosynthesis, some indirect inhibitory
mechanisms cannot be excluded (e.g., impeded use of assimilates, closure of stomata).
The increased loading of PAHs can be a decisive factor for the future diversity of plant
species in the habitat and it often determines the level of economic yields. The monitoring
of PAHs in the environment gives information about a long-term loading of the biotope but
it does not permit to judge the influence of their short-time effect. It was a reason why the
effect of short-time (48 hrs) and a long-time (28 days) exposure of barley seedlings in a
nutrient solution with an increasing concentration (10, 100 and 1 000 mg.l-1) of
fluoranthene was examined with a special regard to their growth and the content
assimilatory pigments at the beginning of ontogenesis. The FLU amount and its
translocation in the plants were investigated too. Higher fluoranthene concentration (100
and 1 000 mg.l-1) caused a significant inhibition of biomass production and of the content of
photosynthetic pigments (chlorophyll a, b, carotenoids) in spring barley plants, both in longtime and short time exposures. The leaf area size and the content of photosynthetic
pigments are, by a lot of authors, included among the primary symptoms of the possible
effect of PAHs on plants. They inform about the injury of the plant organism before the
external symptoms of effect of loading are evident. The results of the present study confirm
the sensitivity of the above-mentioned parameters. The lowest concentration of FLU applied
(10 mg.l-1) caused a stimulation or an inhibition of plant growth which depended on the
length of exposure. The results obtained documented the fact that the inhibition of plant
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growth of spring barley was due to the short-time exposure combined with the higher
concentration of fluoranthene. The FLU content in the plant tissue correlated with the FLU
content in the culture medium. The highest FLU content in the course of the period studied
was found in the roots, the lowest one in the leaves. FLU translocation into the shoot was
demostrated. The FLU effect was more intensive if the length of cultivation extended and it
was the function of the accumulated amount in the tissue. The study has confirmed a
significant effect of short-time exposure to FLU on the growth of plants. It has proved the
fact that the FLU content accumulated by spring barley in short-time exposure can create
comparable symptoms (growth stimulation or inhibition) with the long-term load.
The chemical properties and biological activity of PAHs can be altered either abiotically
or biotically. To the most important abiotic factors belong short-wave radiation. PAHs
strongly absorb radiation in the UV-A and UV-B region. Once excited and transformed to
triplet state by absorbed photons, PAHs act as photosensitizers forming singlet state oxygen,
which is highly reactive and thus dangerous to cellular structures.
Even more serious is the photolytic effect of absorbed radiation. In the past, the PAHs
were considered to be eliminated by exposure to sunlight. As has been demonstrated
recently, they can be modified by absorbed radiation to a complex (more than 20, most of
them unidentified at present) mixture of photolytic products, which may be more toxic than
the parent compounds. Because PAHs are frequently spread as atmospheric depositions, the
probability of their photomodification is high. Plants are particularly endangered, because
their leaves are permanently exposed to dry or wet deposition containing PAHs, and,
simultaneously, to sun radiation. The photomodified PAHs can migrate to soil and exert
toxic effects on roots or seeds of plants.
The new quantitative data on toxicity of intact and photomodified PAHs to seed
germination, root growth and to photosynthetic apparatus, as well as new data about their
uptake, translocation and decomposition rates in plants, will certainly be of considerable
importance for both the general and the applied ecology and ecotoxicology.
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Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
12.2.3 References
Kmentová E., Kummerová M. (1998): Evaluating sensitiveness of seed germination and
root elongation test on fluoranthene in environment. 8th Days of Plant Physiology,
Olomouc, 7-10.7.1998, 118.
Kummerová M., Slovák L., Holoubek I. (1994): Effect of fluoranthene on the growth of
lettuce. Scripta Fac. Sci. Nat. Masaryk Univ. Brun. 24, 53-58.
Kummerová M., Slovák L., Mazánková J., Holoubek I. (1997a): The effect of
fluoranthene on the germination of plants. Toxicol. Environ. Chem. 60, 235-244.
Kummerová M., Slovák L., Holoubek I. (1997b): Growth response of spring barley to
short or long period exposures to fluoranthene. Rostlinná výroba, 43, 209-215.
Kummerová M., Barták M., Koptíková J. (1998): The influence of increasing
concentration of fluoranthene on the primary processes of photosynthesis and the growth of
plants of the faba bean (Vicia faba L.). 8th Days of Plant Physiology, Olomouc, 710.7.1998, 132-133.
Machala M., Hilscherová K., Kubínová R., Ulrich R., Vykusová B., Kolářová J.,
Máchová J., Svobodová Z. (2000): Biochemical monitoring of aquatic pollution II: dioxinlike toxicity and comparison of indices of oxidative stress in bream (Abramis Brama) and
perch (Perca Fluviatilis) in the Elbe river. Submitted to Veterinary Medicine - Czech.
Slovák L., Kummerová M., Holoubek I. (1995): Phytotoxicity studies of benzo[a]pyrene
with Lactuca sativa. Toxicol. Environ. Chem. 51, 197-203.
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and Eastern European Countries - State-of-the-art Report
Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
12.3 Modelling
This chapter will be published during 2000.
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Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
12.4 Study of effects of PBT compounds
In order to characterise the hazard, exposure assessments are compared to the Acceptable
Daily Intake (ADI), the Provisional Tolerable Weekly Intake (PTWI) in the highest "no-observedeffect" (NOEL) levels established by the Joint FAO/WHO Expert Committee on Food Additives
(JECFA) or the Joint FAO/WHO Meeting on Pesticide Residues, if available (Persistant Organic
Pollutants, 1996).
When considering the possible effects of consuming seafood, it is necessary to characterise
communities and individuals according to the amounts they consume, since communities in
different parts of the world are likely to show big differences in their consumption of seafood.
Based on FAO food balance data, the European regional average consumption of seafood is 60 g/
person/day and in East Asia 79 g/person/day. Since fish generally contain higher levels of PCBs
than any other food category, diets containing higher amounts of fish may be expected to lead to
higher PCB intakes.
The Baltic Sea is a sink for a multitude environmentally hazardous substances. For risk
assessment of the hazardous substances in the Baltic Sea following scheme was suggested:
1. Selection of compounds to be studied
2. Selection of bioindicators
3. Selection of appropriate chemical and biological methods
4. Taking and analysing the samples - comparison of the obtained results with the
permissible concentrations (ADI, NOEL, PTWI)
If the results exceed the permissible levels
5. Finding the reason why
6. Trying to decrease or eliminate the source of pollution
An increased risk for low birth weights in humans (especially boys) has been associated with
high consumption of contaminated fish from the Baltic Sea by their mothers. Also, the breast
cancer incidents were higher than expected in women from the Baltic coast (Agrell, 1999).
At present time, long-range transport of POPs from southern sources outside Baltic countries
dominates. This was reflected in a decreasing south-to-north gradient of compounds in
atmospheric deposition and in fish. Transboundary air pollution primarily affects the western
parts of the Baltic countries, which receive long-range pollution from Central and Western
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Europe. The PCB transport by rivers into the Baltic Sea was suggested to be almost at the same
level as atmospheric deposition by rain, 500 kg per year (Johansson, 1994). By other reports
(Agrell, 1999) the yearly atmospheric deposition of POPs to the Baltic Sea was 387.1 kg for PCBs,
19.7 kg for DDTs and 226.8 kg for HCHs, reflecting the combined input through wet deposition
and dry particle deposition. The yearly river transport of POPs to the Baltic Sea was 332 kg for
PCBs (51 congeners), 2.8 kg for DDTs and 47.5 kg for HCHs.
The stations in Latvia consistently showed the highest concentrations of PCBs and DDTs in
air, with a median of 454 pg.m-3 and 12 pg.m-3, respectively. This indicates that Riga acts as a
point source for these substances. Highest median concentrations of HCHs were found in Poland
(103 pg.m-3), which may be due to lack of restrictions against gamma-HCH during the sampling
period in Poland. Emissions of air pollution decreased substantially in all three Baltic countries
due to restructuring of industry and agriculture after the countries had regained their
independence. From the three Baltic countries, Estonia has reduced more air pollution from its
point sources during the last decade than Latvia and Lithuania. In case of urban air, changes in
the quality of fuel and cars are especially important. Unleaded petrol has entered the market and
became quite popular. Russian car and trucks, known for their great fuel consumption, have (to a
big extend) been changed for more economical Western vehicles.
There is a big difference between the Baltic countries in making the results concerning POPs
public. There were no published results in Lithuania. In Latvia, the content of POPs in lakes has
been analysed during the last few years (Valters et al., 1999). Estonia has been the only Baltic
country that has carried out systematic analysis of POPS from the Baltic Sea during the last 20
years (papers by Roots et al.). Organochlorine concentrations were analysed in the mussel tissue
of Baltic herring caught in Estonian coastal waters. Fish were analysed in some studies as a food
source of human exposure.
The comparison of concentrations of chloroorganic compounds in fish of the three Baltic
countries was conducted for the first time in the early 1990s (see Table 12.4-1). Samples of
perch were collected at three different sites along the western coast of the Baltic countries, i.e.
south of the island Hiiumaa in Estonia, the river mouth of Daugava in Latvia and Kuronian Bay
in Lithuania.
Table 12.4-1:
Area
Hiiumaa
(Estonia)
Daugavgriva
(Latvia)
Mean concentrations of organochlorines [mg.kg-1 lipid
weight] in the muscle tissue of perch (Blomkvist et al., 1993)
Number Age of fish Mean lipid p,p´- p,p´- p,p´- Sum of Sum of
of fish
[year]
content [%] DDE DDD DDT DDT
PCBs
19
1-4
0.64
0.06
0.02
0.01
0.09
0.53
22
2-5
0.92
0.41
0.17
0.11
0.68
1.8
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Kuronian
Bay
(Lithuania)
25
1-4
0.6
0.47
0.25
0.04
0.76
2.1
Even the maximum content of chlororganic compounds found in fish caught from the coastal
areas of the three Baltic countries is considerably lower than the norms set by FAO/WHO
(compared to ADI and NOEL values), in case of which the toxicants do not cause any signs of
illness to humans.
Results from other Baltic studies indicate that during the last 5-10 years, the content of
chlororganic compounds in the Baltic Sea has decreased. According to European Environmental
Agency, mainly dioxins/furans and PCB emissions in Europe will decrease 53-62 % by the year
2010 (compared to 1990). On the other hand, HCB emissions will probably increase in Central
and Eastern European countries due to the enlarging (annual) volume of incinerated waste.
Emissions of lindane can also increase.
Romanian environmental legislation follows, with some specific differences, basic rules,
which are stipulate in EU legislation. In last few years Romania developed a strong infrastructure
in the same time with a new environmental legislation and human health protection regulations to
cover the risk assessment activities.
Romania - member of the International Network for the Change of Information concerning
Potentially Toxic Chemicals (IRPTC-UNEP) since 1990 - has already improved the
infrastructure for a proper harmonisation of hazard and risk assessment of persistent organic
compounds.
Starting since 1990, the Environmental Programme for Danube River Basin represents new
framework for the riparian countries (Romania being one of them) in the chemical safety and risk
assessment action (1). The effective assessment and management of the risk in the use of
chemicals is more recently developed in Romania (2), especially after 1989.
The main important steps in the chemical risk assessment framework in Romania are as
follows:
●
Cooperation with the international Chemical Safety Programme (3);
●
Participation on the Environmental Programme for Danube River Basin;
●
Ratification of the Danube River Protection Convention; Trans-boundary Pollution Industrial Accidents Convention; Convention of the International Rivers and Lakes etc.;
●
Generator of the Environmental Strategy and National Environmental Action Plan.
National specific framework
Romanian legislation
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The most relevant Romanian legislation are the following:
●
Environmental protection law (137/95) - promoted in 1995, contents a series of measures
concerning the problems related on risk assessment, such as:
❍
❍
❍
❍
❍
❍
●
in order to obtain the EP, each of existing or proposed activity has to present an
EIA, based on detailed inventories and monitoring results;
special lists and regime for dangerous substances (pesticides, fertilisers, other
chemicals)
Quality Criteria, Quality Objectives, Norms, Standards for emissions and ambient
air and waters;
developing monitoring activity in an integrated approach (chemical, biomonitoring,
bioassay);
identification of the risk zones with high pollution level.
Water Act (107/96) - promoted in 1996, presents the items related to the risk assessment:
❍
❍
●
for a sustainable development is stated that in order to prevent the ecological risk
and damages the measures will focus especially through pollution affecting human
health;
emission monitoring (waste waters - in the future self-monitoring);
immission monitoring system with four subsystems (rivers, lakes, ground waters
and marine waters);
❍
inventories of the emissions and of water users with risk to the environment;
❍
AEPWS - national subsystem provided for the trans-boundary events;
❍
hazardous chemical list.
Other regulations - other acts related to the waste damps, pollution at long distance,
chemicals related to ozone depletion etc.
Programmes
●
Chemical Safety Programme - there is a specific legislation concerning PTC and
dangerous substances for the environment (4) elaborates by the Designated Authority
(CEA) having as copartners Agriculture, Industry, Health, Consumer Protection Agency
representatives.
National Register for Potentially Toxic Chemicals. In accordance with this general framework
it is created an Interministerial Commission with a Technical Office.
●
Environmental Strategy and National Environmental Action Plan are elaborates by
Designated Authority (CEA) having as copartners Agriculture, Industry, Health, Consumer
Protection Agency representatives.
Infrastructure: from technical support and decisional point of view following authorities are
involved:
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●
Environmental Authority
●
Human Health Authority
●
Work Conditions Protection Authority - Ministry and institutes in the field
Databases
●
IRPTC - UNEP, received in 1995 managed by ICIM and IPHI Bucharest;
●
BIG database for the Expert Unit (ICIM) of PIAC.
RISK ASSESSMENT - GENERAL APPROACH
There are two principal steps (5): (i) risk assessment and (ii) risk management. Risk
assessment at the local level is carried out by the counties EPA, which are 41 in Romania.
For existing substances the Environmental Protection Law provides powers to require
information to the companies who produce or import more than 10 tones per year of an existing
substance. The final conclusions are agreed at the Interministerial Commission level.
In the case of new substances potentially dangerous (others then those included in EINECS),
the general rule is that at least 60 days before marketing 2 manufacturers or importers must
submit 2 notifications to the competent authority.
Classification, packaging and labeling are made on the basis of intrinsic properties of substance
according to specific requirements set out in the appropriate standards (harmonized with EC).
Restrictions on substances and products are placed on the marketing and/or use of a substance
if it is found to pose risk and in relation with the emission from the product when it is used (eg.:
vehicle emission). The responsibilities for this work are for the Ministry of Transport and local
EPA´s.
In new activities for the risk identification are used different types of matrixes referring to: risk
to the accidental pollution; risk for water users; risk to the aquatic environment. The score is
based on fourth classes classification from moderate to high risk.
Industrial risk analysis identification follows some important steps: detailed presentation of
considered area; basic information collection regarding risks sources and dimensions; relevant
activities in studied area.
Identification and analysis of the risk for the major accidents have as objectives the
following points:
●
basic elements for a safety operation of an installation;
●
quantification of risk evaluation, primary causes for an accident generation and the
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consequences appraisal;
●
anticipation of the accident generation and preventing possibilities;
●
prioritisation of the risk for an optimal control.
Ecological risk evaluation, generally is calculate like:
R=PxG
or
R = P x (D - B)
where: R represent risk of unpredictable event; P the probability; G the magnitude of dangerous
consequences; D the damage and B the positive (beneficial) effects. Based on this, different
scenarios are created and analysed on short and medium terms.
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12.4.1 References
Agrell C. (1999): Atmospheric transpost of persistent organic pollutants to aquatic
ecosystems. Dissertation, Lund University, 27 p.
Blomkvist G., Jensen S., Olsson M. (1993): Concentrations of organochlorines in perch
(Perca fluviatilis) sampled in coastal areas of the Baltic Republics. Swedish Museum of
Natural History, 10.9.1993, 11p.
Chitimiea S., Varduca A., Toader C. (2000): Elements referring to Romanian regulations
for risk assessment of environmental chemicals. Centr. Europ. J. Public Hlth., in press.
Johansson N. (1994): River transport of PCBs to the Baltic Sea. Lund University, 1-16.
Roots O. (1999): The effect of environmental pollution on human health in the Baltic states
(Assessment and regional differences). Tallinn,
Valters K., Olsson A., Asplund L., Bergman A. (1999): PCB and some pesticides in
perch (Perca fluviatilis) from inland waters of Latvia. Chemosphere, 38, 9, 2053-2064.
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12.5 Ecological risk assessment
12.5.1 Project IDRIS
The project of Czech Ministry of the Environment focus on identification of ecological risks
and ecological risk assessment (Project IDRIS) was performed as a part of the long-term research
project "The Relationships between Environmental Levels of Pollutants and Their Biological
Effects". Project IDRIS was focused on the identification of ecological risks based on study of real
environmental mixtures of persistent environmental pollutants (PEPs) (persistent organic
pollutants and heavy metals) and long-term effects on ecosystems.
It is difficult to provide direct conclusive proof of a causative relationship between
environmental levels of specific PEPs and adverse impacts on a wildlife population. Linkages
between contaminant exposure and effects may nevertheless be identified by evaluating all
available study data and applying a multiple statistical analysis, PCA etc. These topics were
studied from molecular and cell levels to ecosystem. Project had three level of basic approaches:
1. Hazard identification vs. ecotoxicological properties of environmental compartments;
2. Hazard identification and assessment in the field without previous knowledge about the
stress factors involved;
3. Risk assessment focused on sites (area) with known influence of stress factors.
On the molecular and cell level, the effects of potential environmental pollutants on cell
proliferation, differentiation, apoptosis and risk/safety assessment of their role in tumour
promotion were studied. Ecosystem level included the study of effects of anthropogenic and
natural hazards on the population and communities in aquatic and terrestric ecosystems (study of
biodiversity - aquatic toxicology, in vitro tests of toxicity, biochemical markers in vivo in fish
liver, study of parasites).
The results of study of potential harmful effects in very wide laboratory and field study
concerning to environmental/ecological risk assessment or various types of environmental
mixtures of pollutants, which was performed in Czech Republic during the period 1996-1998 as a
example of "from molecullar and cell levels to ecosystem type study" will be presented in this
Chapter.
One part of the Project IDRIS was focused on the sediments - risk identification and exposure
and effects assessment. The results of this very broad project are published now.
Distribution of PAHs in the river ecosystem was studied by sampling of four abiotic
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compartments. Sampling sites were a part of sediment sampling network of Project TOCOEN
(Holoubek et al., 1994, 1998). Surface sediments (S), pore water (PW), suspended matter (SM) and
water (W) samples were collected in the Czech Republic from rivers Morava, Dřevnice and its
tributaries during two different hydrological conditions - in summer (July, low flow season) and
fall (October, rainy higher flow season) 1996. PAHs were detected at significant concentrations in
both the solid and aqueous phase of the river ecosystem.
Water concentrations were relatively low despite greater contamination of sediments. In water
samples the concentrations were higher in summer at most sites, the Sum of 16 PAHs reaching
from 27 to 275 ng.l-1. There was no clear trend between the seasons for pore waters (61 - 394 ng.l1), sediments (2 126 - 60 366 ng.g-1) or suspended matter (823 - 72 459 ng.g-1). The
concentrations in pore waters were greater than in surface waters in fall at all sites (up to 4 times
higher) and in summer at most of them. The highest enrichment between these two compartments
was found for anthracene and chrysene in summer and for fluoranthene, pyrene and phenanthrene
in fall. These compounds are also at high concentration in sediments, which are in direct contact
with pore water. Longer-time contact enables better equilibrium and higher partitioning of PAHs
from sediments to pore waters compared to surface water. There was no clear trend in PAH
concentrations between sediments and suspended matter in fall, but in summer the concentrations
in SM were higher at most sampling sites.
Greater concentration in SM may be due to previously reported comparatively higher organic
content in SM compared to sediments, which results in higher-absorbing capacity for the dissolved
PAHs. Differences in concentrations between both the sites and seasons were much greater in the
solid phase (up to 3 orders of magnitude) than in water phase (up to 6 fold). Lower molecular
weight (MW) PAHs were prevailing in the dissolved phase, higher MW PAHs in particulate
materials.
There are no risk limits for concentrations of PAHs in surface water environment established
in the Czech Republic. However, when comparing our concentrations to the maximal permissible
concentrations (MPCs, concentrations above which the risk of adverse effects is considered
unacceptable) used as environmental risk limits for inland water and sediments in the Netherlands,
concentration of PAHs in sediments exceeded the limits for at least two compounds at all sites.
The predominant compounds were phenanthrene, fluoranthene and pyrene in all studied
compartments. High MW PAHs (MW > 252) were almost entirely found in the solid phase,
especially in the fall samples. The mixture of present PAHs was qualitatively similar in all solid
samples regardless of the absolute concentration, which vary over two orders of magnitude, or
distances from the sources. PAHs composition in the sediments was found to be highly conserved
across sites reflecting combustion generated PAH profile.
Correlation and multivariate statistical analysis have evidenced differences between PAH
patterns in solid and water samples. Principal component analysis (PCA) was applied to depict the
inter-compartmental and inter-seasonal differences in the PAH pattern and to determine which
variables are mainly responsible for the differences, i.e. they show the greatest variability between
the compartments. In aquatic samples and suspended matter, principal component analysis
performed on the PAH concentration data scaled to the total PAH concentration, distinguished two
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separated groups of PAHs with different distribution depending on their molecular weight
(Fig. 12.5-1). Principal component scores afford a clear differentiation between two sample
clusters, the first relatively homogenous with SM and S samples and the second with a great
variation within the cluster with W and PW samples (Fig. 12.5-2A). The third principal
component enables to distinguish a very homogenous S cluster and another SM cluster with good
homogeneity (Fig. 12.5-2B).
Figure 12.5-2: Component score plots from PCA: distribution of different
types of samples based on PAH pattern for all samples.
Abbreviations: S = sediments, SM = suspended matter, W =
surface water, PW = pore water; s = summer, f = fall.
The separation into clusters was better in fall samples than in the summer ones, reflecting a
more conserved typical PAH pattern within the same type of samples in fall and greater variation
in summer. The suspended matter and sediment clusters are located closely around the cluster with
higher MW PAHs, whereas the water and pore water samples are more spread around the low MW
PAHs and also PYR. No significant differences in PAH profiles were found between seasons,
except of the sediment samples. In-situ partition coefficients between the solid and aqueous phase
did not differ very much between seasons. The role of organic carbon for PAHs partitioning to
sediments in situ was examined. PAHs concentrations correlated to OC content only in summer.
In-situ Kocs were up to two orders of magnitude greater than tabulated Kocs based on the
equilibrium-partitioning model. The main reasons are the lower availibility of PAHs bound to
particles from combustion sources to partition into the aqueous phase and dynamic conditions in
the river ecosystem which do not enable the full equilibrium to appear.
A number of compounds present in the environment have been reported to elicit disrupting
effects on normal physiological function of the endocrine system of mammals, fish, birds, reptiles
as well as in invertebrates (Hilscherová et al., 2000b). These chemicals are present as complex
mixtures with other compounds, often in low concentrations, in environmental matrices. They can
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have a variety of structures, and thus, their analytical determination would be daunting. Moreover,
for a number of compounds, the endocrine disrupting potency is unknown. Thus, the analytical
determination of total estrogenic activity of the complex mixture is not possible at this point. Some
integrative measures of exposure with ED-chemicals are needed to determine total estrogenicity of
complex mixtures. Despite their various structures, a number of chemicals can elicit effects via a
mechanism of action similar to estrogen. For this reason in vitro bioassays, which can account for
estrogenic activity mediated by specific mechanism of action, have been developed.
In this paper extracts of sediment samples from rivers in an industrialised area (model area,
Zlín, East Moravia) in the Czech Republic were used to evaluate suitability of a simple in vitro
bioassay system to detect estrogen receptor-mediated (ER) activity in the complex mixture. Total
estrogenic activity was detected by measuring luciferase activity in a stably transfected cell line
containing an estrogen-responsive element linked to a luciferase reporter gene. Estrogenic activity
was assayed in the presence or absence of competing 17-beta-estradiol (E2). Significant induction
of luciferase activity was observed with total extracts of all sediment samples. The addition of
natural ligand did not change the response. All samples elicited pronounced estrogenic effects
even in the presence of E2. The activity in most samples was compromised by cytotoxicity of the
cells at higher extract concentrations. While examining receptor mediated responses for the
environmental samples, it is important to test the effect of extracts on cell condition to avoid
misrepresentation of the results due to cytotoxicity.
Normalisation to the viability index to account for cytotoxicity observed at high extract
concentrations is plausible if the viability index and estrogenicity are measured simultaneously in
the same microplate wells. Estrogenic equivalents in the mixture are calculated as the sum of the
products of the concentrations of individual compounds multiplied by their potency relative to E2
(ERP). Because not all of the compounds in the mixture could be quantified and ERP were not
available for all of the compounds that were quantified, only limited mass-balance calculations
could be performed to determine the relative contribution of the estrogenic compounds analysed to
the total E2 equivalents. E2-EQs calculated from bioassays based on the EC20 and EC30 from the
standard dose-response and EEqs from analytical results (based on PAHs and alkylphenols) are
shown in Figure 12.5-3. The E2-EQs of the samples varied significantly among samples ranging
from 10 to 1 200 pg E2.g-1 sample, they were in good agreement with calculated EEq.
Figure 12.5-3: Estrogenic equivalents in sediment from the Czech
Republic [pg E2 equivalents.g-1 dry weight]. E2-EQs
calculated from the analytical results were based on the
equivalency approach and those from the bioassays were
based on EC20 and EC30 standard response.
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Fractionation of extracts enables the study of separate classes of compounds with different
effects, such as estrogenic and anti-estrogenic activities. Thus, fractionation assists in
characterisation of the complex mixtures while assisting in determining the most active classes of
compounds. Bioassays of the total extract coupled with the results of assays on individual fractions
can account for interactions within complex mixtures that are not possible to consider in
conventional chemical residue analysis and also to account for compounds for which the ERmediated activity is not known. Some of the compounds separated to the first fraction including
PCDDs, PCDFs and PCBs have been suggested to exert anti-estrogenic activity. No significant
anti-estrogenic activity was observed in this fraction when tested in the E2 stripped media.
However, addition of E2 to the medium caused anti-estrogenic activity in the first fraction of some
samples. The small amount of effect reflects the low concentrations of organochlorine compounds
in samples. The Florisil fraction, that was intermediate in polarity, was the most estrogenic, both
before or after the addition of E2.
Pesticides that have been shown to elicit weak estrogenic activity, such as p,p´-DDT,
endosulfan, toxaphene, chlordecone would have eluted in this fraction. Another major group of
compounds found in this fraction was PAHs. Mass-balance calculations confirmed that certain
polycyclic aromatic hydrocarbons (PAHs) were the most likely compounds contributing to
estrogenicity, they accounted for more than 98 % of the calculated E2-EQ. Instrumental analysis
documented that the concentration of the degradation products of alkylphenol ethoxylates (NPE)
eluted in this fraction did not occur at sufficient concentrations to account for the estrogenic
activity. This is the first report of concentrations of alkylphenols in Czech sediments. The
concentrations ranged from 1.7 to 154 ng.g-1, dry weight (dw). Their contribution to the total E2EQ was less than 2 % in all the samples. Antiestrogenicity was apparent in the third fraction for
some samples. The contributors to antiestrogenic effects in the third fraction are probably some
polar compounds, which remain to be identified.
Some other compounds that were present in significant quantities in the first and second
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fraction were tested for their potential estrogenic activity. We tested some PAHs derivatives with
four or less rings and with methyl or hydroxyl substitution. The results of these studies
demonstrated that the concentration of E2 in the medium is very important parameter in the assay.
All (anti)estrogenic effects caused by studied compounds were very small and close to the limit of
significance. Significant dose-dependent anti-estrogenicity was found only for 3,9 CH3-BaA at all
three levels of E2. Only this compound also elicited dose-dependent induction induction in dioxinlike activity in H4IIE-luc cells. Other compounds tested for potential (anti)estrogenicity were
polychlorinated napthalenes. Slight induction was observed for PCN congeners 48, 53 and 74.
Compounds that elicited significant antiestrogenic effect were mostly AhR-agonists (congeners
66, 68, 73). Three of the technical PCN preparations (Halowaxes 1013, 1014, 1051) were found to
be antiestrogenic. These mixtures also elicited significant AhR-mediated activity. The active
preparations consist primarily of higher chlorinated PCNs (tetra- through octa-CNs). The (anti)
estrogenic potency of the studied compounds is dependent on their concentrations and
concentrations of ER-ligand. Probably not only E2, but also other ER-ligands within the complex
mixtures can influence the anti(estrogenic) potential of PAH-derivatives in environmental
samples.
Biochemical markers of impacts of aquatic pollutants are defined as parameters, the changes of
which can be related to exposure to or toxic effects of chemicals (Machala et al., 2000). Alterations
in biochemical markers appear to be the responses reflecting rather the mechanisms of adverse
effects than an exposure of organisms to a specific class of compounds. Simultaneous
determination of more than one biomarker is necessary for in situ bioindication of adverse effects
of pollutants. Multivariate statistical analyses help to interpret the modulations of biochemical
markers. Modulations of biochemical markers of impacts of aquatic pollutants in liver tissue of
chub (Leuciscus cephalus), caught at several sampling sites of a river with various pollution types
and rates, were matched against analytical data of concentrations of organochlorine compounds,
polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls, dibenzo-p-dioxins and
dibenzofurans, and heavy metals.
The following biochemical responses associated with the major mechanisms of adverse effects
of aquatic contaminants have been studied the most extensively as potential biomarkers:
1. The Ah receptor-mediated induction of cytochrome P4501A (CYP1A);
2. The CYP activities, especially steroid hydroxylation, which are not probably modulated by
CYP1A-inducing agents;
3. Modulations of glutathione-dependent enzymes involved in the antioxidant defense and
phase II biotransformation;
4. In vitro production of reactive oxygen species and breakdown products of lipid peroxidation
as parameters of susceptibility to oxidative damage;
5. Metallothioneins as potential biomarkers of the impact of heavy metals.
The results of analyses for PCBs, PAHs, OCP, PCDD/Fs, and heavy metals in the river
sediments are shown in Fig. 12.5-4. Multivariate principal component analysis (PCA) of the field
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data showed general patterns of biochemical responses to different types of pollutants and
relationships among the biomarkers. Cytochrome P4501A-dependent 7-ethoxyresorufin Odeethylase (EROD) activity, inducible by 2,3,7,8-tetrachlorodibenzo-p-dioxin and structurally
related planar compounds, was strongly enhanced in the more contaminated areas. The induction
fitted well with the concentrations of PCBs and PCDD/Fs. Compared with polychlorinated
aromatic hydrocarbons, the inducing potential of PAHs was probably not as high and PAHs did
not contribute so significantly to EROD induction. Steroid hydroxylase activity, especially
hydroxylation of progesterone or testosterone in the 6beta-position, is mediated by cytochrome
P4503A27 protein(s) and perhaps also partly by fish cytochrome P4502K. A suppression of the
6beta-hydroxylation of steroids may be a specific marker of exposure to and/or adverse effects of
some organochlorine and other aquatic contaminants that do not induce CYP1A. In our study,
testosterone 6beta- and 16alpha-hydroxylase activities, as an expression of the CYP3A27 enzyme
(s), were slightly increased at low-contaminated sites, but significantly decreased in samples from
heavily polluted areas. However, a strong depression of the activities was found also at the
moderately polluted site. Therefore, specific modulatory effects of the chemicals on the
biochemical markers are still to be investigated. Besides the organochlorines and PCBs or their
metabolites, other not yet monitored classes of chemicals, such as agonists or antagonists of
steroid receptors, may affect the CYP3A activities.
In this study, similar patterns of modulations of glutathione-dependent enzymatic activities
were demonstrated; the activities were strongly increased at sites heavily polluted by
organochlorines and polychlorinated aromatic compounds, which are known to induce oxidative
stress. Three glutathione-dependent activities were analyzed in the hepatic subcellular fractions:
the microsomal GST activity towards 1-chloro-2,4-dinitrobenzene as a substrate (mGST), the
cytosolic GST towards ethacrynic acid (GST-ETHA) and the cytosolic glutathione reductase
activity (GR). PCA demonstrated similar modulations of all these prospective biochemical
enhanced by Fe(II) and NADPH, was found to be another
indicators of oxidative stress. LP
in vitro
potential biomarker reflecting chemical stress. The pattern of its modulations differed from the
responses of the rest of oxidative stress parameters at some sampling sites.
Further biochemical markers of oxidative stress under study, including in vivo lipid
peroxidation, in vitro production of reactive oxygen species detected by dichlorofluorescein probe,
and the concentration of metallothioneins in the cytosolic fraction of chub liver, elicited only small
among all the sites and did not correlate well with the concentrations of the contaminants in
sediment and fish muscle samples.
In conclusion, multivariate analysis demonstrated that the measurement of the EROD,
testosterone 6beta-hydroxylase, selected glutathione-dependent enzyme activities and in vitro lipid
peroxidation represent a suitable battery of biomarkers of toxicity on the biochemical level.
Contaminants are present in environmental media as complex mixtures (Hilscherová et al.,
2000c). Therefore the determination of total toxic potency is complicated. Comprehensive methods
that can assess the overall toxic potential, including interactions within mixtures are needed. A
valuable approach is development of bioassays that can account for all compounds acting through
specific mode of action, such as receptor-mediated effects. So far the most widely studied are
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effects mediated through aryl hydrocarbon (AhR) and estrogen receptor (ER). In vitro bioassays
with recombinant cell lines where specific exogenous response gene is under control of dioxinresponsive or estrogen-responsive DNA enhancer element were shown to elicit higher sensitivity
and lower variability than endogenous receptor-mediated responses. Complex organic extracts
from soils and sediments collected in an industrial region of the Czech Republic were tested with
in vitro recombinant cell lines for their potential dioxin-like and estrogenic activity and
cytotoxicity. The extracts were analysed for the compounds potentially causing the observed
activity, such as PCDD/Fs, PCBs, PAHs and alkylphenols. The toxic and estrogenic equivalency
factors were derived from both bioassays (TCDD-EQ and E2-EQ) and analytical results (TEQ and
EEq).
Both recombinant cell lines proved to be very useful tool for screening dioxin-like and
estrogenic activities, with MCF-7-luc cell line being more sensitive for cytotoxicity. Complex
mixtures extracted from soils and sediments contained both dioxin-like activity (ranging up to
23 000 pg TCDD.g-1 dw) and estrogenic activity (up to 1 200 pg E2.g-1 dw). For dioxin-like
toxicity tested on H4IIE-luc cells complete dose-responses were obtained with all soil and
sediment extracts. There was very good correlation between toxic equivalencies based on bioassay
measurements (TCDD-EQ) and total analytical-TEQ or TEQ based only on concentrations of
PAHs, or total concentration of PAHs in sediment and soil samples (Fig. 12.5-5). Mass-balance
analysis revealed that PAHs are the dominant group of compounds in soils (representing 65-100 %
of total TEQs) as well as in sediment extracts (more than 99 % of total TEQ).
Figure 12.5-5: Relationship of toxic equivalency factors [pg TCDD.g-1 dw
sample] derived from bioassay results (TCDD-EQ) and
calculated from chemical analysis results (TEQ).
triangles = sediments, circles = soils.
Cytotoxicity was observed only at the greatest concentration of the extract with some samples.
The MCF-7-luc cell line used for determination of estrogen receptor-mediated activity was
sensitive to the cytotoxic effects of the soil and sediment extracts. Dose dependent cytotoxicity
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was observed with most samples and strongly correlated to the cell protein content. Significant
estrogenic activity was found in all samples. Normalisation of the luciferase induction data to
viability index increased the linear range of response of samples and relative induction compared
to standard maximum and did not increase the variability. Estrogenic equivalents relative to 17beta-estradiol based on standard EC50 values were calculated from the normalized dose-response
curves for sediment extracts. Only limited mass-balance for estrogenic activity was possible due to
non-existing E2-equivalents for majority of compounds. The most active fraction contained
alkyphenols and PAHs. Contribution of alkylphenols to the total EEq equivalent was less than
2 %. PAHs accounted for more than 98 % of the EEq. The bioassay derived E2-EQs were in good
agreement with EEq calculated based on PAHs and alkylphenols, suggesting that these two classes
of compounds (especially PAHs) account for majority of the ER-mediated effects observed.
Fractionation along with mass-balance calculation enabled identification of the most active
fraction and classes of compounds. Polycyclic aromatic hydrocarbons were identified as the group
of compounds responsible for most of the TCDD-like activity in sediments as well as for
important portion of estrogenic activity.
Synthetic organic chemicals are present in all environmental compartments as complex
mixtures, and therefore their potential effects are difficult to predict (Hilscherová et al., 2000d).
Environmental matrices such as sediments contain complex mixtures of residues. Instrumental
quantification methods are available for some compounds, whereas other compounds for which
neither methods nor standards are available may not be identified or quantified. The application of
instrumental analyses to quantify specific compounds in combination with bioassays to quantify
the total activity along with specific fractionation techniques can be applied to assess the potential
effects of complex mixtures and determine putative causative agents. Classical chemical analysis
of complex mixtures of organic residues present in sediments can be both resource- and timeintensive. These methods provide little information on the biological effects of the complex
mixture and they do not account for possible interactions between or among individual chemicals.
In vitro bioassays can serve as simple, rapid and sensitive screening systems for presence of
and mutual interactions of chemicals with specific mode of action. In vitro bioassays using wild
type fish and rat hepatoma cell lines and their corresponding recombinant cell systems were used
to evaluate 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)-like activity (mediated through the AhReceptor) in extracts of sediments collected from rivers in an industrial area of the Czech
Republic.
Organic compounds known to bind to the AhR include, among others, polychlorinated dibenzop-dioxins and dibenzofurans (PCDD/DFs), polychlorinated biphenyls (PCBs) and polycyclic
aromatic hydrocarbons (PAHs). The relative potencies of complex mixtures can be expressed as
TCDD equivalent units, determined either by bioassays or calculated from the concentrations of
individual compounds and their relative potency factors (TEFs).
In the first part the responsiveness of different cell lines to dioxin standard was compared.
EC50 values for the different cell types studied ranged from 23 to 75 pM TCDD as determined by
probit analysis. Statistically significant differences were observed between the EC50 values for
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mammalian and fish cell lines. EC50 values were generally greater for fish than mammalian cell
lines. The EC50 value for H4IIE wild type cells was significantly greater than that for the
recombinant H4IIE-luc cells. Variability in three different parts of the dose-response curve (lower,
middle, upper) was less than 25 %. The maximal induction factor, defined as the magnitude of
induction over solvent control, was 1.5- to 3-fold greater for the recombinant cell lines. The linear
working range was approximately 30-fold for the H4IIE-wt, but up to 100-fold for the other cell
lines.
All the extracts of the complex mixtures of contaminants present in sediments elicited
statistically significant responses in all cell lines tested. For most sediment extracts a complete
dose-response relationship was obtained. The maximal efficacy induced by the samples was
between 57 and 143 % of the maximal induction elicited by TCDD. All cell types were
sufficiently sensitive to determine TCDD-EQs in sediment extracts. Greater responsiveness,
sensitivity and reproducibility were observed for recombinant than wild-type cells. Depending on
the cell line and sampling site, extract equivalent to as little as 0.03 - 1 mg sediment were
sufficient to cause significant induction relative to the solvent control. No significant cytotoxicity
was observed except at the greatest dosed concentration. TCDD equivalents determined from the
different bioassays (TCDD-EQ) were well correlated. Cell line-specific differences in the
sensitivity to compounds present in the complex sediment extracts were observed.
Relatively great concentrations of most of the 16 PAHs were measured in all samples. The sum
of the 16 PAHs ranged from 1 132 to 40 000 ng.g-1 dw. Fluoranthene, pyrene and benzo(b)
fluoranthene occurred at the greatest concentrations. No risk limits for concentrations of PAHs in
sediments have been promulgated in the Czech Republic. However, in comparison to maximal
permissible concentrations (MPCs, concentrations above which the risk of adverse effects is
considered unacceptable) used as risk limits in the Netherlands at least two of the PAHs in each
sample except of one have exceeded the tolerance limits. In some samples collected before the
floods concentrations of most PAHs were greater than the MPCs for sediments. Concentrations of
organochlorine compounds were rather small at all sites. This is the first study to report
concentrations of PCDDs/Fs and coplanar PCBs in the study area. Concentrations of both PCDDs
and PCDFs were generally near the limit of detection of 0.02 pg.g-1 dw, in F1, with the total
concentration less than 2.2 pg.g-1 dw. Coplanar PCB concentrations were less than 90 pg.g-1 dw,
with major contributions from congeners 77 and 126. The Sum of other PCBs studied ranged from
14 to 114 ng.g-1 dw. There was no significant difference in concentrations of PCDD/Fs or
coplanar PCBs among locations.
TCDD equivalents calculated from the results of chemical analysis (TEQs) were in good
agreement with those determined by bioassays. This indicates that all of the TCDD-like activity
was accounted for by the compounds identified and quantified by instrumental analysis.
Fractionation along with mass-balance calculations allowed identification of the active fractions
and classes of compounds. Polycyclic aromatic hydrocarbons (PAHs) were determined to be the
group of compounds responsible for greatest portion of the AhR-mediated activity in the
sediments studied.
In vitro cell bioassays are useful techniques for the determination of receptor-mediated
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activities in environmental samples containing complex mixtures of contaminants (Hilscherová et
al., 2000e). The cell bioassays determine contamination by pollutants that act through specific
modes of action. Two groups of toxicants of current interest are dioxin-like and (anti-)estrogenic
chemicals. This comprehensive summary of dioxin-like and xenoestrogenic compounds including
natural and major classes of industrial contaminants along with the method used to determine their
relative estrogenic potency was prepared (Hilscherová et al., 2000e).
This article is concerned with strategies for the evaluation of aryl hydrocarbon receptor (AhR)(hereafter referred as dioxin-like) or estrogen receptor (ER)- mediated activities of potential
endocrine disrupting compounds (EDCs) in complex environmental mixtures. Extracts from
various types of environmental or food matrices can be tested by this technique to evaluate their
2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TCDD-EQs) or estrogenic equivalents (E2-EQs)
and to identify contaminated samples that need further investigation using resource-intensive
instrumental analyses. Bioassays based on the responses of either wild type or genetically
engineered eukaryotic cells enable the assessment of potencies of individual chemicals or complex
mixtures of environmental contaminants in extracts to cause AhR- or ER-mediated effects. Either
endogenous responses or exogenous reporter systems incorporated into the cell are used for the
measurements. The induction of transcription by the responsive genes following the exposure of
cells to specific ligands or mixtures of compounds can be assessed by measuring endogenous or
genetically engineered responses such as protein expression by measuring the amount of protein
directly or by measuring an enzyme activity. Both estrogenic and antiestrogenic effects can be
assessed with ER-responsive cell lines.
Antiestrogenicity can be detected directly by growing cells in medium deficient in 17betaestradiol (E2) or by the antagonism of co-administered E2. In extracts containing complex mixtures
of compounds, potential cytotoxicity should be evaluated in bioassays with the same cells that
were used in receptor mediated effects. This is because the cytotoxic effects could mask potential
antiestrogenic or other types of effects. Anti-estrogenic potential of some compounds changes
depending on the E2 concentration, thus testing only in media without any E2 does not adequately
assess the physiological situation where there is always some E2 present.
Fractionation of sample extracts exhibiting significant activities, and subsequent reanalysis
with the bioassays can identify important classes of contaminants that are responsible for the
observed activity. Effect-directed chemical analysis is performed only for the active fractions to
determine the responsible compounds. Mass-balance estimates of all major compounds
contributing to the observed effects can be calculated to determine if all of the activity has been
identified, and to assess the potential for interactions such as synergism or antagonism among
contaminants present in the complex mixtures. The general steps of recommended strategy for
toxicants identification and evaluation (TIE) in complex mixtures are (Fig. 12.5-8):
1. Screening of the whole extract - to determine the samples containing significant toxic
potencies, which require further chemical analysis. If no significant response is observed,
there is no need to conduct expensive, time- and material-consuming chemical analysis.
Since the method detection limit is known for the bioassay, an upper limit of concentration
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of toxic equivalents in the sample can be defined;
2. Fractionation of the samples that were active in bioassays and chromatographic analysis can
be used to determine the most probable contributors to the total activity;
3. Generating the full dose-response relationship of the unfractionated sample or fractions
thereof, so that the total activity of the sample can be determined as response equivalents.
Calculation of the mass-balance is accomplished by comparing the activity observed in the
bioassay with the potential activity based identification and quantification by instrumental
analyses. If the values derived and fractionation does not indicate that there were
antagonistic effects in the whole extract, it can be concluded that all of the significant
contributors to the total complex mixture have been identified.
The bioassay approach is an efficient (fast and cost effective) screening system to identify the
samples of interest and to provide basic information for further analysis and risk evaluation. Many
studies have demonstrated the utility of bioassays in assessment of receptor-mediated activities of
both individual chemicals and complex mixtures. Bioassays can be used for the detection and
quantification of receptor agonists/antagonists in complex mixtures, thus providing a relative
measure of bioactive compounds in food, biological, or abiotic samples. Bioassays can also be
useful for identification and characterisation of novel receptor agonists, for examination of species
differences in receptor-mediated responses or effectiveness of remediation procedures designed to
decrease specific type of contamination. Bioassays are also useful screening tools for identifying
responsible compounds following fractionation of a complex mixture, they enable to prioritise
samples which require further investigation. Bioassays, based on in vitro responses of cells,
including both wild type or recombinant (genetically modified) cell lines can also be used for
assessment of other toxicologically and pharmacologically important chemicals where liganddependent induction of gene expression has been demonstrated. Such compounds include
xenoandrogens, heavy metals and compounds that can cause induction of peroxisome
proliferation.
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TOCOEN REPORT
Persistent, Bioaccumulative and Toxic Chemicals in Central
and Eastern European Countries - State-of-the-art Report
Content | Chapter 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12
12.5.2 References
Hilscherova K., Ansorgova A., Holoubek I. (2000a): Distribution of polycyclic aromatic
hydrocarbons among different compartments of river ecosystem. Submitted to
Chemosphere.
Hilscherova K., Kannan K., Holoubek I., Giesy J. P. (2000b): Characterization of
Estrogenic Activity of Riverine Sediments from the Czech Republic. Submitted to Environ.
Toxicol. Chem.
Hilscherová K., Dušek L., Kannan K., Giesy J. P., Machala M., Holoubek I. (2000c):
Evaluation of Cytotoxicity, Dioxin-like Activity and Estrogenicity of Complex
Environmental Mixtures.Submitted to Centr. Eur. J. Pub. Hlth.
Hilscherova K., Kannan K., Kang Y.-S., Holoubek I., Machala M., Masunaga S.,
Nakanishi J., Giesy J. P. (2000d): Characterization of Dioxin-Like Activity of Riverine
Sediments from the Czech Republic. Submitted to Environ. Toxicol. Chem.
Hilscherova K., Machala M., Kannan K., Blankenship A. P., Giesy J. P. (2000e): Cell
Bioassays for Detection of Aryl Hydrocarbon (AhR) and Estrogen Receptor (ER) Mediated
Activity in Environmental Samples. Submitted to Environ. Sci. Pollut. Res.
Holoubek I., Čáslavský J., Helešic J., Vančura R., Kohoutek J., Kočan A., Petrik J.,
Chovancová J. (1994): Project TOCOEN. The fate of selected organic pollutants in the
environment. Part XXI. The contents of PAHs, PCBs, PCDDs/Fs in sediments from Danube
river catchment area. Toxicol. Environ. Chem. 43, 203-215.
Holoubek I., Machala M., Štaffová K., Helešic J., Ansorgová A., Schramm K.-W.,
Kettrup A., Giesy J. P., Kannan K., Mitera J. (1998): PCDDs/Fs in sediments from
Morava river catchment area. DIOXIN 98. Organohalogen Compounds, 39, 261-266.
Machala M., Dušek L., Hilscherová K., Kubínová R., Jurajda P., Neča J., Ulrich R.,
Gelnar M., Studničková Z., Holoubek I. (2000): Determination and multivariate
statistical analysis of biochemical responses to environmental contaminants in feral
freshwater fish Leuciscus cephalus. Submitted to Environ. Toxicol. Chem.
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TOCOEN REPORT
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