Low POP Content Limit OF ISBN 978-91-620

Low POP Content Limit
OF PCDD/F in Waste
Evaluation of human health risks
rEport 6418 • MARCH 2011
Low POP Content Limit OF
PCDD/F in Waste
Evaluation of human health risks
SWEDISH ENVIRONMENTAL
PROTECTION AGENCY
Orders
Phone: + 46 (0)8-505 933 40
Fax: + 46 (0)8-505 933 99
E-mail: [email protected]
Address: CM Gruppen AB, Box 110 93, SE-161 11 Bromma, Sweden
Internet: www.naturvardsverket.se/publikationer
The Swedish Environmental Protection Agency
Phone: +46 (0)8-698 10 00 Fax: +46 (0)8-20 29 25
E-mail: [email protected]
Address: Naturvårdsverket, SE-106 48 Stockholm, Sweden
Internet: www.naturvardsverket.se
ISBN 978-91-620-6418-1
ISSN 0282-7298
© Naturvårdsverket 2011
Print: CM Gruppen AB, Bromma 2011
Cover photo: Viktor Sjöblom, Umeå
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Preface
This study was initiated by the Swedish Environmental Protection Agency with the
aim to investigate whether the suggested 15 ppb (15 000 ng TEQ kg-1) Low POP
Content Limit (LPCL) for dioxin in waste is low enough to protect humans from
toxicological health risks. The main focus of the study was to identify and quantify
risk scenarios where contaminants originating from wastes are transferred from the
environment to human food chains.
The work consisted of three parts:
i) a literature study to collect and analyse existing data and relevant
information from the open literature,
ii) two field measurement studies at sites where dioxin contaminated waste is
produced and managed, and
iii) a human health risk assessment including prediction of risks on the basis of
the field data obtained
Participants in the project were Annika Åberg (Umeå University), Karin Wiberg
(Umeå University), and Annika Hanberg (Karolinska Institutet).
This report is a first approach to investigate human health risks associated to
PCDD/Fs and dl-PCBs in waste and waste management practices in the society.
The issue is very complex and is not easily handled since it involves environmental
and toxicological sciences as well as political, technical and economical
perspectives. Therefore, the report does not aim to suggest new Low POP Content
Limits for PCDD/Fs (or dl-PCBs) in waste, but rather highlight some issues that
are important from the human health perspective. Hopefully, the results in the
report may lead to stimulation of the scientific community to pick up this topic and
develop science based new Low POPs Limits. The results do not reflect risks
associated to diffuse pollution of PCDD/Fs or dl-PCBs in the environment and the
fact that humans are exposed to environmental background concentrations. The
basis for the study was to investigate how point sources may increase
environmental levels and human body burdens in addition to exposure that
originates from the atmosphere.
Although the information in this report has been funded wholly or in part by the
Swedish Environmental Protection Agency, it may not necessarily reflect the views
of the Agency and no official endorsement should be inferred.
Swedish Environmental Protection Agency, March 2011
Anders Johnson
Head of a Environmental Assessment Department
3
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
4
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Abbreviations
BAF
BSAF
BCF
BIPRO
b.w.
BTF
CNP
COR
CP
DDT
dl-PCB
HCH
HpCDD
HpCDF
HxCDD
HxCDF
IPEN
I-TEF
I-TEQ
LPCL
MSWI
NGO
OCDD
OCDF
PCB
PCDD/F
Bioaccumulation factor – the ratio of the concentration of a chemical in
an exposed organism (all possible exposure routes) and the
concentration of the chemical in an environmental compartment or in
food.
Biota-to-sediment or biota-to-soil accumulation factor - the ratio of the
concentration of a chemical in an exposed organism (lipid normalised)
and the concentration of the chemical in the sediment/soil (organic
carbon-normalised).
Bioconcentration factor - the ratio of the concentration of a chemical in
an organism and the concentration of the chemical in the water at steady
state.
Beratungsgesellschaft für integrierte Problemlösungen, technical
consultants in Germany.
Bodyweight
Biotransfer factor – the ratio of a chemical in an exposed organism and
the daily contaminant input flux.
Chlornitrofen, organochlorine herbicide
Carry over rate, transfer efficiency between environmental media and
biota.
Chlorophenol
Dichlorodiphenyltrichloroethane, organochlorine insecticide
Dioxin-like PCBs, a group of twelve PCB congeners that exhibit the
same mode of toxic action as PCDD/Fs.
Hexachlorocyclohexane, organochlorine insecticide
Heptachloro-dibenzo-p-dioxin
Heptachloro-dibenzofuran
Hexachloro-dibenzo-p-dioxin
Hexachloro-dibenzofuran
The International POPs Elimination Network
Toxic equivalence factors for calculation of TEQ. Adopted by an
international expert group (NATO/CCMS, 1988).
Toxic equivalents, the product of the analytical concentration of a
PCDD/F congener and its I-TEF.
Low POP Content Limit, maximum residue limit for dioxins in waste
products where recycling and/or management practices are not
restricted.
Municipal solid waste incineration
Non-governmental organisation
Octachloro-dibenzo-p-dioxin
Octachloro-dibenzofuran
Polychlorinated biphenyl
Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans
5
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
PCP
PeCDD
PeCDF
POP
ppb
TDI
Pentachlorophenol
Pentachloro-dibenzo-p-dioxin
Pentachloro-dibenzofuran
Persistent Organic Pollutant
parts per billion, 1 µg kg-1 or 1000 ng kg-1
Tolerable Daily Intake – the tolerable average intake of a compound
over a long term that does not result in human health risks.
TCDD
Tetrachloro-dibenzo-p-dioxin
TCDF
Tetrachloro-dibenzofuran
TEQ
Toxic equivalents, the sum of the products of the analytical
concentrations of each dioxins or dioxin-like compounds multiplied
with their individual TEF.
TWI
Tolerable Weekly Intake – the tolerable average intake of a compound
over a long term that does not result in human health risks.
WHO-TEF Toxic equivalents factors for calculation of TEQ for dioxins and dioxinlike com-pounds, adopted by WHO.
WHO-TEQ Toxic equivalents, the sum of the products of the analytical
concentration of dioxins and dioxin-like compounds and their individual
WHO-TEF.
6
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Contents
PREFACE
3
ABBREVIATIONS
5
1
1.1
SAMMANFATTNING
Dioxinförorenat avfall i befintliga fallstudier
11
11
1.2
Halter i föda och exponering relaterat till lokala källor
12
1.3
Granskning av BIPROs riskbedömning
13
1.4
Exponeringsbedömning
13
1.5
Syntes
14
2
2.1
SUMMARY
Dioxin contaminated waste in current case studies
17
17
2.2
Food and exposure levels related to local sources
18
2.3
Review of the BIPRO assessment
19
2.4
The exposure assessment
20
2.5
Synthesis
20
3
BACKGROUND
22
4
DIOXINS
23
5
5.1
DIOXIN CONTAMINATED WASTE
Waste categories
25
25
5.2
Residues from thermal processes
26
5.2.1
Concentrations of pollutants
26
5.2.2
Case studies
27
5.3
Impregnated wood and waste wood litter
30
5.3.1
Concentrations of pollutants
30
5.3.2
Case studies
31
5.4
Chemical waste
32
5.4.1
Concentrations of pollutants
32
5.4.2
Case studies
32
5.5
E-waste recycling
33
5.5.1
Concentrations of pollutants
33
5.5.2
Case studies
33
6
6.1
HUMAN EXPOSURE
Exposure via dietary intake
35
35
7
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
6.2
Exposure routes near local pollution sources
37
6.3
Human body burdens in local contamination scenarios
38
7
7.1
FOOD CHAIN CONTAMINATION RELATED TO LOCAL SOURCES 42
Agricultural food chains
43
7.1.1
Eggs and chickens
43
7.1.2
Milk and meat
45
7.1.3
Factors affecting transfer of soil pollutants to agricultural food chains
46
7.2
The aquatic food chain
49
8
8.1
REVIEW OF THE BIPRO RISK ASSESSMENT
Application of safety factors and tolerable daily intake (TDI)
51
51
8.2
Correlating environmental levels to uptake into eggs
52
8.3
Contribution of dl-PCBs
52
8.4
Exposure from other sources
53
9
9.1
CASE STUDIES IN PERU AND THAILAND
Case study 1: Zapallal waste site, Peru
54
54
9.1.1
Pollution of soil and sediment related to management of ashes
56
9.1.2
Bioaccumulation in biota
58
9.1.3
Conclusions
60
9.2
Case study 2: Phuket MSW Incinerator, Thailand
60
9.2.1
Pollution of soil and sediment related to management of ashes
61
9.2.2
Bioaccumulation in biota
64
9.2.3
Conclusions
64
10
10.1
HUMAN EXPOSURE ASSESSMENT RELATED TO
ENVIRONMENTAL CONTAMINATION
Method
65
65
10.2
Human exposure scenarios
66
10.3
Modelling bioaccumulation and exposure levels
67
10.4
Results
68
10.4.1
Ingestion of eggs
68
10.4.2
Ingestion of milk
69
10.4.3
Ingestion of meat
71
10.4.4
Ingestion of leafy vegetables
72
10.4.5
Ingestion of soil
73
10.5
Critical soil concentration levels
73
10.5
Critical soil concentration levels
74
8
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
11
11.1
SYNTHESIS OF THE RESULTS
Risk scenarios
78
78
11.2
Exposure assessment
80
11.3
Uncertainties in the results
83
11.3.1
Identifying risk scenarios related to improper management of PCDD/F
contaminated waste
83
11.3.2
Correlating environmental levels to human food chain contamination
11.3.3
Correlating environmental levels to improper management of waste in
the field studies
84
11.3.4
Human exposure assessment
85
11.3.5
Estimated critical soil concentrations
87
11.3.6
Degree of protection with current Low POP Content Limits
87
12
CONCLUSIONS
89
13
RECOMMENDATIONS FOR FUTURE WORK
91
84
APPENDIX A
Emission and Pollution Problem by dioxin in Peru
92
92
Introduction
92
Objectives
93
Methodology
93
Location of Zapallal Landfill
94
Description of the storage places of waste and residues
95
Types of identified residues
96
Storage of residues
98
Access to the landfill and the surrounding
99
Acknowledgment
100
References
100
APPENDIX B
102
APPENDIX C
103
APPENDIX C
104
APPENDIX C
105
APPENDIX D
121
REFERENCES
127
9
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
10
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
1
Sammanfattning
Syftet med denna undersökning var att identifiera riskscenarier där förekomst av
polyklorerade dibenso-p-dioxiner och dibensofuraner (PCDD/F:er) och dioxinlika
polyklorerade bifenyler (dl-PCB:er) i avfall orsakar spridning av dessa toxiska
föroreningar i miljön och överförs till människor genom föda och andra
exponeringsvägar. Två fältstudier genomfördes på platser där avfall och aska förvaras
och hanteras öppet, en i Peru och en i Thailand. Syftet med dessa var att studera
graden av inverkan på omgivande miljö.
För att kunna relatera människors exponeringsnivåer till det föreslagna Low POP
Content Limit (LPCL)-värdet för PCDD/F genomfördes en riskbedömning med hjälp
av en spridnings- och exponeringsmodell (CalTOX) samt med stöd av fältdata från
Peru. Genom exponeringsberäkningar uppskattades punktkällors bidrag till
humanexponering utöver den som man oundvikligen utsätts via diffusa utsläpp.
1.1
Dioxinförorenat avfall i befintliga
fallstudier
Vi identifierade fyra avfallskategorier som potentiellt viktiga inom ramen för
projektets syfte:
i)
förbränningsrester,
ii)
kemiskt avfall,
iii)
träavfall samt
iv)
avfall från el-avfallsåtervinning.
För kategorierna i, iii och iv finns ett fåtal antal rapporterade nutida fallstudier, medan
det för kemiskt avfall framförallt är historiska incidenter som publicerats. Handel med
och återvinning av träavfall kan vara av särskilt intresse då ett par nyligen genomförda
fallstudier visar att denna avfallsfraktion har kontaminerat födokedjor i
produktionssteget. För aska existerar i huvudsak en fallstudie och den rapporteras från
Storbritannien, där bottenaska och flygaska från kommunal avfallsförbränning
användes som gångmaterial inom ett odlingsområde, vilket ledde till kraftigt förhöjda
halter i ägg från frigående höns.
Samtliga incidenter som involverar träavfall eller förbränningsrester rapporteras från
europeiska länder. Detta utesluter inte att allvarliga riskscenarier kan finnas även för
utvecklingsländer. Tvärtom indikerar detta att om dessa problem kan uppstå i Europa,
trots en i många fall väl förankrad och tillämpad lagstiftning, är sannolikheten att de
ska inträffa i utvecklingsländer med svagare miljöövervakning förmodligen högre.
Från dessa områden saknas dock ofta relevanta data. Eftersom flera typer av farliga
ämnen kan förekomma i avfall och öppna deponeringsområden finns det en risk för att
vissa människogrupper i utvecklingsländer (t.ex. skräpletare) utsätts för förhöjd
11
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
exponering. Hantering av avfall som innehåller PCDD/F kan därför vara ett allvarligt,
om än inte väldokumenterat, problem för människor i fattiga länder.
Det är ofta svårt att relatera en miljöpåverkan till hantering av avfall eftersom flera
olika föroreningskällor kan existera inom avfallsområdet. Det är t.ex. svårt att skilja på
förorening som sker genom spridning av aska från förorening som sker genom
deposition av luftemissioner som orsakats av förbränning av avfall. I fältstudierna från
Peru och Phuket kunde därför konsekvenser av öppen och oskyddad förvaring av aska
inte utredas separat från luftemissionernas påverkan.
1.2
Halter i föda och exponering relaterat till
lokala källor
Flertalet studier har rapporterat om lokal förorening av mark och vatten som en följd
av industriella punktkällor, spill, olyckor eller andra förorenande aktiviteter. Vid
sådana platser kan förhöjd exponering av människor förekomma. Ofta är den relaterad
till intag av lokalt producerad föda. I vissa fall, där t.ex. luft och jord är kraftigt
förorenade, kan även kontakt med den abiotiska miljön, t.ex. intag av jord, ge upphov
till hög exponering hos lokalbefolkning.
Alla animaliska livsmedelsprodukter innehåller PCDD/F:er som ackumulerats från
omgivningen och som härrör från historiska och dagsaktuella källor. Föroreningsnivån
i livsmedel som producerats nära punktkällor är ofta relaterad till förhöjda halter i
miljön. Detta kan i sin tur leda till en högre exponering hos människor som bor i
närheten av källan jämfört med genomsnittsbefolkningen.
Många studier har visat att intag av lokalt producerade frigående kycklingar/höns och
deras ägg utgör ett högriskscenario. Det finns även studier som visar att
bakgrundskoncentrationer i lantliga miljöer utan lokala s.k. hot-spots är tillräckligt
höga för att ge upphov till höga halter av PCDD/F i ägg från frigående höns. Det är
svårt att prediktera föroreningshalter i ägg med god noggrannhet. Överföringsvägarna
mellan miljön och frigående hönor är många och komplexa, vilket innebär att
exponeringsvägarna inte är lätta att beskriva med hjälp av modeller. Olika faktorer,
som förorenings-sammansättning, uppfödningsförhållanden, jordtyp och
växttäckningsgrad, m.fl. påverkar bioackumulationen. Resultat från enskilda studier
kan därför inte användas för att ta fram generella bioöverföringsfaktorer mellan jord
och ägg. Produktion av andra animaliska livsmedelsprodukter, såsom mjölk och kött,
utgör också högriskscenarier i närheten av lokala källor.
Enligt födointagsstudier från olika länder har den allmänna befolkningen ofta ett intag
av PCDD/F som ligger nära eller överskrider WHO:s tolerabla intagsgränser, TDI,
som anger det uppskattade dagliga intag som kan tolereras under lång tid utan att det
förväntas ge upphov till hälsorisker för människor. Skillnaderna i intag är dock stora
mellan olika länder. Ett fåtal studier har rapporterat om intag och kroppsbelastning i
utvecklingsländer. Eftersom födointag och andra levnadsvillkor skiljer sig åt mellan
12
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
olika länder är det inte möjligt att använda data från den industrialiserade världen för
att uttala sig om PCDD/F-exponering för människor i utvecklingsländerna.
1.3
Granskning av BIPROs riskbedömning
I den riskbedömningen av PCDD/F som gjordes av en tysk konsultbyrå (BIPRO) på
uppdrag av Europeiska Kommissionen utgick man från att det lagstiftade gränsvärdet
för kommersiellt producerade ägg är korrelerat till risker för människors hälsa baserat
på TDI. Eftersom det lagstiftade gränsvärdet i livsmedel inte grundar sig på en
hälsoriskbedömning, kan en jämförelse mellan halter i livsmedel och gränsvärdet inte
indikera risknivån avseende hälsoeffekter. Riskbedömningar bör därför inte enbart
baseras på denna typ av jämförelser.
I BIPROs riskbedömning utgår man ifrån att en PCDD/F koncentration på 30 pg
WHO-TEQ g-1 fett kan accepteras för ägg. Genom att använda överföringsfaktorer
mellan jord och ägg (s.k. BTFs, biotransfer factors) från två olika studier uppskattade
man att den kritiska PCDD/F koncentration på 30 pg WHO-TEQ g-1 fett i ägg
motsvarar en markkoncentration på 1 000 ng TEQ kg (1 ppb).
En konsumtion av ett ägg per dag är tillräckligt för att ge ett signifikant bidrag till TDI
om äggkoncentrationen är 3 pg TEQ g-1 fett eller högre. I motsats till slutsatserna i
BIPRO-rapporten, tyder dessa intagsberäkningar på att koncentrationer i ägg inte bör
vara högre än EU:s gränsvärde (3 pg TEQ g-1 fett). En sammanställning av
litteraturdata och beräknade överföringsfaktorer från jord till ägg baserade på dessa
data visade att överföringsfaktorerna varierar i hög grad och att dl-PCB är betydligt
mer tillgängliga än PCDD/F. Med hänsyn till den stora variationen kan BTF från ett
fåtal studier inte anses representativa för mer generella scenarier. Den
överföringsfaktor som användes av BIPRO låg i det övre intervallet och deras
riskbedömning underskattar därför förmodligen risken för upptag i ägg vid
markkoncentrationer på 1 000 ng TEQ kg-1 torrvikt (1 ppb). Enligt
överföringsfaktorerna som beräknades i denna rapport kan gränsvärdet för PCDD/F i
ägg nås redan vid 1-70 ng TEQ i jorden (0,001-0,07 ppb).
TDI omfattar toxiskt bidrag (TEQ-bidrag) från både PCDD/F och dl-PCB. Bidraget
från dl-PCB beaktas inte i BIPROs riskbedömning, vilket ger en skev bild av riskerna.
1.4
Exponeringsbedömning
Inom ramen för denna studie gjordes en exponeringsbedömning där kritiska
markkoncentrationer beräknades. I denna bedömning användes uppmätta
markkoncentrationer från fältstudien i Peru i två föroreningsscenarier: en med
bakgrundshalter i marken (1,1 ng WHO-TEQ kg-1 torrvikt eller 0,001 ppb) och en
med en lokal föroreningsnivå motsvarande 69 ng WHO-TEQ kg-1 torrvikt (0,069
ppb). Exponeringsnivåer för två olika populationer undersöktes. Skillnaderna mellan
populationerna var relaterade till olika levnadsvillkor för landsbygd respektive stad,
13
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
vilket simulerade förväntade skillnader mellan industrialiserade länder och
utvecklingsländer. Beräkningar gjordes i både för vuxna och barn. De
exponeringsvägar som beaktades var intag av jord samt intag av lokalt producerad
mat. Eftersom bioackumulationsdata för dl-PCB inte fanns tillgängliga inkluderades
inte dl-PCB i detta steg av riskbedömningen.
Det modellerade upptaget av PCDD/F i föda stämde i stort sett väl överens med
fältdata från Peru och andra fallstudier. Den största avvikelsen erhölls för ägg, där
modellen underskattade upptaget relativt kraftigt. Vid 1,1 ng WHO-TEQ våtvikt i
marken (0,001 ppb) överskred aldrig exponeringen från respektive exponeringsväg 10
% av TDI för den mest känsliga populationen (barn i utvecklingsscenariot). Vid 69 ng
WHO-TEQ våtvikt i marken (0,069 ppb) erhöll både barn och vuxna i
utvecklingsscenariot en signifikant exponering via alla exponeringsvägar. För flera av
exponeringsvägarna var de beräknade doserna för barn nära eller högre än TDI. För
intag av jord kan dock risken vara överskattad då det antogs att tillgängligheten för
absorption i matsmältningssystemet är 100 %, medan experiment har visat att
biotillgängligheten för PCDD/F i jord är begränsad. Kritiska markkoncentrationer,
som tillåter en lantlig livsstil för barn med högt intag av lokalt producerad mat men
med acceptabla exponeringsnivåer, låg inom 7-25 ng WHO-TEQ kg-1 våtvikt (0,0070,025 ppb) för PCDD/F. Detta intervall minskar dock till 3-13 ng WHO-TEQ våtvikt
(0,003-0,013 ppb) om man antar att 50 % av den totala TEQ exponeringen även
kommer från dl-PCB.
Det beräknade intervallet samt intervallets storlek påverkas av flera osäkerheter i
modellerings-antagandena, t.ex. i) i vilken omfattning som enskilda exponeringsvägar
förekommer tillsammans eller separat, ii) hur stor del av den intagna födan som är
lokalt producerad, iii) mängden föda som intas, iv) mängden jord som intas. Eftersom
riskbedömningen var baserad på hypotetiska populationer ansågs det mer lämpligt att
identifiera ett intervall för kritiska markkoncentrationer snarare än ett enskilt värde.
1.5
Syntes
Med stöd av resultat från flera befintliga studier samt en uppskattning av möjliga
exponeringsnivåer för människor kan gränsvärdet på 15 ppb för PCDD/F i avfall anses
förknippad med risk för människor. Allvarliga risker uppstår bl.a. om impregnerat trä
eller aska tillåts komma in i produktionscykeln för animaliska livsmedel och naturliga
betesmarker eller om människor utsätts för direktkontakt med jord/aska.
Det begränsade antalet fallstudier som identifierats kan eventuellt indikera att
olämplig hantering av PCDD/F kontaminerat avfall inte är särskilt vanligt. Å andra
sidan finns tydliga indikationer på att PCDD/F kontaminerat avfall inte alltid hanteras
på ett sätt som gagnar miljön eller människors hälsa. Öppna deponeringsområden och
vattendrag i t.ex. Asien och Sydamerika är bevisligen recipienter för dumpning av
högkontaminerat avfall. Om sådana aktiviteter har en lokal påverkan på halter av
PCDD/F och dl-PCB i miljön eller för människor, tycks hittills inte vara fastställt
14
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
genom fältstudier av tillräcklig omfattning. Resultaten från fältstudierna i detta projekt
visade att platser med öppen hantering och förbränning av avfall och aska har förhöjda
halter av PCDD/F och dl-PCB, och dessa aktiviteter kan leda till förhöjda halter i
omgivande miljön. Eftersom provtagningsplatserna var påverkad av flera källor (t.ex.
luftburna emissioner från förbränning inom området) var det inte möjligt att särskilja
bidraget från askhanteringen och bidraget från förbränningen.
I riskbedömningen identifierades en kritisk markkoncentration för PCDD/F till 7-25
ng WHO-TEQ kg-1 våtvikt (0,007-0,025 ppb), eller 3-13 ng WHO-TEQ våtvikt
(0,003-0,013 ppb) om man antar att dl-PCB kan stå för 50 % av TDI. För barn som
lever i en lantlig miljö och vars mat är lokalt producerad motsvarar den kritiska
markkoncentrationen en föroreningsnivå som sannolikt inte medför en exponering
högre än TDI. Denna bedömning innehåller dock en rad osäkerheter, t.ex. teoretiska
antaganden som inte verifierats samt naturliga variationer för de parametrar som ingår.
En riskbedömning för hypotetiska populationer kommer alltid att innehålla stora
osäkerheter då den är just hypotetisk. För vuxna individer kan intag av jord/aska vara
en betydelsefull exponeringsväg i samband med yrkesmässig exponering. Preliminärt
har den kritiska halten i fasta matriser för denna exponeringsväg bedömts ligga kring
200-1 000 ng WHO-TEQ kg-1 våtvikt (0.2-1 ppb), men denna bedömning beror bland
annat på vilken biotillgänglighet man antar. Här saknas data för askmatriser.
Fältdata visar att dl-PCB ackumuleras i biota i högre utsträckning än PCDD/F. De
bidrar också signifikant till TEQ-värdet i livsmedel och ingår i TDI. Det faktum att dlPCB inte omfattas av föreslaget LPCL för PCDD/F kan bidra till felaktig bedömning
av den totala risken som är kopplad till bioackumulation.
15
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
16
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
2
Summary
The main focus of the current study was to identify risk scenarios where
polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like
polychlorinated biphenyls (dl-PCBs) in wastes are distributed in the environment and
transferred to humans via food and other exposure pathways. Two field studies were
conducted at sites where wastes and ashes are managed and stored open, one in
Thailand and one in Peru. The aim of these studies was to investigate the degree of
local environmental impact.
To be able to relate human exposure levels to the suggested LPCL for PCDD/F, a risk
assessment was performed using a fate and exposure model (CalTOX), supported by
field data from Peru. Additional human exposure from local sources was estimated in
relation to inevitable human exposure related to diffuse emissions by exposure
calculations.
The aim of the exposure assessment was to establish whether point sources may
contribute to human body burdens above the exposure levels that we are inevitably
subject to from existing background levels as a result of diffuse pollution.
2.1
Dioxin contaminated waste in current
case studies
We identified four major waste categories as being potentially important in the context
of this study:
i)
incineration residues,
ii)
chemical waste,
iii)
waste wood fractions and
iv)
waste from e-waste recycling sites
A limited number of recent case studies are reported for categories i, ii and iv, while
case studies for chemical waste mostly are related to historical incidents. Trading and
shipping of waste wood fractions may be of special importance since there are recently
reported incidents where this waste fraction has contaminated human food chains at
animal food production facilities. For ashes, we only identified one study, and it is
reported from Britain, where bottom ash and some fly ash from a municipal waste
incinerator were recycled as path material in an allotment area. This resulted in
elevated concentrations in free-range chicken eggs.
All incidents for waste wood and ash are reported from European countries, but this
certainly does not exclude the possibility that that serious risk scenarios exist for
developing countries as well. Since these problems can arise in Europe, in spite of
well established and robust regulatory frameworks and practices, the probability of
similar events occurring in countries with more limited environmental control is even
17
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
higher. However, environmental and food/feed control data from developing countries
are often lacking. Since several hazardous pollutants may be present at high levels in
waste and open waste dumping sites, some exposed subpopulations (e.g. waste
pickers) are at risk for increased exposure. Management of PCDD/F contaminated
waste may thus be a serious, but a so far, not well-documented problem. It can be
difficult to relate an environmental impact to management of waste in areas where
other sources co-exist. In the field studies in Peru and Phuket, consequences of open
and unprotected storage of ash could therefore not be investigated separately from the
influence of local air emissions.
2.2
Food and exposure levels related to local
sources
Several studies have reported local PCDD/F contamination of soils and waters related
to industrial point sources, spills, accidents and other polluting activities. At these
sites, elevated exposure levels of humans may occur, often related to consumption of
locally produced food. In cases where abiotic media, such as soil or air, are severely
polluted, direct exposure of the media, e.g. via ingestion of soil, could also result in
high exposure of local inhabitants.
All animal food and feed products contain PCDD/Fs as a result of accumulation from
historic and current emissions from various sources. Levels of contamination in food
and feed produced near local sources are therefore often related to elevated levels in
the environment. This can then result in higher exposure of people residing in vicinity
of the source, compared with the exposure levels for the overall population.
A number of studies show that consumption of locally produced free range chickens
and eggs is a high risk scenario. Some studies also show that environmental
background concentrations in rural scenarios with no local pollution ‘hotspots’ can
cause relatively high PCDD/F levels in free-range eggs. It is difficult to predict
concentrations in eggs with high accuracy. The transfer routes between the
environment and chickens are numerous and complex, and are not easily described by
models. Factors such as congener composition (relative abundance of congeners)
breeding and feeding conditions, soil type and vegetation cover, etc., will affect the
bioaccumulation. Results from single case studies can therefore not be used to
establish generic soil-to-egg transfer ratios. Production of other animal food products,
such as milk and meat, is also a high risk scenario in the presence of local sources.
According to dietary intake studies in different countries, generic population
exposures are often close to, or exceed, the WHO Tolerable Daily Intake (TDI) value.
The TDI is an estimate of the average daily intake of a contaminant that can be
ingested over a lifetime without appreciable health risk. However, the intake levels
differ considerably between different countries. A limited number of studies have
dealt with human body burdens and dietary intakes for populations in developing
countries. Since food consumption habits and living conditions differ between
18
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
different countries, it may be problematic to use data from industrialised country
conditions to express an opinion of the PCDD/F exposure of humans in developing
countries.
2.3
Review of the BIPRO assessment
In the risk assessment of PCDD/Fs conducted by a German consultant (BIPRO) for
the European Commission it was assumed that the legislated maximum level in
commercial eggs is correlated to human health risks based on the tolerable daily intake
(TDI). Since the maximum level in food is not based on a human health risk
assessment, compliance of PCDD/Fs levels in eggs (or other food items) with the
legislated limits is not an indicator of the risk level and should not be used as a criteria
in a risk assessment.
The risk assessment by BIPRO assumes that a PCDD/F concentration of 30 pg WHOTEQ g-1 fat is acceptable in eggs. By using soil-to-egg transfer factors (so called BTF,
biotransfer factors) from two studies, they estimated that the critical PCDD/F
concentration of 30 pg WHO-TEQ g-1 fat in eggs corresponds to soil concentrations
of 1 000 ng TEQ kg-1 d.w. (1 ppb).
A consumption of one egg per day is enough to yield a significant contribution to TDI
if the eggs contain 3 pg WHO-TEQ g-1 fat or more. In contrast to the conclusions in
the BIPRO report, these intake calculations indicate that egg concentrations should not
exceed the EU limit value (3 pg WHO-TEQ g-1 fat). A compilation of literature data
showed that estimations of soil-to-egg transfer of PCDD/Fs and dl-PCBs are highly
variable, and that dl-PCBs are much more available than PCDD/Fs. Considering the
large variability of the soil-to-egg transfer factors, selected bio-transfer factors from
only a few studies are not representative of generic scenarios. The adopted transfer
factor by BIPRO was in the upper range of those calculated from the literature. Thus,
there is a risk that BIPRO significantly underestimates the risk for transfer of PCDD/F
into eggs at soil concentrations of 1 000 ng TEQ kg-1 d.w. (1 ppb). According to the
BTFs calculated from the literature, 3 pg WHO-TEQ g-1 fat in eggs can be reached
already at soil concentrations of 1-70 ng TEQ kg-1 d.w. (0.001-0.07 ppb).
The TDI includes exposure both for PCDD/Fs and dl-PCBs, and both compound
groups may be transferred from solid waste matrices into human food chains, even
though dl-PCBs are more available than PCDD/Fs. Since BIPRO did not consider the
contribution from dl-PCBs in waste to the food chain transfer, their assessment does
not reflect the total risk.
19
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
2.4
The exposure assessment
The exposure assessment conducted within the current study was based on two
contamination scenarios: one background scenario (1 ng WHO-TEQ kg-1 w.w. or
0.001 ppb in the soil) and one local contamination scenario (70 ng WHO-TEQ kg-1
w.w. or 0.07 ppb in the soil). Exposure levels of two different populations were
investigated, reflecting different living conditions for rural/urban life styles and
simulated expected differences between industrialised and developing countries. Each
population consisted of adults and young children. Exposure pathways considered
were ingestion of soil and locally produced food. Because of limited access to
important bioaccumulation data needed for the model calculation, dl-PCBs were not
included in the exposure assessment at this stage.
The modelled accumulation in food was generally in good agreement with field data
from Peru or other case studies. The most distinctive disagreement was for
concentrations in eggs, where the model underestimated the risk. At 1.1 ng WHOTEQ kg-1 w.w. (0.001 ppb) in soil, the exposure levels of single exposure routes never
exceeded 10% of TDI for the most sensitive target population (children in the
Development setting). At 69 ng WHO-TEQ kg-1 w.w. (0.069 ppb) in soil, children
and adults in the Development setting received significant exposure levels via all the
exposure routes. For most of the routes, single doses of the children were close to or
above the TDI. For ingestion of soil, however, the risk may be over-estimated since
the availability for absorption in the digestive tract was assumed to be 100%, while
experimental data have shown that the bioavailability is significantly reduced for
pollutants present in soil matrices. Critical soil concentrations, which allow a rural life
style with high ingestion rates of locally produced food but acceptable exposure levels
in relation to TDI, were identified in the range 7-25 ng WHO-TEQ kg-1 w.w. (0.0070.025 ppb) soil for PCDD/F. The range is reduced to 3-13 ng WHO-TEQ kg-1 d.w.
(0.003-0.013) if it is assumed that dl-PCBs will add to 50% of the total TEQ exposure.
The precision of the range is affected by several uncertainties in the modelling
assumptions, e.g. i) to what extent the exposure routes will exist simultaneously or
alone, ii) the amount of ingested food that is locally produced, iii) food ingestion rates,
and iv) the amount of ingested soil. Since the assessment were based on hypothetical
populations, it was considered as more reasonable to identify an interval of critical soil
concentrations, rather than one single value.
2.5
Synthesis
Supported by results from existing case studies and the human exposure assessment,
the suggested limit of 15 ppb for PCDD/Fs in waste is considered to be associated
with risks for humans. There are e.g. risks if impregnated wood or ash is introduced in
the production of animal food items or natural pastures, or if humans are subject to
direct contact with soil/ash.
20
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
The limited number of existing case studies may indicate that improper management
of PCDD/F waste is uncommon. On the other hand, there are indications that PCDD/F
contaminated waste is not always managed having protection of the environment and
human health in mind. Open waste dump sites and rivers in e.g. Asia and South
America are potential targets for dumping of highly contaminated waste. If such
activities do have an impact on local environmental PCDD/F or dl-PCB
concentrations or human exposure levels, it is, so far, not well investigated.
The minor field studies in Peru and Thailand confirmed that highly contaminated
ashes are stored on open ground at sites where the waste is produced. The results
indicated that such sites constitute PCDD/F and PCB pollution hot spots that may
affect the surroundings by wind-blown distribution of ashes. Our field study did,
however, not allow apportionment between contamination from ash residues and local
air emissions from the recycling activities.
In the risk assessment, a critical soil concentration of 7-25 ng WHO-TEQ kg-1 w.w.
(0.007-0.025 ppb), or 3-13 ng WHO-TEQ kg-1 w.w. (0.003-0.013 ppb) if one assumes
that dl-PCB contribute to 50% of the TDI, was identified. For children in rural setting
and where the food is locally produced, the critical soil concentration corresponds to a
level where the exposure is not likely to exceed TDI. The assessment includes a
number of uncertainties, e.g. some of the assumptions have not been verified and the
natural variability of the parameters was not taken into account. A risk assessment
which is made for hypothetical populations will always suffer from a large degree of
uncertainty. For adults, ingestion of soil and ash can constitute an important exposure
route in occupational exposure scenarios. A critical solid matrices concentration has
preliminary been assessed to 200-1 000 ng WHO-TEQ kg-1 w.w. (0.2-1 ppb) for this
exposure route, depending on assumed internal bioaccessibility. Such data is lacking
for ash matrices.
Field data from several scientific studies show that dl-PCBs accumulate to a higher
extent than PCDD/F in biota. Dl-PCBs contribute significantly to the total TEQ in
food and risks can be assessed by comparing daily intake to the TDI for PCDD/Fs and
dl-PCBs. Since dl-PCBs are not included in the suggested LPCL for PCDD/F, the total
risk associated to exposure of PCDD/F and dl-PCB contaminated waste can be
underestimated.
21
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
3
Background
The production, use and release of persistent organic pollutants (POPs) are dealt with
by the Stockholm Convention, which aims to reduce and eliminate the flows of these
substances in the environment. PCDD/Fs and PCBs are two substance groups that are
categorised as POPs in terms of persistence, environmental behaviour and toxicology.
In order to classify and manage waste products in an environmentally sound manner, a
suggested maximum level of 15 µg TEQ kg-1 (15 ppb) for PCDD/F in waste was first
proposed by the Basel convention, and was later adopted by EU (BIPRO, 2005). The
corresponding level for ∑PCB6 is 50 mg kg-1 (50 ppm). These levels are commonly
referred to as the Low POP Content Limits (LPCL). Some PCDD/F contaminated
waste products may be recycled in the society, and contaminants in the waste can
therefore be distributed into the environment.
There is an increased concern of environmental problems caused by uncontrolled
dispose and recycling of waste and waste products. Urbanisation and industrial growth
in developing countries stimulates the production of hazardous waste, and proper
disposal strategies are needed to reduce environmental harm and human health risks in
these countries (Omran & Gavrilescu, 2008). While many industrialised countries
have an environmentally sound management of hazardous waste, developing countries
lack much of the financial and political resources needed to treat the waste in a proper
manner or to control possible health impacts from hazardous waste (Sonak et al.,
2008; Yousif & Scott, 2007; Mbuligwe & Kaseva, 2006). These countries face also
problems related to the absence of sanitary landfills, limited public knowledge about
proper waste management practices and increasing illegal dumping. In some cases,
hazardous waste is neither treated nor separated from the non-hazardous waste
fraction, and the dump sites are neither lined nor covered. Local authorities do not
necessarily consider environmental impacts of new or existing dump sites. Thus,
waste deposits can be allocated to areas without considering the potential transport of
hazardous pollutants, and monitoring and safeties practices such as covering and
fences are neglected. Inspection of waste before dumping is not always occurring, and
illegal dumping of toxic chemicals is not uncommon. Regulation of maximum levels
of PCDD/Fs and dioxin-like compounds in waste is therefore important, both at
national and international scales, in order to prevent further distribution of POPs in the
environment and to protect human health.
22
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
4
Dioxins
The chemical substances covered in this report are polychlorinated dibenzo-p-dioxins
(PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated
biphenyls (dl-PCB). PCDDs and PCDFs are usually treated as one compound group
with the acronym PCDD/Fs and commonly referred to as dioxins. In this report, only
2,3,7,8-substituted congeners were considered.
A number of PCBs share the same toxic mode of action as 2,3,7,8-substituted
PCDD/Fs. These substances are called dioxin-like PCBs (dl-PCBs) or co-planar PCBs.
Dl-PCBs consist of 12 non-ortho and mono-ortho substituted PCBs (PCBs 77, 81,
105, 114, 118, 123 126, 156, 157, 167, 169, 189; numbering according to IUPAC).
2,3,7,8-substituted PCDD/Fs and dl-PCBs have been assigned toxicological
equivalence factors (TEFs) according to a scheme that originally was developed for
PCDD/Fs (Van den Berg et al., 2006). TEFs are used to calculate toxic equivalence
concentrations (TEQs) from analytical concentrations of single congeners. The total
toxicity of a mixture of congeners is the sum of products of the analytical congener
concentrations and their TEFs. There is no consistency of reported TEQ units in the
literature since different TEF schemes have been developed (I-TEF, WHO-TEF, etc).
When citing data, originally reported TEQ units have usually been cited. However, in
some data compilations, it was not convenient to keep the original TEQ units and the
generic expression “TEQ” was used instead. Empirical data from the field studies are
reported as WHO-TEQ, following the TEF scheme from 2005 as presented in Table 1.
23
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Table 1. TEF scheme according to WHO (Van den Berg et al., 2006).
Congener
WHO-TEF 2005
2,3,7,8-TCDD
1
1,2,3,7,8-PeCDD
1
1,2,3,4,7,8-HxCDD
0.1
1,2,3,6,7,8-HxCDD
0.1
1,2,3,7,8,9-HxCDD
0.1
1,2,3,4,6,7,8-HpCDD
0.01
OCDD
0.0003
2,3,7,8 -TeCDF
0.1
1,2,3,7,8 -PeCDF
0.03
2,3,4,7,8 -PeCDF
0.3
1,2,3,4,7,8 -HxCDF
0.1
1,2,3,6,7,8 -HxCDF
0.1
2,3,4,6,7,8-HxCDF
0.1
1,2,3,7,8,9-HxCDF
0.1
1,2,3,4,6,7,8 -HpCDF
0.01
1,2,3,4,7,8,9-HpCDF
0.01
OCDF
0.0003
PCB #77
0.0001
PCB #81
0.0003
PCB #105
0.00003
PCB #114
0.00003
PCB #118
0.00003
PCB #123
0.00003
PCB #126
0.1
PCB #156
0.00003
PCB #157
0.00003
PCB #167
0.00003
PCB #169
0.03
PCB #189
0.00003
So far, Low POP Content Limits are only suggested for PCDD/Fs and the sum of
seven PCBs (∑PCB7), while dl-PCBs are not yet suggested to be regulated. Because
of their dioxin-like properties, however, they should ultimately be included in the
LPCL for PCDD/Fs, since human health risks depend on both compound groups. This
is also the reason to why both PCDD/Fs and dl-PCBs were addressed in this report.
Two different concentration units for solid matrices are used in the cited literature.
The units “ppb” and “ppm” are applied for the Low POP Content Limits, while
universal units such as “ng kg-1” or “pg g-1” are used for empirical data in the open
literature. The units are translated into each other according to
ppb = parts per billion = µg kg-1 (or 1000 ng kg-1) = ng g-1
ppm = parts per million = mg kg-1= µg g-1
24
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
5
Dioxin contaminated waste
5.1
Waste categories
Dioxin contaminated wastes are generated by different activities in the society and
consist mainly of solid matrices. The industrial sector is the major producer of waste,
and major amounts origin from municipal waste incineration (MSWI), power
production, and metallurgical and steel alloy industries. A more comprehensive
compilation of sources and dioxin waste flows is presented in BIPRO (2005).
It was beyond the scope of this study to present a full review of dioxin levels in
different waste fractions, but a selection of existing data is presented below to
illustrate the contamination levels of different waste categories that were confirmed to
be of importance in the context of this study:
i)
residues from thermal processes,
ii)
impregnated wood and waste wood litter,
iii)
chemical waste, and
iv)
residues from e-waste recycling
These waste fractions are considered as important in relation to the produced amounts
and known contamination levels (categories i-iii), or from case studies of sites were
management/recycling of PCDD/F contaminated waste has harmed the environment or
human food chains (categories i-iv).
A thorough literature search for case studies and incidents that exemplifies
environmental harm or human health risks caused by improper management of
PCDD/F contaminated waste was conducted, but only a few relevant studies were
found. These are presented in the following paragraphs. On the contrary, there are a
number of studies that report upon national food contamination incidents, where
human food chains were severely contaminated by PCBs or PCDD/Fs (Hoogenboom
et al., 2004). Many of these cases were probably caused by illegal actions, accidents or
unawareness of PCDD/F or PCB residue levels in products and ingredients that later
were introduced into feed and food chains. However, the incidents were often tracked
to small producers, which in the end had a large and negative financial impact on
affected feed and food markets (Fürst, P., Plenary lecture Dioxin Conference 2009).
The cases illustrate the ease in which food chains becomes negatively affected if
materials are contaminated by processes in the modern society.
25
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
5.2
Residues from thermal processes
5.2.1
Concentrations of pollutants
Incineration generates different types of solid residues, such as fly ashes, filter dusts,
bottom ash and boiler ash. Major producers include municipal waste incineration
plants (MSWI), power plants, metallurgical and chemical industries. Residues from
thermal processes are also generated from metal recycling. These residues contain
various levels of PCDD/Fs and dl-PCBs. Fly ash measurements have been numerous,
while MSWI bottom ash and boiler ash are less frequently investigated. In Table 2,
data from a number of references are compiled to illustrate expected PCDD/F levels.
However, the compilation covers only a selection of studies and matrices.
Table 2. Concentrations (ng TEQ kg-1) of PCDD/Fs in different incineration residues.
Waste type
PCDD/F
(ng TEQ kg-1)
Country
Reference
Fly ash, industrial & medical
refuse
8 500-67 500
Colombia
Aristizabal et al., 2008
Fly ash, power production
2.2-190
Mauritius
Yive & Tiroumalechetty, 2008
Filter dust, galvanising plant
127-8 075
Spain
Martinez et al., 2008
Ash, Waelz process
103 000
Taiwan
Chi et al., 2008
Fly ash, secondary steel plant
1 899
Thailand
UNEP, 2001
Bottom ash, MSWI
5-10
Thailand
"
Fly ash, MSWI
228-686
Thailand
"
Bottom ash, MSWI
0.2-245a
various
Vehlow et al., 2006
Boiler ash, MSWI
0.3-400b
various
"
Fly ash, MSWI
120-41 4000a
various
"
Bottom ash, MSWI
0.1-200
Sweden
Svenska Renhållningsverksföreningen, 2001
Fly ash, MSWI
140-18 000
Sweden
"
Fly ash, bio fuels
120-270
Sweden
Oehme & Muller, 1995
Bottom ash, bio fuels
0.2-1.1
Sweden
"
a
b
samples from 1990-2004; samples from 1990-1999
The expected range of PCDD/F concentrations in bottom ash from modern MSWI
facilities is 1-30 ng TEQ kg-1. For recently produced fly ashes, the range is 100-10
000 ng TEQ kg-1 (Vehlow et al., 2006). During the past decade, PCDD/F
concentrations in fly ash have decreased (Vehlow et al., 2006).
The fuel type is of major importance for the final levels in the residues. Fly ash and
bottom ash from bio fuel combustion usually contain lower levels (<300 ng TEQ kg-1;
Table 2), than ashes from MSWI. However, mixing with PCDD/F contaminated wood
fractions may elevate the levels by orders of magnitude (Oehme & Muller, 1995).
Limited data exist for PCB levels in MSWI solid residues (Vehlow et al., 2006). When
measured, dl-PCBs are generally not reported separately from other PCBs. Thus, it is
26
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
difficult to get good estimates of general levels in incineration residues. In the study
by Vehlow and co-authors (2006), dl-PCBs contributed by 2-7% of the total TEQ in
MSWI bottom ash, and by <1-10 % in MSWI fly ash. Other studies have reported a
TEQ fraction of 1% for dl-PCBs in fly ash (Sakurai et al., 2003).
Accidental fires will also result in residues contaminated with PCDD/Fs. Swedish
experiments with e-waste and car tyre fires resulted in waste that contained 11-2 100
ng I-TEQ kg-1 (SP Swedish National Testing and Research Institute, 2005). The
highest PCDD/F level was found in e-waste fire residues, while dl-PCBs were not
analysed.
There are different types of incineration waste that may contain PCDD/Fs
or dl-PCBs.
It seems that expected ranges in most waste products will fall below the
suggested LPCL for PCDD/F. For dl-PCBs, knowledge about
concentrations is limited.
5.2.2
Case studies
A recent publication by Mari et al. (2009) reported on the impact on environmental
levels and human health from a hazardous waste landfill in Catalonia (Spain) that
receives PCDD/F contaminated residues. The landfill site operates according to
national regulations, and waste management practices follows principles set by EU.
The authors found a slight increase of PCDD/F concentrations in air and soil at the
landfill, but in general terms, the concentrations were low and the human health
assessment indicated no risk for local residents exposed to air or soil. The soil
concentrations were 1.5 and 2.1 ng WHO-TEQ kg-1 d.w. However, this landfill is
sealed and protected and is not representative of open landfills or other non-regulated
waste sites.
In the UK, there is one relevant case study (Pless-Mulloli et al., 2001) that illustrates
how dioxin contaminated incineration residues will contaminate the environment and
human food chains if the management and recycling practices are not fully controlled.
During a period of 5 years (1994-1999), 2 000 tons of ash was recycled at 51 sites
across Newcastle.
27
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
The egg concentrations in the Newcastle case correspond to 0.04-5.6 pg I-TEQ g-1 fresh
weight (assuming a fat content of 10% in whole eggs).
A daily consumption of one Newcastle egg (60 g) per day equals a human dose of 0.04 to 5.6
pg I-TEQ kg-1 b.w. and day (assuming a bodyweight of 60 kg).
The recommended tolerable daily intake (TDI) for PCDD/Fs and dl-PCBs is 2 pg TEQ kg-1 b.w.
and day.
One of the sites consisted of allotment areas where animals (hen, ducks, pigeons and
horses) also were raised. Ash samples from foot paths contained up to 9 500 ng I-TEQ
kg-1, which is below the suggested LPCL of 15 000 ng TEQ kg-1, while the highest
recorded soil concentration was 272 ng I-TEQ kg-1. Eggs from the allotments
contained 0.4-56 pg I-TEQ g-1 fat, and the congener distribution patterns were similar
to that of ash. It was concluded that PCDD/Fs had been transferred into chicken eggs,
even when the animals did not have direct access to the contaminated footpaths. In the
risk assessment, it was recommended that poultry and egg production should be
restricted until the ash was removed.
Other studies indicate that management of ashes might be a source of PCDD/Fs in
local environments in poor countries, and that some populations might be at risk for
elevated exposure, even though no cases studies are reported. In some countries,
PCDD/F levels in incineration ashes is not regulated at all, and the residues are often
mixed with household waste and disposed of in municipal solid waste landfills without
previous treatment or protection of human health (Aristizabal et al., 2008). Elevated
exposure to hazardous pollutant is therefore possible for people scavenging the
landfills for recyclable material. The field sampling at the waste site Zapallal (Peru)
that was performed within the current project showed that levels of PCDD/Fs in ash
stored on open ground were close to the suggested LPCL of 15 ppb (Chapter 9). The
final fate of the contaminated residues is not known, but according to a preinvestigation of the area by local NGOs, a nearby river is used for dumping of waste.
In Europe, local NGOs have reported upon dumping of ash-like residues of unknown,
European origin in Belaruchi (Belarus, Figure 1). The material was dumped on open,
unprotected ground, and the residues contained approximately 1 000 ng TEQ kg-1 (1
ppb; personal communication J. Petrlik, Arnika, Czech Republic).
28
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Figure 1. Dumping of PCDD/F contaminated residues in Belaruchi, Belarus (J. Petrlik, Arnika).
Open dumping of POP-contaminated waste can also affect wildlife (Watanabe et al.,
2005). Uncontrolled management strategies will therefore result in that toxic
substances are transferred into the environment with reduced possibilities to detect or
measure impacts on the environment or human health.
Regardless if dumping of PCDD/F contaminated ashes is a legal or illegal action, it
will increase the environmental hazard at open dump sites. These areas are already
known to contain elevated levels of hazardous compounds, such as DDT, PCBs and
HCH (Minh et al., 2006). Dump sites may also contain elevated concentrations of
PCDD/F due to e.g. open burning and recycling activities (Minh et al., 2003; Table 3).
Dumping of PCDD/F contaminated waste from other activities will therefore become
an additional source.
Table 3. Reported PCDD/F soil concentrations (ng WHO-TEQ kg-1 d.w.) from open dump sites
and control sites in Asian countries (Minh et al., 2003).
Philippines
Cambodia
India
VietnamHanoi
VietnamHo Chi Minh
Dump site
400-630
1.4-1 700
9.9-200
0.4-850
0.02-4.4
Control site
-
0.031-4.5
0.05-0.34
1.0
0.36-1.2
Other risk scenarios for solid residues from thermal processes are related to recycling
in e.g. geotechnical applications, construction materials and agriculture (Ferreira et al.,
2003). However, few investigations have focused on the environmental impact with
respect to organic contaminants for these recycling options. At the same time, there
are known examples where town refuse waste ash has been used as fertiliser to
increase the fertility of soil (Pasquini, 2006).
29
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Residues from electric arc furnaces and ashes containing high levels of zinc can be
recycled in industrial processes, such as the Waelz process, to extract the metals. Since
PCDD/Fs are regenerated in the process, the recycling may result in high emissions to
air if the air pollution control devices are inefficient (Chi et al., 2006). Chi and coauthors demonstrated that 560 ng TEQ kg-1 recycled ash was emitted from one
facility. This recycling option will therefore result in large emissions to air and highly
contaminated solid waste residues are generated (Chi et al., 2008; Table 2)
The management of PCDD/F contaminated waste is poorly regulated in some
countries. Open, unprotected storage and dumping practices in poor countries
may be risk scenarios with limited possibilities to detect and measure impacts
of the environment and human health.
5.3
Impregnated wood and waste wood litter
5.3.1
Concentrations of pollutants
PCDD/Fs are unintentionally formed during the production of e.g. wood impregnation
chemicals (such as Ky-5, Dowicide G and other chlorophenol based agents). The
production of these pesticides has ceased, but CP treated wood may still contain high
levels of PCDD/Fs. In Table 4, wood and wood litter TEQ concentrations reported in
the open literature are compiled.
Table 4. Reported PCDD/F and dl-PCB concentrations (ng TEQ kg-1) in different wood
fractions.
Waste type
PCDD/F
dl-PCB
Country
Reference
Wood at animal prod.
facilities
n.d.-91 620
-
USA
Huwe et al., 2004
Sleepers
21 000
0.93
Japan
Asari et al., 2004
Waste wood chips
0.94
0.51
"
"
Untreated wood
0.006
0.30
"
"
Litter
0-0.86
0.19-240
"
"
PCP treated wood
11-315 000
-
-
Fries et al., 2002
Impregnated wood
67- 38 000
-
various
SEPA, 2009
-
Italy
Brambilla et al., 2009
Wood litter
a
50
n.d.; not detected, a the concentration was published as 50 000 ng WHO-TEQ kg-1 but was corrected
to 50 ng WHO-TEQ kg-1 after correspondence with the author; PCP: penta-chlorophenol
Even though the TEQs are mostly related to PCDD/Fs, dl-PCBs can in some cases
contribute significantly as well. However, not all studies have included dl-PCBs in the
30
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
analysis. The range of reported concentrations is large, but it is obvious that waste
wood fractions will fall above and below the currently suggested LPCL.
5.3.2
Case studies
As long as CP treated wood is in use, demolition of
old wood constructions may result in highly
contaminated waste wood fractions. Recent studies
have shown that waste wood fractions may enter
the human food chain via animal food production
facilities (Brambilla et al., 2009; Diletti et al., 2005;
Asari et al., 2004), and that shipping of
contaminated wood between countries is a risk
scenario.
Maximum levels are legislated
limit values for contaminants in
food (see also Table 4).
PCDD/F in eggs and egg
products:
3 pg WHO-TEQ g-1 fat
PCDD/F and dl-PCB in eggs
and egg products:
6 pg WHO-TEQ g-1 fat
PCDD/F in milk and dairy
Two case studies report serious contamination of
products:
chicken eggs by penta-chlorophenol (PCP)
3 pg WHO-TEQ g-1 fat
contaminated wood litter (Brambilla et al., 2009;
PCDD/F and dl-PCB in milk
Diletti et al., 2005). Both incidents took place in
and dairy products:
Italy. In one study, the wood litter contained 50 ng
6 pg WHO-TEQ g-1 fat
WHO-TEQ kg-1, resulting in mean chicken egg
concentrations of 46 pg WHO-TEQ g-1 fat (Brambilla et al., 2009; the published
wood litter concentration of 50 000 ng WHO-TEQ kg-1 has here been corrected to 50
ng WHO-TEQ kg-1 after correspondence with the author). Brambilla and co-authors
point also out that there is no legislation to prevent exposure of food-producing
animals to bioaccumulative substances via materials, such as barns, stables or litter. In
the other study, contaminated wood litter (50.8 ng WHO-TEQ kg-1) and wood
shavings (40.1 ng WHO-TEQ kg-1) was used at the farm (Diletti et al., 2005).
Chicken egg and chicken meat contained PCDD/Fs at levels significantly exceeding
legislated maximum levels for food stuffs (eggs: 33 and 88 pg WHO-TEQ g-1 fat;
meat: 45.2 pg WHO-TEQ g-1 fat).
Recent incidents in Europe show that recycling of PCDD/F contaminated
wood is a risk scenario for animal food production facilities. Waste wood
concentrations were far below the suggested limit of 15 ppb for PCDD/F.
31
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
5.4
Chemical waste
5.4.1
Concentrations of pollutants
The use and production of chlorinated pesticides and chemicals have polluted the
environment with PCDD/Fs in several countries (Holt et al., 2010, Weber et al., 2008).
Table 5 summarises concentrations of PCDD/Fs and dl-PCBs in some chemical
products.
Table 5. Reported PCDD/F concentrations (ng TEQ kg-1) of technical formulations.
Product
PCDD/F
Country
Reference
PCP
140 000-5 400 000
Japan
Masunaga et al., 2001
CNP
2 600-10 000 000
"
"
Chloranil
20-16 300
China
Zhu et al., 2008; Zhang et al.,
2002
Pentachlorophenol (PCP) and chlornitrofen (CNP) products may contain extremely
high concentrations of PCDD/Fs. High levels may also be found in dye ingredients,
e.g. chloranil, that are currently used in textiles, plastics and paints (Zhang et al. 2002;
Zhu et al. 2008). The contamination levels seem to depend on the production date,
since lower levels are often found in more recently produced chemicals (Masunaga et
al., 2001; Zhu et al., 2008; Zhang et al., 2002).
Since PCDD/Fs are detected in chemical formulations that are currently in use (Holt et
al., 2010; Zhang et al., 2002; Zhu et al., 2008), waste from the production may also
contain levels that are of concern. There is, however, limited data on PCDD/Fs
concentrations of production waste categories in the open literature. Historically, the
chemical industry has a large record of PCDD/F contamination incidents related to
production of chemicals and handling of waste (Weber et al., 2008). Due to the high
production volumes of the chemical industry in e.g. China, Zhu et al. (2008) addressed
their importance as a relevant PCDD/F source.
The problems related to pollutants in chemical waste are complex, since chemical
recycling and remediation processes may generate emissions of other toxic
compounds than the original ones (Braga et al., 2002). The toxicity of chemical waste
is also dependent on mixtures of pollutants, and not only to PCDD/Fs. Chemical waste
often consists of technical chemical formulations such as pesticides. The presence of a
mixture of hazardous pollutants may result in that this waste category can be classified
as a POP-waste based on other criteria than the abundance of PCDD/Fs. Chemical
waste has been recognised as a growing environmental and human health risk problem
in poor countries, as well as in industrialised ones (Holt et al., 2010).
5.4.2
Case studies
Identified case studies related to management of PCDD/F contaminated chemicalwaste are mostly related to historical incidents (Asmus et al., 2008; Lee et al., 2006a
32
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
and b; Wu et al., 2001; Isosaari et al., 2000). The cases are characterised by large
emissions of chemicals or production wastes to soil or waters. The magnitude of the
contamination have resulted in severely contaminated food chains and elevated
exposure of humans (Asmus et al., 2008; Lee et al., 2006a; Braga et al., 2002). No
reports on recent incidents were found.
5.5
E-waste recycling
5.5.1
Concentrations of pollutants
An ongoing formation source of PCDD/Fs is the recycling of e-waste in developing
countries (Sepúlveda et al., 2009; Wong et al 2007; Leung et al 2007, Gullett et al.,
2007). Besides of air emissions, incineration and recycling residues may contain high
levels of organic pollutants. In
Table 6, PCDD/F levels in different types of residues from the e-waste megasite
Guiyu (China) are compiled. Since dl-PCBs were not included in the measurements,
total TEQ levels in the waste fractions are most likely even higher.
Table 1. Reported PCDD/F levels (ng TEQ kg-1) in waste products from e-waste recycling in
China.
Waste type
PCDD/F
Reference
Ash
5 700
Zhu et al., 2008
Electronic shredder waste
66.9
Ma et al., 2008
Acid leachate
203-1 100
Leung et al., 2008
Cable wiring and plastic combustion
residues
84-174
"
Ash
155-14 400
Luksemburg et al., 2002
5.5.2
Case studies
Even though e-waste sites are known for on-going contamination of the environment,
few measurements of PCDD/F contamination related to management of residues from
the recycling activities have been reported (Sepúlveda et al., 2009). Most concern has
been raised about air emissions, and less focus has so far been paid to the management
of the solid/liquid residues. However, in one study from the mega-site Guiyu, it was
reported that PCDD/F polluted ash from the e-waste site at had been dumped in the
adjacent Lianjing River (Luksemburg et al., 2002). Sediment samples from the
dumping site showed extremely high contamination levels (up to 35 200 ng WHOTEQ kg-1 d.w.). At this site, the residents used water from the river for washing
clothes and cleaning cookery utensils. Sediment samples 20 and 50 km downstream
the e-waste site did, however, not contain elevated levels, which was tentatively
explained by the low flow of the river.
33
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
E-waste recycling activities are known as on-going sources for formation of
PCDD/Fs. Residues from the recycling are known to be contaminated with
PCDD/Fs. However, limited data exist, and dl-PCBs have not been
investigated. Dumping of PCDD/F contaminated e-waste residues in the
local environment has been reported.
34
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
6
Human exposure
There is a general consensus that humans are mainly exposed to PCDD/Fs and dlPCBs via the diet (Mato et al., 2007; European Commission, 1999). Most important
are ingestion of food of animal origin, such as meat, dairy products, eggs and fat fish.
In pristine environments, the background concentrations of both PCDD/Fs and dlPCBs are low and exposure via ingestion of soil and water or inhalation of air is
insignificant.
Tolerable weekly intakes (TWI) of PCDD/Fs and dl-PCBs for humans stand for a
long-term weekly intake with no risk of negative effects of human health. The TWI
recommended by the Scientific Committee on Food of the European Commission is
currently set to 14 pg TEQ kg-1 b.w. week-1 (SCF, 2000). This recommendation is
often expressed as a tolerable daily intake (TDI) of 2 pg TEQ kg-1 b.w. day-1. In
2000, WHO came up with a TDI of 1-4 pg TEQ kg-1 b.w. day-1, where the lowest
level is a long term goal (WHO, 2000). The TDI is often used to evaluate results from
dietary intake studies of different populations.
6.1
Exposure via dietary intake
Dietary intake studies are used to estimate human exposure of pollutants from
ingestion of food based on food concentration and food ingestion data. A compilation
of data from dietary exposure studies for PCDD/Fs and dl-PCBs from different
countries are presented in Table 7. The compilation should not be considered as
complete, but illustrates the variation of human exposure levels for different age
classes and countries.
35
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Table 2. Reported estimations of dietary intake of PCDD/Fs and dl-PCBs (pg TEQ kg-1 b.w.
day-1) for human populations.
Country
Age
Mean/median
90th or 95th
percentile
Netherlands
40
1.1
1.7
Baars et al., 2004
"
10
1.5
2.3
"
"
2
2.8
4.4
"
Italy
13-94
2.28
-
Fattore et al., 2006
Reference
"
7-12
3.37
-
"
"
0-6
5.34
-
"
Finland
adult
1.5
-
Kiviranta et al, 2004
Sweden
<10
2.7-4.5b
4.6-9.3
Bergkvist et al., 2008
b
"
11-24
1.5-2.1
3.3-5.1
"
China
-
1.4
-
Zhang et al., 2008
Li et al., 2007
China
18-45
0.15-0.96
-
Japan
-
1.52 or 1.78a
2.91
Japan
17-72
1.06/0.79
-
Arisawa et al., 2008
USA
0-1
42.0
-
Schecter et al., 2001
"
1-11
6.3/6.1c
-
"
"
12-19
3.5/2.7 c
-
"
"
20-79
2.4/2.2
c
-
"
"
80+
1.8/2.0 c
-
"
Egypt
-
6.04-6.68
-
Loutfy et al., 2006
estimated by deterministic or probabilistic approach; bdifferent genders and age classes; cmales and
females, respectively;
a
As illustrated by Table 7, the estimated dietary intake levels differ between different
countries. Some of the variation is likely related to differences in the applied
methodology of the investigations, but more important factors are probably dietary
habits, national and local contamination levels of food and geographical location of
the populations (Arisawa et al., 2008; Chen et al., 2003; Undemann et al., 2009)
36
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Available data needed for estimation of
Little is known about dietary exposure
dietary intake exposure and human body
levels of populations in developing
burdens of environmental pollutants in
countries. There are a large number
developing countries and remote areas are
of factors that contribute to the dietary
exposure levels. Thus, it is not
limited (Linderholm et al., 2009; Sun et al.,
possible to extract data for a
2005; Sun et al., 2006). Significant
population in a specific region and
uncertainties will therefore remain about
then apply these data for populations
the exposure levels of general populations
in other parts of the world.
and subpopulations in these areas, but
A compilation of international data
might be reduced by the global POPs
shows that many populations are
exposed for dioxins and dioxin-like
monitoring program related to the
PCBs at doses near or above the
Stockholm Convention and the ongoing
tolerable daily intake (TDI) of 2 pg
global human milk study. The study by
WHO-TEQ kg-1 b.w. and day.
Loutfy et al. (2006) indicates that the
exposure levels of general populations in
developing countries may exceed the current exposure of the populations in
industrialised countries. In contrast, low exposure levels have been estimated for
populations in remote areas of e.g. China (Sun et al., 2005). In an international
screening study of POPs in butter, it was concluded that butter from Asia, America
and South African regions were less contaminated than butter from Europe, which
indicate that the overall exposure level is lower in these countries (Santillo et al.,
2003). However, the authors of this study stated that limited food concentration data
from these regions exist, and the representativeness of existing samples for each
region could not be guaranteed.
Environmental and human living conditions are not the same in developing countries
as in industrialised ones, and local sources such as waste dump sites and back-yard
burning, may add to the total exposure, directly or indirectly (Kunisue et al., 2004).
Since many poor people depend on food from the local environment, they are more
vulnerable for contamination of food chains via local sources. In contrast,
industrialised populations buy most of their food via groceries, where the food is
commercially produced and controlled by national and international legislations.
Dietary habits might also differ between urban and rural populations.
6.2
Exposure routes near local pollution
sources
Local PCDD/F sources may affect biotic and abiotic exposure media via emissions to
air, water or soil. Direct exposure via these media contributes in general to no more
than a few percent of the total dietary exposure. In local contamination scenarios,
contaminated local food chains are often identified as the main risk scenario (Kao et
al., 2007; Pirard et al., 2005; Pless-Mulloli et al., 2005). However, there are cases
when local emissions have caused incremental human exposure by contact with soil
and air.
37
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
The contamination of most concern in local contamination scenarios is the
contamination of agricultural food chains, such as free-range chickens and eggs, and
milk and meat from grazing animals (Chen et al., 2008; Turrio-Baldassarri et al.,
2008; Cerna et al., 2007; Turrio-Baldassarri et al., 2007; Goldman et al., 2000; Harnly
et al., 2000). Also aquatic food chains, such as fish and seashells for food
consumption, may become contaminated. As presented in the following chapter, these
dietary routes are widely associated to elevated human body burdens in the presence
of local sources.
Ingestion of vegetables, which normally contribute insignificantly to the daily
exposure, may become significant if soil concentrations close to local sources are
elevated (Nakagawa et al., 2002; Donato et al., 2006). Root crops grown in
contaminated soil will contain higher levels of PCDD/Fs (Åberg et al., 2010), mostly
due to accumulation in the peels (Engwall & Hjelm, 2000; Hülster & Marschner,
1993), and leafy vegetables may become contaminated by soil and dust particles that
adsorb to leaf surfaces.
6.3
Human body burdens in local
contamination scenarios
Open waste dump sites have been recognised to contain high concentrations of organic
pollutants, including PCDD/F. Millions of people in developing countries must rely on
scavenging waste to earn their own living. Two studies report on body burdens of
POPs in populations characterised by an intense contact with waste dump sites.
Cuadra et al. (2006) found that children (age 11-15) working at a waste dump sites
were more exposed to POPs than children in industrialised countries. They also found
a gradient with decreasing exposure at increasing distance from the waste site. Santos
et al. (2003) found that people living at a waste site displayed 2-155 times higher
serum concentrations of POPs compared to a control group. None of the studies
included measurements of PCDD/Fs or dl-PCBs.
Several studies show that locally contaminated food chains may cause high exposure
and/or elevated body burdens of local residents (Turrio-Baldassari et al., 2008; Ma et
al., 2008; Chan et al., 2007; Lee et al., 2006a; Goldman et al., 2000; Harnly et al.,
2000). Table 8 summarises results from a selection of studies where residential human
body burdens of PCDD/F were studied in connection to various local exposure
scenarios. Even though the studies are not fully comparable, the results are consistent
in that they illustrate the significance of local exposure from human food chain
contamination. The study by Kunisue et al. (2004) was performed at open waste dump
sites for which environmental levels are reported in Table 3. In this study, elevated
body burdens in people living near the dump sites were only found in India,
presumably since a local animal food chain was contaminated via the waste site. High
concentrations in soil at waste sites in Vietnam and Cambodia did not affect the body
burdens of the residents (Table 8).
38
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Table 3. Reported human body burdens of PCDD/Fs (pg TEQ g-1 fat or pg TEQ g-1 hair) of
residentials in local contamination scenarios together with reference values.
Specimen
Exposure
scenario
Exposed
population
Reference
Population
Country
Reference
Human milk
e-waste site
21
9.35
China
Chan et al.,
2007
Placenta
"
35.1
"
"
11.9
a
a
Hair
"
33.8
5.59
"
"
Human milk
PCP contaminated
site
17.5-187
9.65
China
Wu et al., 2001
Serum
PCP contaminated
site, egg
26.7
17.0
USA
Goldman et al.,
2000
Serum
egg and beef
63.7
17.0
USA
"
Serum
MSWI, locally prod.
food
49
31
Belgium
Fierens et al.,
2003
Serum
MSWI, industrial
area
31
31
"
"
Serum
Hazardous waste
incineration, locally
prod. food
22.7±11.1
20±8.3
Taiwan
Chen et al.,
2006
Breast milk
Dumping site,
locally prod. food
21
8.3
India
Kunisue et al.,
2004
"
Dumping site
5.6
5.3
Cambodia
"
Dumping site
6.0
6.3
Vietnam
"
"
a
pg g-1 dry weight
The significance of dietary exposure routes is also illustrated in Figure 2, using data
from Turrio-Baldassari and co-authors (2008) who investigated PCDD/F and dl-PCB
TEQ serum levels in former workers and residents from a PCB contaminated area in
Italy. People that consumed locally produced food were more exposed than people
who were just living in the contaminated area. The study stresses also the fact that
local sources may have a significant impact on human body burdens several decades
after cessation of the contamination. However, Goldman et al. (2000) found that even
short term (2 years) exposure from ingestion of locally produced food had a negative
impact of human serum concentrations.
39
pg WHO-TEQ g-1 fat, upperbound estimates
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Non-ortho PCB
400
Mono-ortho-PCB
350
PCDD/F
300
Total TEQ
250
200
150
100
50
0
GPB
R-SE
R-S
R-SSW
PWF
FWP
CCF
Figure 1. Serum concentrations (pg WHO-TEQ g-1 fat, upper-bound estimates) of sub-populations in
Brescia, Italy (Turrio-Baldassari et al., 2008). GPB=general population in Brescia; R-SE, R-S and RSSW=local residents in contaminated subareas southeast, south and southwest of the industrial area;
PW =present workers at the industrial area; FWP=former workers of the PCB factor; CCF=consumers
of locally produced food.
High consumption of fish and seafood is usually correlated to high PCDD/F body
burden even at background level conditions (Mato et al., 2007; Lee et al., 2007; Chen
et al., 2003; Kiviranta et al., 2002). Contamination of aquatic food chains is therefore a
risk scenario that significantly can increase human body burdens in the presence of
local sources (Lee et al., 2006b; Chen et al., 2006b; Wu et al., 2001). Since fishing
populations generally are at higher risk than non-fishing populations (Harris & Jones,
2008; Weintraub. & Birnbaum, 2008; Bilau et al., 2007), these risk scenarios are
relevant for e.g. Asian countries, where the consumption of fish and sea food usually
is high. Contaminated aquatic food chains may also affect human exposure via
consumption of wild-bird eggs (Ryan et al., 1997).
No studies were found for cases that related contaminated aquatic food chains to
current management practices of PCDD/F contaminated waste. There are indications
on that contaminated waste is dumped into e.g. rivers close to waste dumping and
recycling sites, but no detailed investigations were performed (Luksemburg et al.,
2002). Known examples of serious contamination incidents are mostly related to
former chemical production activities (Chen et al., 2006b; Lee et al., 2006a and b; Wu
et al., 2001; Isosaari et al., 2000).
40
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Studies of human exposure related to open waste dump sites show that
people with intense contact with the sites have elevated concentrations of
POPs in their bodies. In local contamination scenarios where human food
chains are contaminated, elevated human body burdens have been detected
regularly. In some cases, ingestion of soil may be important as well.
41
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
7
Food chain contamination
related to local sources
In order to control and reduce human dietary exposure of dioxins and dioxin-like
compounds for the general population, the European Union has legislated maximum
levels for PCDD/F and dl-PCB of 1.5-6.0 pg WHO-TEQ g-1 fat in commercially
produced food products (European Commission, 2006; Table 9). Maximum levels
have also been laid for PCDD/F in animal feed stuff (European Commission, 2000),
where 0.75 pg TEQ g-1 is applicable for vegetable feed.
Table 4. Maximum levels of PCDD/Fs and dl-PCB in food stuffs (European Commission, 2006).
Food stuff
Origin
PCDD/F
PCDD/F +
dl-PCB
maximum
levels
maximum
levels
Meat and meat
products
pg WHO-TEQ g-1 fat
4.5
1.0
“
1.5
2.0
“
4.0
pg WHO-TEQ g-1 ww
8.0a
pg WHO-TEQ g-1 fat
6.0
“
6.0
Beef, sheep
3.0
Pork
Poultry
Fish and fish
products
-
4.0
Milk and dairy
products
-
3.0
Eggs and egg
products
-
3.0
The maximum levels are usually referred to when contamination of food products is
investigated. However, they are not based on human health risks; instead they are
founded on a statistical assessment of levels in European food stuff. Thus, if the
maximum levels are used as reference levels in a risk assessment, it is important to
remember that they do not represent “safe” food contamination levels with respect to
human health risk.
A good understanding of the bioaccumulation process of PCDD/Fs and dl-PCBs into
human food chains is required for adequate human health risk assessment in
connection to management of contaminated waste. In the following, the current
knowledge on the transfer of PCDD/Fs and PCBs in to agricultural and aquatic food
chains in the presence of local pollution sources is briefly reviewed.
42
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
7.1
Agricultural food chains
7.1.1
Eggs and chickens
It has been shown that poultry are extremely vulnerable for exposure of environmental
contaminants. High levels of PCDD/Fs in eggs, chickens and ducks have been
reported for areas close to waste incinerators (Pirard et al., 2005), chlorophenol
contaminated land (Åberg et al., 2010; Goldman et al., 2000, Harnly et al., 2000),
metal processing plants (Hsu et al., 2007), ash contaminated areas (Pless-Mulloli et
al., 2001) and other industrial facilities (e.g. cement kilns, chemical manufacturing,
incinerators, waste dump sites, IPEN, 2005). In the study conducted by IPEN, 20
chicken egg samples collected in 17 different countries were analysed for PCDD/Fs
and dl-PCBs. The sampling sites were selected to represent different local
contamination scenarios, and the levels found generally exceeded the legislated
maximum level (3.2-140 pg WHO-TEQ g-1 fat; Figure 3), once again demonstrating
the risk for enhanced human exposure in connection to food production and
contaminated sites.
160
140
dl-PCB
PCDD/F
pg WHO-TEQ/ g fat
120
100
80
60
40
20
C
C
ze
ch
ze Rep
ch u
R bli c
ep
u
Pa bli
ki c
s
C Ta tan
ze n
,
ch z a
R nia
ep ,
ub
Tu li c
r
U key
ru
gu ,
ay
,
M
oz US
am A
,
Ph bi q
i li ue,
pp
in
Be es
la ,
ru
s,
In
d
Sl
i
ov a,
ak
R ia ,
us
s
M i a,
ex
ic
o,
In
di
Ke a,
n
Se ya,
ne
g
R al,
us
Bu si a
lg ,
ar
ia
Eg ,
yp
t,
0
Figure 3. Egg concentrations (pg WHO-TEQ g-1 fat) reported by IPEN (2005).
43
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Despite low internal bioaccessibility of
One experimental study show that
PCDD/Fs that are adsorbed to solid matrices
free range chickens that are
(Budinsky et al., 2008; Wittsiepe et al., 2007;
exposed to PCDD/F contaminated
ash may produce eggs containing
Morinello et al., 2006; Ruby et al., 2002), a
PCDD/F levels that exceeded the
recent study by Shih and co-authors (2009)
legislated maximum limit of 3 pg
showed that fly ash contaminated feed can
WHO-TEQ g-1 fat by far.
increase the PCDD/F levels in eggs. In a
The PCDD/F concentration ash
controlled experiment, chickens were fed by
was below the suggested Low
fly ash (containing 201 ng TEQ kg-1) at 0.3
and 0.6 weight % of the commercial feed. The eggs reached maximum levels of 2.2
and 3.7 pg WHO-TEQ g-1 fat during the feeding trials, while the maximum levels of
the control group were 1.4 pg WHO-TEQ g-1 fat. Lee et al. (2009) also reported
elevated PCDD/F levels in duck eggs in a field case, where farmers used fly ash as a
feed additive to improve the colour of the yolk.
The high susceptibility for environmental
pollutants of poultry often results in high
levels of PCDD/Fs and dl-PCBs in free
range eggs already at low environmental
levels (Van Overmeire et al., 2009a and
b; Schoeters & Hoogenboom, 2006;
Pussemier et al., 2004). Contamination
levels of free-range eggs reported from
international studies are compiled in
Table 10.
Based on existing case studies from
Europe, the suggested provisional Low
POP Content Limit is not low enough to
prevent severe food chain contamination
if recycled waste wood is introduced to
chicken production facilities.
Empirical data show that chickens that
are exposed to wood containing 50 ng
WHO-TEQ kg-1 (0.05 ppb) may produce
eggs with concentrations significantly
exceeding the maximum limits (88 pg
WHO-TEQ g-1 fat or 8.8 pg WHO-TEQ g-1
whole egg).
For a person (60 kg) that consumes one
egg per day (60 g), the intake equals a
dose of 8.8 pg WHO-TEQ kg-1 b.w. and
day. The exposure of children eating the
same amount will be even higher.
The tolerable daily intake (TDI) that
44
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Table 5. Concentrations of PCDD/Fs and dl-PCBs (pg TEQ g-1 fat) in free range egg
(compilation of data from Schoeters & Hoogenboom, 2006). Country
Breeding
cond.
PCDD/Fs
Mean
Min-Max
Mean
Min-Max
Switzerland
Free range
-
2.3-19
-
-
Germany
Free range
-
0.4-22.8
-
-
Germany
Free range
4.4
<d.l.-22.8
-
-
0.7-7-7
-
0.7-5.8
12.9
2.1-26
-
-
Netherlands
Organic
U.K.
Free range
dl-PCBs
Site description
After fly ash removal
France
Free range
-
6.3-121.6
-
0.35-46.4
MSWI surroundings
Belgium
Free range
9.9
-
-
-
Private gardens
Belgium
Free range
0.4-18
-
0.4-270
Private farms
Ireland
Free range
0.5
<d.l.-0.8
0.3
0.4
Ireland
Organic
1.3
2.7
1.4
3.9
d.l.: detection limit
A major exposure route of free range chickens is ingestion of soil (Van Overmeire et
al., 2009b; Schuler et al., 1997), but other exposure routes may contribute. There is a
consensus that free-range chickens are more exposed for environmental pollutants
than caged chickens, which are completely fed with commercial and controlled
chicken feed (Schoeters & Hoogenboom, 2006; Pirard et al., 2005).
There are also examples of how PCDD/F or PCB contaminated waste products and
recycled substrates have been introduced in to the poultry food chain via production of
animal feed (Bernard et al., 2002; Hoogenboom et al., 2009; Hoogenboom et al.,
2004; Llerena et al., 2003; Malisch, 2000). The cases differ in how the contamination
aroused, but together they illustrate the ease in which human food chains can become
severely polluted by accidental, illegal or unconscious use of recycled substrates and
materials.
Another risk scenario is recycling of PCDD/F contaminated wood that is used as
animal bedding in chicken production facilities (Diletti et al., 2005; Brambilla et al.,
2009). The wood shaving litter reported by Diletti and co-authors contained only 4050 ng WHO-TEQ kg-1, which resulted in egg and meat concentrations as high as 88.1
and 45.2 pg WHO-TEQ g-1 fat. Considerable risks related to recycling of PCDD/F
contaminated waste will therefore exist at residue levels corresponding to the
suggested LPCL of 15 000 ng TEQ kg-1 (15 ppb).
7.1.2
Milk and meat
PCDD/Fs and PCBs accumulate in milk and meat products from grazing cattle. At low
environmental concentrations (background levels), feed and grass appears to be the
major exposure pathways (McLachlan et al., 1990). Bioaccumulation may account for
a 6-fold increase of PCDD/F levels in cow’s milk as compared to levels in the diet
(Huwe & Smith, 2005).
45
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Elevated soil concentrations constitute risk scenarios for grazing cattle due to direct
ingestion of contaminated soil or feed. A number of studies report contamination of
cow’s milk and other animal food products due to local sources (Esposito et al., 2009;
Turrio-Baldassari et al., 2007; Costera et al., 2006; Lindström et al., 2005; Schulz et
al., 2005: Table 11).
Table 6. Concentrations of PCDD//Fs and dl-PCBs (pg TEQ g-1 fat) in contaminated meat and
milk products produced near local sources.
Product
PCDD/F
dl-PCB
Country
Reference
Milk from goat
2.84-6.93
2.01-2.58
France
Costera et al., 2006
Fat from beef
27.2
-
USA
Goldman et al., 2000
Mutton
3.2
3.9a
Sweden
Lindström et al., 2005
Beef
0.46
-
Germany
Schulz et al., 2005
Milk from cows
3.47-6.13
-
"
"
Mutton
0.6
-
"
"
Milk from sheep
1.63
-
"
"
Milk from cow
5.07-8.14
-
Brazil
Braga et al., 2002
a
PCB 77, 126 and 169 only
PCDD/F in contaminated sediments may also affect agricultural food chains due to
flooding (Stachel et al., 2006; Lake et al., 2005; Alcock et al., 2002). An important
case study illustrating this risk scenario is the flooding of river Elbe, where grazing
animals were affected by contaminated feed and soil (http://elib.tihohannover.de/dissertations/gudek_ws08.html).
As for poultry and egg, there are several known incidents where the agricultural food
chain has been contaminated via feed additives from recycled substrates (Malisch,
2000), the use of CP treated wood in animal production facilities (Brambilla et al.,
2009; Fries et al., 2002; Huwe et al., 2004) or when contaminated wood was used for
drying animal feed substrates (Hoogenboom et al., 2004). Recent studies by Diletti et
al. (2008) and Esposito et al. (2009) show that improper waste management strategies
related to burning and dumping of waste, can affect animal food and feed
contamination levels on regional scales.
7.1.3
Factors affecting transfer of soil pollutants to agricultural food
chains
There is a wide range of factors that governs the rate of migration of pollutants from
soils to animals, e.g. the characteristics of the pollutant source, soil type, vegetation
cover, climatic and hydrological conditions, behaviour of the animals, breeding and
feeding conditions, physical-chemical properties of the pollutants, etc. A detailed
assessment of each factor is not possible in most investigations; an overall uncertainty
can be obtained when studying the food chain transfer.
46
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
In order to illustrate the range of uncertainty in the migration from soil to egg, egg/soil
concentration ratios (egg concentrations in pg TEQ g-1 fat and soil concentrations in
pg TEQ g-1 d.w.) were calculated for PCDD/Fs, dl-PCBs, and the sum of PCDD/F
and dl-PCB using data from a number of studies (Åberg et al., 2010; van Overmeire et
al., 2009b; Pirard et al., 2005, Harnly et al., 2001; Schuler et al., 1997; Figure 4). The
approach assumes that soil is a major source for PCDD/Fs and dl-PCBs in eggs, and
contribution from additional sources, such as animal or organic feed, are disregarded.
The total number of soil and egg data pairs was 45 for PCDD/Fs and 35 for dl-PCBs
and PCDD/Fs+dl-PCBs, respectively. The two studies used in the BIPRO risk
assessment, yielding a soil-to-egg transfer factor of 33, are not included in the
calculation which was based solely on data in the peer-reviewed journals.
) 120,0
Q
E
T
( 100,0
s
o
it
80,0
a
r.
c 60,0
n
o
c
li 40,0
o
s
o
-t 20,0
g
g
E 0,0
PCDD/F
dl-PCB
PCDD/F+dl-PCB
1
4
7 10 13 16 19 22 25 28 31 34 37 40 43
total number of data pairs
Figure 4. Calculated egg/soil concentration ratios (pg TEQ g-1 fat/pg g-1 d.w. soil) obtained by using
published data.
47
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
The results illustrate two important aspects: i)
the egg/soil concentration ratio for transfer of
PCDD/F from soil to egg in the BIPRO
assessment was 33, which exceeds the highest
ratio found in our study, and ii) the
biotransfer of dl-PCBs is much higher than
for PCDD/F. This implies that they may
constitute a significant food chain risk even if
the environmental TEQ levels are lower than
for PCDD/Fs. In the data set, dl-PCBs
contributed on average to 47% of the total
TEQ in eggs, while the average TEQ
contribution in soil was 17%.
The risk assessment presented in
the BIPRO report used a soil-toegg transfer ratio of 33. This value
is in the upper range of those that
were calculated from a large
number of data in the open
literature (see Figure 4).
The transfer of dl-PCBs from soil to
egg is more efficient than the
transfer of PCDD/Fs. Dl-PCBs can
therefore constitute a significant
risk for food chain transfer, even at
Statistics for the ratios in Figure 3 are summarised in Table 12. The mean ratio for dlPCBs is 6 times higher than the ratio for PCDD/Fs, and the mean ratio for PCDD/F +
dl-PCBs are almost twice as high as for PCDD/Fs solely. The coefficient of variance
(COV) exceeds 100%, which indicate a high variability of the data.
Table 12. Statistics for egg/soil concentration ratios (pg TEQ g-1 fat/pg g-1 d.w. soil) calculated
from published data. (COV = coefficient of variance, standard deviation as a percentage of the
mean value).
Min
PCDD/F
dl-PCB
Sum of PCDD/F
and dl-PCB
0.4
1.1
0.5
Max
26
101
22
Mean
3
17
5
Std. dev.
4
20
5
COV (%)
134
119
104
Although some of the variation probably can be attributed to application of different
TEF-concepts, differences in data processing, congener composition of the soil etc.,
the results clearly demonstrate that a generic transfer ratio for soil to egg for PCDD/Fs
and dl-PCBs is hard to establish. Since the uncertainty of predicting the transfer is
high, precaution is required when trying to generalize the expected transfer. It has
been stated, that PCBs are of minor toxicological importance for incineration residues
compared to the PCDD/Fs because of low dl-PCB TEQ fractions in the residues
(Vehlow et al., 2006), Since dl-PCBs apparently are transferred to a higher extent than
PCDD/Fs, such assumption may lead to biased risk assessment.
Even though it would be of great importance, a similar uncertainty analysis was not
made for transfer from soil into milk and meat food chains for a very simple reason;
data to investigate the relation between soil contamination levels and milk and meat
concentrations from grazing animals is quite limited. However, the range of
48
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
uncertainty for milk and meat transfer is expected to be just as large as for free-range
eggs.
The soil-to-biota transfer ratios measured on the basis of total TEQ-levels depends
partly on the congener composition of the source, since the transfer efficiency and
persistence of pollutants in tissue depend on factors such as the chlorination degree
and substitution pattern of the congeners (Costera et al., 2006; Schuler et al., 1997:
McLachlan et al., 1990: Thomas et al., 1999a and b). For 2,3,7,8-substituted CDD/Fs,
lower chlorinated congeners has usually a higher transfer rate than highly chlorinated
congeners, depending on congener specific availability in the matrices (Schoeters &
Hoogenboom, 2006; Hoogenboom et al., 2006; Schuler et al., 2007; McLachlan et al.,
1990). Biotransfer assessments that only consider total TEQs in different media may
therefore be of limited use for extrapolating risks to other scenarios with another
composition of the PCDD/F source.
7.2
The aquatic food chain
The biotransfer and bioaccumulation processes in the aquatic environment follows the
same principles as described for the terrestrial environment, but aquatic contamination
scenarios are often more complex since sediment dynamics, hydrology and
bioconcentration (passive uptake of truly dissolve contaminants in water) becomes
additional factors.
Temporary pollution events, such as serious accidents or spills as well as long-term
dumping of PCDD/F contaminated waste, can negatively harm aquatic systems for
long times (Birch et al., 2007; Marvin et al., 2007; Suarez et al., 2005; Malve et al.,
2003). PCDD/F and PCB contaminated waters and sediments may also cause transfer
of the pollutants to agricultural food chains if the water is used for irrigation or if
pastures are flooded (Zhao et al., 2006; Lake et al., 2005).
As mentioned before, few cases studies of aquatic systems that are directly related to
the aim of this study were found. Instead, there are several examples of large scale,
historical contamination of water and sediment caused by former direct emissions of
chemicals or residues from chemical production (Shen et al., 2008; Birch et al., 2007;
Micheletti et al., 2007; Knutzen et al., 2003; Isosaari et al., 2002; Bopp et al., 1991;
Wu et al., 2001), or situations were multiple anthropogenic sources and atmospheric
deposition have affected waters and sediment, (e.g. Shen et al., 2009; Zhang et al.,
2009; Castro-Jimenez et al., 2008; Micheletti et al., 2007, Bruckmeier et al., 1997).
The limited number of relevant reports may indicate that such events do not occur
frequently, or that the extension of the pollution results in detectable impacts of lakes
and rivers. However, a few case studies indicate that such activities actually are
occurring. In the pre-investigation report for the Zapallal waste site in Peru, it was
stated that solid residues were regularly dumped in a nearby river, and Luksemburg et
al. (2002) found high PCDD/F concentrations in sediment in Lianjing River due to
dumping of ash from a nearby e-waste recycling site. It is also possible that
49
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
environmental PCDD/F concentrations have not been monitored at on-going aquatic
dumping sites.
Historically, aquatic systems have been severely polluted by emissions from
chemical production facilities. No recent incidents related to the scope of this
report were found. However, there are indications on that PCDD/F
contaminated waste is dumped in rivers close to areas where the waste was
generated.
50
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
8
Review of the BIPRO risk
assessment
In the BIPRO report, safe levels of PCDD/Fs in waste (< 1 000 ng TEQ kg-1) were
estimated by considering a worst case scenario where human health risks are related to
consumption of home-produced chicken eggs (page 349-351; BIPRO, 2005). This risk
assessment is reviewed here from a human health perspective.
8.1
Application of safety factors and tolerable
daily intake (TDI)
The BIPRO report refers to the European maximum levels of PCDD/F in eggs of 3 pg
TEQ g-1 fat, and states that this level is based on TDI estimations for a safe level of
exposure proposed by WHO (page 350). This statement is not correct as the maximum
levels for dioxin-like pollutants in food were introduced because it was concluded by
the European Commission that there is no safety margin between the current exposure
of the European population and the TDI. The TDI means the life-long daily intake of
contaminants without risk of negative health effects. For PCDD/Fs, EU's Scientific
Committee on Food (SCF, 2001) has decided on a TDI of 2 pg TEQ kg-1 b.w. day-1.
The European maximum levels for food were set in order to enforce reduction of the
highest concentrations of PCDD/F and dl-PCBs in the most contaminated food and
thereby reduce the exposure of the European population. The maximum levels are
therefore not directly based on the TDI and human consumption rates of different food
items. This means that if humans are exposed to food with levels of PCDD/F and dlPCBs below the limit, the total exposure will decrease, but the exposure level may or
may not be lower than TDI. The frequency of consuming dioxin contaminated food
items will decide if TDI is exceeded or not.
In calculating a TDI from a no-effect level in an animal toxicity study, uncertainty
factors are usually applied to compensate for lack of knowledge regarding possible
interspecies (rat-to-human) and inter-individual variation in sensitivity. In the risk
assessment from SCF, an assessment factor of 10 was used. This factor was based on
known variability in the biological half-life of PCDD/F between individuals (factor
3.2) and a factor for extrapolation from an effect-level to a non-effect level (factor 3).
The factor of 10 used in this case is exceptionally small; usually a factor of 100 is
applied. In the BIPRO report, it was stated that only intra-species variation (variation
in response of individuals, usually a factor 10) had to be taken into account and this
statement justified an increase of the maximum level in eggs from 3 pg TEQ g-1 fat to
30 pg TEQ g-1 fat. Considering the unusually small uncertainty factor underlying the
TDI, this adjustment is not appropriate.
51
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
The BIPRO report states further “Consequently 30 pg/g fat must be assumed as
critical contamination level.” and “It has to be taken into account that these limits
include safety factors following the precautionary principle which have been excluded
for the above worst case estimation.” The uncertainty factor of 10 used for the TDI
calculation is based on extrapolation to a no-effect level as well as to account for
known inter-individual variation in elimination of dioxins from the body, i.e. to
protect also more sensitive individuals. The factor of 10 is not used based on the
precautionary principle, which on the contrary is used in the risk management step,
often based on lack of data. The precautionary principle is not used in risk assessment
and is not handled with assessment factors. The intake level of TDI * 10 (assessment
factors) thus corresponds to the dioxin level in rats causing toxic effects. Thus the
factor of 10 was used to come to a safe level for (also sensitive groups of) humans.
8.2
Correlating environmental levels to
uptake into eggs
The BIPRO assessment used a soil-to-egg concentration ratio that was adopted from
two studies only, and from these two studies they concluded that a soil concentration
of 1 000 ng TEQ kg-1 (1 ppb) would result in a critical value of 30 pg TEQ g-1 fat in
eggs. As previously shown, the applied correlation exceeded the highest egg/soil
concentration ratio that was calculated from other studies (Figure 4). If one assumes
that egg/soil concentration ratios for PCDD/Fs ranges between 0.4 and 7 (minimum
level and mean + one standard deviation; Table 12), this implies that 30 pg TEQ g-1
fat in egg will be exceeded at concentrations of approx. 4-75 ng TEQ kg-1 d.w. in the
soil. Consequently, the European maximum level of 3 pg TEQ g-1 fat in eggs can be
exceeded at levels that are ten times lower, i.e. at soil concentrations of approx. 0.47.5 ng TEQ kg-1 d.w. The estimated “safe” waste concentration of 1 000 ng TEQ kg-1
of BIPRO therefore underestimates the risk related to ingestion of home produced
chicken eggs.
8.3
Contribution of dl-PCBs
The risk assessment of BIPRO never discussed if and how the presence of dl-PCBs in
waste will affect the risk assessment. Even though the LPCL for PCDD/F refers to this
compound group only, the exclusion of dl-PCBs may result in biased risk assessments.
Since the TDI includes both PCDD/Fs and dl-PCBs, only a fraction of this value
should be TEQs deriving from PCDD/Fs. Even though the literature survey showed
that information of dl-PCBs in waste is limited, it was clearly shown that the food
chain transfer efficiency of this compound group is high compared to PCDD/Fs. As
long as dl-PCBs are not included in the LPCL for PCDD/Fs, the estimated risk
associated to food chain transfer of pollutants in waste may be underestimated.
52
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
8.4
Exposure from other sources
Most populations are exposed to PCDD/F and dl-PCBs primarily via their diet
(Chapter 6). This overall exposure is caused by low environmental levels that exist
even in pristine environments. The safety margin between the recommended TDI (2
pg TEQ kg-1 b.w.) and the overall, baseline exposure is generally low, which indicates
that most populations do not tolerate additional exposure from local sources. From a
human health perspective, it is therefore not recommended that 100% of TDI is
allowed to origin from local sources without including other exposure.
53
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
9
Case studies in Peru and
Thailand
As a first attempt to achieve empirical data that correlate PCDD/F and dl-PCB levels
in waste to those in the nearby environment, a field sampling study was performed at
two sites where PCDD/F contaminated waste is produced and managed. The sampling
sites were identified in discussion with the non-profit environmental organisations
Arnika and IPEN, and criteria for the selection of the sites were:
i) open and unprotected storage of ashes in areas close to residential surroundings,
ii) potential exposure via residential human activities and
iii) unproblematic access to the area to avoid political conflicts
After pre-investigations of a limited number of possible sites, the waste site Zapallal
(Peru, Appendix A) and the Phuket waste incineration facility (Thailand) were chosen.
The objectives of the field sampling were to investigate if the local environments were
affected by solid waste residues (ashes) and to produce data for a human exposure
assessment from a generic perspective.
9.1
Case study 1: Zapallal waste site, Peru
The Zapallal waste site is situated north of Lima, Peru. The area is used for recycling
and dumping of different waste types (Figure 5). Activities in the area are e.g. cable
burning, burning of lead batteries, metal smelting, disposal of urban waste, etc.
Management of the ashes include disposal at a nearby garbage dump site for solid
waste and dumping into the nearby Chillon River. The climate is very arid, and there
are two main wind directions, towards east or west.
Figure 5. Photos from Zapallal waste site, Peru.
It is estimated that 30 000 people live in the vicinity of the waste site area, and that
the zone around the landfill has 54 consolidated urban allotments (Appendix A).
The distance between the landfill and nearest inhabitants is approximately 800
meter. The area with burning and melting activities is situated next to the
54
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
residential areas, and free range chickens and ducks are held close to the site. Open
ash piles are stored on the ground, and the risk of windblown transport in the area
is therefore very high. Because of the dry climate, no vegetables are grown in the
area. However, drought resistant plants, such as Yucca, Agave and Ficus are found.
The field sampling at Zapallal took place in the end of May, 2009. In total, 22
samples of soil, ash, eggs, plants and sediment from the waste site and the
surroundings and 6 reference samples of soil, sediment and eggs from the rural area
Trapiche, more than 50 km from Zapallal, were collected (Table 13).
Table 13. Samples from the Zapallal waste site, May and July 2009.
Sample
Sampling area
(Appendix B)
Site description
Picture
(Appendix C)
Soil 1:1,2,4,5
Soil 1
Near industrial allotments at Zapallal waste site
6
Soil 2
Soil 2
200 m from industrial allotments
6
Soil 3
Soil 3
300 m from industrial allotments
6
Soil 5
Soil 5
1500 m from industrial allotments
7
Soil 7 (ref)
-
Reference area,4 km from Zapallal
23
Soil 8 (ref)
-
Reference area, 11 km from Trapiche
24
Soil 9 (ref)
-
Reference area, 22 km from Trapiche
25
Soil 10 (ref)
-
Reference area, 30 km from Trapiche
-
Ash 1
Ash 1
Cable burning
11
Ash 2
Ash 2
Burning of plastic film
12
Ash 3
Ash 3
Burning of lead batteries
13
Sediment 1
-
Chillon River, 2-3 km south of Zapallal
14
Sediment 2 (ref)
-
Reference area, Chillon River, Trapiche, 50 km
upstream sediment 1
16
Plant 1:1,2,4
Soil 1
Near industrial allotments at Zapallal waste site
at soil sampling sites
19
Plant 2
Soil 2
200 m from industrial allotments
20
Plant 3
Soil 3
300 m from industrial allotments
21
Plant 4
Soil 4
500 m from industrial allotments
22
Plant 5
Soil 5
1500 m from industrial allotments
7
Plant 6
Soil 6
4000 m from industrial allotments
8
Egg 1
Eggs 1
Free range chicken, 500 m west of industrial
allotments
17
Egg 2
Eggs 1
Free range ducks, 500 m west of industrial
allotments
18
Egg 3
Eggs 2
Free range ducks, western parts of waste site
12
Egg 4 (ref)
Trapiche
Reference samples, free range chickens
55
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
9.1.1
Pollution of soil and sediment related to management of
ashes
Results for soil, ash and sediment samples from Zapallal and the surroundings are
presented in Table 14. Soil from the waste site (soil 1:1-5) contained 6.5-15 ng
TEQ kg-1 d.w., and was significantly elevated compared to soil sampled 1500 m
distance from the site (0.4 ng TEQ kg-1 d.w.). Reference soil from Trapiche
contained 0.068 to 1.7 ng WHO-TEQ g-1 d.w. The soil concentrations decreased
with distance from the waste site, which show that Zapallal is a local source. DlPCBs contributed to approximately 20 %, of the total TEQ in soil. The organic
carbon (OC) content was estimated from loss-on-ignition values (LOI), assuming
that the OC-content constituted half of LOI. The OC-content in the soil samples
varied from 0.4 to 2.5% and no correlation was found between OC and TEQconcentrations.
Sediment from close to the waste site (Sediment 1) contained higher levels (1.7 ng
TEQ kg-1 d.w.) than the reference (upstream) sample (Sediment 2, 0.3 ng TEQ kg1 d.w.).
TEQ concentrations in ash samples varied. Ash pile 1 contained almost 14 000 ng
TEQ kg-1 d.w., which is close to the suggested LPCL of 15 000 ng TEQ kg-1 for
PCDD/Fs. Ash samples 2 and 3 contained much lower levels, 56 and 150 ng TEQ
kg-1 d.w.. Dl-PCBs contributed to 8-13 % of the total TEQ in ashes.
Table 14. Concentrations (ng TEQ kg-1 d.w.) of PCDD/Fs and dl-PCBs in soil, ash and
sediment samples from Zapallal waste site and Trapiche (ref).
PCDD/F
dl-PCB
Sum TEQ
ng TEQ kg-1 d.w.
ng TEQ kg-1 d.w.
ng TEQ kg-1 d.w.
Soil 1:1
8.8
2.6
12
Soil 1:2
10
2.9
13
Soil 1:4
11
3.5
15
Soil 1:5
5.3
1.3
6.5
Soil 2, 200 m
3.3
0.86
4.2
Soil 3, 300 m
3.6
0.94
4.5
Soil 5, 1500 m
0.32
0.10
0.4
Soils 7-10 (ref)
0.05-1.2
0.018-0.48
0.068-1.7
Ash 1
12 000
1 700
14 000
Ash 2
50
6.1
56
Ash 3
140
12
150
Sediment 1
1.3
0.41
1.7
Sediment 2 (ref)
0.23
0.09
0.3
56
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
PCDD/F homologue group distribution profiles for soil and ash samples are
presented in Figure 6. The ash profile is characterised by a large fraction of PCDF
in relation to PCDD. The most dominating congeners belong to the HxCDF and
HpCDF homologue groups. PCDF made up 80% of total PCDD/F levels in ash.
Soil samples from the waste site area contained lower levels of PCDFs; here they
made up only 55% (average for soil 1-3). The presence of HxCDF and HpCDF was
not as dominating as in ash. In soil 5, sampled at 1500 m distance from the waste
site, the PCDF fraction was even lower (approx. 40 %), and the abundance of
HxCDF and HpCDF was also lower. In the reference soil samples from Trapiche,
PCDDs were more abundant than PCDFs, which constituted only 30% of the total
levels (average for soils 7-10). OCDD was the most abundant congener in the
reference soil. This pattern is usually attributed to long range transport and is
typical for pristine, unpolluted environments. The dissimilarities between ash and
waste site soil samples (average soil 1-3) indicate that also other sources, such as
atmospheric deposition, are contributing to the soil contamination.
TCDD
Average soil 7‐10 (ref)
PeCDD
HxCDD
Soil 5 (1 500 m)
HpCDD
OCDD
TCDF
Average soil 1‐3
PeCDF
HxCDF
Average Ash 1‐3
HpCDF
OCDF
0%
20%
40%
60%
80%
100%
Figure 6. Homologue profiles for PCDD/F in soil and ash samples from Zapallal and Trapiche
(reference soil). The concentrations are expressed as fractions (%) of total PCDD/F
concentrations (pg g-1or ng kg-1).
The homologue profile of the sediment sample from the waste site area (Sediment
1, Figure 7) was not similar to the ash samples, indicating that dumping of
incineration residues did not cause the elevation. The pattern seen in both sediment
samples remind of the reference soil pattern, with a high abundance of OCDD.
57
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Figure 7. Homologue profiles for PCDD/F concentrations in sediment samples from Zapallal and
Trapiche. The concentrations are expressed as fractions (%) of total PCDD/F concentrations (pg
g-1or ng kg-1).
9.1.2
Bioaccumulation in biota
Egg yolk from the waste site and the surroundings contained 5.8 to 7.7 pg TEQ g-1
fat, where dl-PCBs contributed to 40-60 % of the total TEQs (Table 15). In
contrast, egg concentrations from the reference site Trapiche were up to 55 times
lower. PCDD/F concentration in eggs from Zapallal exceeded the European
legislated maximum levels of 3 pg WHO-TEQ g-1 fat.
Table 15. Concentrations (pg TEQ g-1fat) of PCDD/Fs and dl-PCBs in egg yolk from
Zapallal waste site and Trapiche (ref).
Egg 1 (chicken)
PCDD/F
dl-PCB
Sum TEQ
pg TEQ g-1fat
pg TEQ g-1fat
pg TEQ g-1fat
3.4
2.4
5.8
Egg 2 (duck)
3.8
2.4
6.2
Egg 3 (chicken)
4.4
3.3
7.7
Egg 4 (chicken, ref)
0.12
0.2
0.14
PCDD/F homologue distribution patterns in eggs did not differ much between the
sampling sites (Figure 8). Despite a high presence of PCDF in soil at the waste site
compared to the reference site, this pattern was not reflected in the egg samples.
The PCDD/F pattern in eggs did not indicate a high impact from contaminated ash.
58
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
TCDD
PeCDD
Egg 4 (ref)
HxCDD
HpCDD
OCDD
TCDF
PeCDF
Average Egg 1‐3
HxCDF
HpCDF
OCDF
0%
20%
40%
60%
80%
100%
Figure 8. Homologue profiles for PCDD/F in egg samples from Zapallal and Trapiche. The
concentrations are expressed as fractions (%) of total PCDD/F concentrations (pg g-1or ng kg-1).
Plants from the waste site contained various levels of PCDD/Fs and dl-PCBs
(Table 16). In general, it seems that plant species in close proximity to the waste
site were more contaminated (0.013 to 9.1 pg TEQ g-1 w.w.) than the reference
samples (0.8 and 1.7 pg TEQ g-1 w.w.). However, some of these differences are
likely due to species-specific variation. Yucca and Agave concentrations differed
by more than two orders of magnitude for samples originating from the waste site.
The concentrations in Agave from the waste site were also 60-130 times lower
compared to the reference site samples of an unknown species. Dl-PCBs accounted
for 11-65% of the total TEQ in Yucca samples from the waste site.
Table 16. Concentrations (pg TEQ g-1 w.w.) of PCDD/Fs and dl-PCBs in plants from
Zapallal waste site and its surroundings.
dl-PCB
Sum TEQ
pg TEQ g w.w.
pg TEQ g-1
w.w.
pg TEQ g-1
w.w.
Plant 1:1 (Yucca)
5.2
3.9
9.1
Plant 1:2 (Yucca)
3.2
1.8
5.0
Plant 1:4 (Agave)
0.012
0.001
0.013
Plant 2, 200 m (Ficus)
2.2
2.0
4.2
Plant 3, 300 m (Ficus)
4.4
3.1
7.5
Plant 4, 500 m (Ficus)
2.0
2.3
4.3
PCDD/F
-1
Plant 5, 1 500 m (ref, unknown species)
0.6
1.1
1.7
Plant 6, 4 000 m (ref, unknown species)
0.3
0.5
0.8
PCDD/F homologue distribution patterns of plants from the waste site (average
plant 1:1-2 and average plant 2-4) were not remarkably different from each other
(Figure 9). In general, all plant samples had high accumulation of PCDFs in
relation to PCDDs.
59
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
TCDD
Average Plant 5‐6 (ref)
PeCDD
HxCDD
HpCDD
Plant 2‐4 (Ficus)
OCDD
TCDF
PeCDF
HxCDF
Average Plant 1:1‐2 (Yucca)
HpCDF
0%
20%
40%
60%
80%
100%
OCDF
Figure 9. Homologue profiles for PCDD/F in plant samples from Zapallal and Trapiche. The
concentrations are expressed as fractions (%) of total PCDD/F concentrations (pg g-1or ng kg-1).
9.1.3
Conclusions
Soil from the waste site was clearly enriched with PCDF compared to the reference
soils, indicating dioxin contamination from the waste management activities at the
site. Eggs sampled closed to the waste site contained levels that exceed European
maximum levels for PCDD/Fs in eggs, and the levels in eggs and plants were
clearly elevated as compared to levels in samples from reference sites.
Based on homologue distribution patterns in ash and soil samples, it can be
concluded that the waste site is a source for PCDD/Fs and PCBs affecting the
surroundings. It is, however, not possible to conclude from our investigation
whether it is air emissions and deposition from the recycling activities or
distribution of contaminated ash that is the main cause of the impact. It is also
worth to note that our results reflect only a momentary picture of existing sources
and their environmental impact.
9.2
Case study 2: Phuket MSW Incinerator,
Thailand
A minor field sampling study was made in the area of the Phuket MSW incinerator
in Thailand in June 2009 (Appendix D). The plant receives municipal waste from
Phuket city, and had earlier problems with high PCDD/F emissions. Today, the
incineration process and the flue gas cleaning have been improved, and the
PCDD/F emissions have decreased. However, ash from the incineration process is
stored in open piles at the facility (Figure 10). Industrial waste water ponds
discharge into surface waters outside the plant, where local inhabitants catch fish
for consumption.
60
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Figure 10. Ash deposit area and ash sampling at Phuket Incineration facility.
A total of 10 samples of soil, sediment, ash, and fish from the incinerator area, and
2 reference soil samples 10 km from Phuket city were collected (Table 17).
Table 17. Field samples from Phuket MSW incinerator, June 2009.
Sample
Description
Soil 1 (ref)
Patong Beach town, 10 km from Phuket town
Soil 2 (ref)
Patong Beach town, 10 km from Phuket town
Soil 3
Soil sample in front of main office
Soil 4
Soil from landfill area
Sediment 1
Sediment from ash deposit lake
Sediment 2
Sediment from lake near comb
Ash 1
Ash, one week old, taken from laboratory
Ash 2
Ash from ash deposit
Ash 3
Ash from landfill
Ash 4
Grey ash from lower part of site
Ash 5
Ash samples (grey) from close to house where family is living
Fish 1-3
Fish from lake down side ash store
9.2.1
Pollution of soil and sediment related to management of
ashes
Soil from the incineration area contained 5 and 12 ng TEQ kg-1 d.w., while the
reference soil samples from Patong Beach had significantly lower levels (0.7 and
1.0 ng TEQ kg-1 d.w.; Table 18). Dl-PCBs contributed to <4% of the total TEQ in
the soil samples. Sediment from the ash deposit lake was severely contaminated,
containing 2 800 ng TEQ kg-1 d.w.. In comparison, sediment from the outlet
outside the industrial area contained only low levels of PCDD/Fs and dl-PCBs (1.8
ng TEQ kg-1 d.w.). The OC content (estimated from LOI, see section 9.1.1) in the
soil samples varied (1.5-8%), but no apparent correlation was found between OC
and TEQ-concentrations.
61
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Concentrations in ash samples ranged from 6.6 to 8 300 ng TEQ kg-1d.w.. The ash
sample that was taken close to the residential houses contained 3 200 ng TEQ kg-1
d.w.. Dl-PCBs contributed to less than 5% of the total TEQ in ash.
Table 18. Concentrations (ng TEQ kg1- d.w.) of PCDD/Fs and dl-PCBs in soil, ash and
sediment samples taken at or near the Phuket incineration facility.
PCDD/F
dl-PCB
Sum TEQ
ng TEQ kg-1
d.w.
ng TEQ kg1
d.w.
ng TEQ kg1
d.w.
Soil 1 (ref)
0.68
0.022
0.7
Soil 2 (ref)
1.0
0.028
1.0
Soil 3, office
4.7
0.20
5.0
Soil 4, landfill
11
0.42
12
Sediment 1, ash deposit lake
2 700
97
2 800
Sediment 2, outlet
1.8
0.066
1.8
Ash 1, bottom ash from burner
6.2
0.35
6.6
Ash 2, ash deposit
7 200
210
7 400
Ash 3, landfill
8 000
255
8 300
Ash 4, industrial area
3 600
68
3 700
Ash 5, industrial area, close to families
3 200
72
3 300
Average PCDD/F homologue distribution profiles of soil samples from the facility
were not similar to the pattern found in ashes (Figure 11). In general, the ash
samples had a higher fraction of PCDF relative to PCDD. The soil at the facility
was dominated by OCDD, which had a much lower abundance in ash. The
divergence in congener composition in soil and ash matrices indicates that ash is
not a major source for soil contamination at this site. The homologue profiles in the
soil reference samples was completely dominated by OCDD, which accounted for
94% of total PCDD/F. Similar patterns have been found elsewhere in the world
(Muller et al., 2002; Prange et al., 2002).
62
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
TCDD
Average soil 1‐2 (ref)
PeCDD
HxCDD
HpCDD
Average Soil 3‐4
OCDD
TCDF
PeCDF
HxCDF
Average ash 1‐5
HpCDF
OCDF
0%
20%
40%
60%
80%
100%
Figure 11. Relative homologue distribution patterns for PCDD/F in soil and ash samples from
Phuket and the reference area. The concentrations are expressed as fractions (%) of total
PCDD/Fs (pg g-1or ng kg-1) for the homologue groups.
The homologue distribution pattern of the contaminated sediment sample
(sediment 1) from the pond was similar to that of ash (Figure 12). The pattern of
sediment sample 2 from the discharge area outside the industrial facility was more
similar to the pattern in soil from the facility. The results do not indicate at
transport of contaminants from the contaminated pond to the recipient.
TCDD
PeCDD
Sediment 2
HxCDD
HpCDD
OCDD
TCDF
PeCDF
Sediment 1
HxCDF
HpCDF
OCDF
0%
20%
40%
60%
80%
100%
Figure 12. Relative homologue distribution patterns for PCDD/F in sediment from Phuket. The
concentrations are expressed as fractions (%) of total PCDD/Fs (pg g-1or ng kg-1) for the homologue groups.
63
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
9.2.2
Bioaccumulation in biota
The fish samples contained 1.2 to 5.6 pg TEQ g-1 fat, where dl-PCBs added to 530 % of the total TEQ. Since no reference samples exist from the area, it is difficult
to estimate the impact of the contamination in a regional/national perspective.
Compared to international data, the concentrations are in the lower range of those
measured in other studies (Moon & Choi, 2009). The homologue distribution
pattern did not indicate any impact related to ash management practices (not
illustrated).
9.2.3
Conclusions
Soil concentrations at the Phuket incineration plant were somewhat elevated
compared to the reference site, but PCDD/F homologue distribution patterns
indicate that the soil is mainly affected by another source than incineration
residues. Ash samples that were stored in open piles in the area contained up to
8490 ng TEQ kg-1, and high concentrations (2 170 ng TEQ kg-1) were also found
in ash piles close to residential houses. The same homologue distribution pattern as
in ash was found in a contaminated sediment sample from the waste water pond.
However, there were no indications of further contamination of recreational surface
water in the discharge area outside the facility or in fish.
64
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
10 Human exposure assessment
related to environmental
contamination
10.1 Method
This chapter presents a human exposure assessment where elevated environmental
PCDD/F concentrations are coupled to exposure levels and human health risks. The
assessment is based upon PCDD/F congener distribution patterns from Peru, and
fate and exposure modelling was used as a complementary method to examine the
relation between environmental concentrations and human exposure. Even though
dl-PCBs contribute to the total exposure of humans, the modelling and evaluation
of model outputs was made only for PCDD/F because experimental BTFs that are
necessary to describe the uptake from soil and feed into animals was not easily
available for dl-PCBs.
As a foundation in the assessment, two human exposure scenarios were created to
illustrate differences in human behaviour and food consumption characteristics
related to industrial and developing countries, respectively. Each exposure scenario
contained also two different receptors: adults and children, to cover age related
differences, such as body weights and behaviour. Since exposure of humans to
PCDD/Fs and dl-PCBs is primarily related to ingestion of food, and in some cases
soil, other exposure routes (such as dermal contact, inhalation and ingestion of
drinking water, fish or root-crops) were not considered in the assessment. For
aquatic exposure pathways, it is difficult to relate the bioaccumulation to local soil
concentrations and a different modelling approach is needed. The aquatic system is
also affected by several sources that are distributed over a regional scale. Inhalation
exposure of PCDD/F is more relevant for e.g. occupational scenarios (Shih et al.,
2006) since indoor air concentrations might be affected by contaminated dust
particles from occupational activities (Åberg et al., 2010) and limited air exchange
rates may increase contamination of air. It is less important for residential outdoor
exposure. Root crops were excluded since they are affected by contaminants in the
root zone and in our scenarios we assumed that contamination from improper waste
management strategies (e.g. dumping) will affect only surface soils.
For food ingestion pathways, the external dose was estimated by modelling the
uptake of contaminants in biota as a function of two different soil concentrations in
the scenarios. The input soil concentration was selected to represent a background
scenario (1 ng TEQ kg-1) and a local contamination scenario with a high (but not
extremely high) soil concentration of 70 ng TEQ kg-1, yielding model out puts
expressed on fresh weight basis. Estimated exposure doses of PCDD/Fs in the
scenarios were evaluated against the TDI of 2 pg TEQ kg-1 b.w. day-1.
65
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
10.2
Human exposure scenarios
The two exposure scenarios will here after be called the Industrial setting and the
Development setting. Each scenario included two age groups: children (4 years)
and adults (>17 years).
Average food consumption data for Swedish children (NFA, 2003) and adults
(NFA, 2002) was used as food consumption rates in the Industrial setting, which
aims to represent European conditions. The scenario included the same soil
ingestion rates that are used for sensitive land use in the Swedish model for setting
remediation soil guideline values: 120 mg day-1 for children and 50 mg for adults.
To compensate for that most of the food in industrialised countries is bought from
groceries, only a fraction of the totally ingested food (10 % of vegetables and root
crops, 10 % of milk and meat and 50% of eggs) was assumed to be locally
produced. Bodyweights of the children and adults were 18 and 70 kg, respectively.
The Development setting aimed to represent underprivileged living conditions in
developing countries and assumes that all the food stuff is collected or produced in
the nearby surroundings. Food ingestion data from Wang et al., (2009) were used
for adults. Since food ingestion data for children was not included in this reference,
the relative differences of food intake rates for adults in the developing and the
industrial settings was assumed to be the same for the children. It was further
assumed that:
a) 100 % of ingested food was of local origin
b) the amount of ingested soil was 10 times higher than in the industrialised
setting due to a rural life style and limited access to hygienic facilities,
such as tap water for rinsing and cleaning food, hands, etc.
Bodyweights of children and adults were lower than in the Industrial setting (12
and 60 kg, respectively) to account for lower body weights of e.g. Asian people. It
is important to stress that this scenario does not necessarily represent a specific
region or country, but illustrates how different living conditions will affect human
exposure levels. Table 19 summarise the human exposure parameterisation.
66
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Table 19. Exposure parameters for adults and children in the Industrial and Development
settings.
Industrial setting
Development setting
Exposure parameters
Adult
Child
Adult
Child
Bodyweight (kg)
70
18
60
12
Ingestion of eggs (g kg-1b.w. day-1)
0.2
0.3
0.5
1
-1
-1
Ingestion of milk (g kg b.w. day )
4.9
22
1
6
Ingestion of meat (g kg-1b.w. day-1)
1.6
3.8
1.9
7
-1
-1
Ingestion of vegetables (g kg b.w. day )
3.6
7
3.9
11
Ingestion of soil (mg day-1)
50
120
500
1 200
Fraction of local prod. eggs (%)
50
50
100
100
Fraction of local prod. milk (%)
10
10
100
100
Fraction of local prod. meat (%)
10
10
100
100
Fraction of local prod. vegetables (%)
10
10
100
100
10.3 Modelling bioaccumulation and
exposure levels
The four exposure scenarios were coupled to bioaccumulation of PCDD/Fs by the
multimedia fate and exposure model CalTOX, which previously was applied and
evaluated for PCDD/F contaminated land (Wiberg et al., 2007, Åberg et al., in
preparation). A simple evaluation procedure was applied to reduce some of the
uncertainties that are coupled to a model based risk assessment, where biotic
samples from Peru and other relevant studies were used to evaluate the
bioaccumulation predicted by CalTOX. By adding this step in the risk assessment,
higher confidence in the interpretation of the final results is achieved.
A reference soil concentration of 1 ng WHO-TEQ kg-1 was used as input for a
background concentration scenario (BS), which serves as a baseline with no
influence of a local source. This level corresponds to reference soil concentrations
from Peru. A soil concentration of 70 ng WHO-TEQ kg-1) was used as input for a
local contamination scenario (LCS). This level was chosen in order to illustrate the
impact from a site with high, but not extremely high, soil contamination. The
modelling scheme is summarised in Table 20. Since the model scenarios included
PCDD/Fs only, the estimated TEQs do not reflect the total dioxin exposure since
the contribution from dl-PCBs are not considered.
Table 20. Modelling scheme for the Industrial and Development setting at two input soil
concentration levels. BS=background concentration scenario, LCS= local contamination
scenario
BS
(1 ng WHO-TEQ kg-1)
LCS
(70 ng WHO-TEQ kg-1)
Industrial setting
Adult/children
Adult/children
Development setting
Adult/children
Adult/children
67
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
10.4 Results
10.4.1
Ingestion of eggs
As discussed in Chapter 7, reliable estimates of bioaccumulation of PCDD/Fs into
eggs are usually difficult to achieve. At the same time, there is a consensus that
ingestion of free-range eggs could be a risk even at non-polluted sites and there is a
need to correlate environmental PCDD/F concentrations to those in free-range eggs
for different scenarios.
In Table 21, egg concentration outputs from the BS and LCS scenarios are
compared to estimated levels in eggs using mean soil-to-egg BTFs from literature
data (Chapter 7; Table 12) and measured egg concentrations from the field study in
Peru. The comparison shows that the model outputs for the BS soil contamination
levels were in agreement with egg concentrations from Zapallal and Trapiche.
Since the exact soil concentrations at the egg sampling sites were not analysed, the
site specific egg-soil concentrations ratios are not known and the agreement
between modelled and measured concentrations cannot be fully evaluated.
However, we expect that the site at Zapallal is less contaminated than our local
contamination scenario. According to literature derived soil-to-egg BTFs, 10 times
higher egg concentrations than estimated by the model is to be expected at the BS
and LCS soil contamination levels. The modelled exposure doses for the Industrial
and Development settings might therefore be biased so that exposure levels are
underestimated at least one order of magnitude.
Table 21. Modelled, estimated and measured egg concentrations (pg TEQ g-1 w.w.).
BS=Background scenario, LCS=local contamination scenario, BTF=average egg-soil
concentration ratios calculated from literature data (see Chapter 7).
Egg concentrations
(pg TEQ g-1 w.w.)
Model output, BS
0.018
Model output, LCS
0.33
Estimated with mean egg-soil BTF=3, for BS soil conc. (1 ng
TEQ kg-1).
0.3a
Estimated with mean egg-soil BTF=3, for LCS soil conc. (70
ng TEQ kg-1 d.w.)
21a
Reference egg sample, Peru
0.01a
Egg samples Zapallal, Peru
0.3-0.4a
a
ssuming 10 % fat in whole eggs
Modelled exposure doses via ingestion of free range eggs for adults and children in
the Industrial and Development settings are presented in Table 22. At background
concentrations, the highest predicted exposure level did not exceed 1% of TDI. At
the higher soil contamination level of 70 ng TEQ/kg, the maximum exposure dose
approximated 17% of the TDI for children in the Development setting. Since we
68
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
expect that the model has underestimated the egg concentrations at least one order
of magnitude, it is well justified to multiply the doses by a factor of 10.
Consumption of locally produced eggs contributes then to 13 and 25 % of the TDI
for the Industrial setting at 70 ng TEQ kg-1 and to 65-170 % of the TDI in the
Development setting.
Table 22. Modelled exposure doses (% of TDI) via ingestion of free-range eggs for adults
and children in the Industrial and Development settings. A 10-fold adjustment upwards is
justified since the model probably have underestimated the egg concentrations according
to Table 21.
Soil conc.
(ng TEQ kg-1)
Exposure dose
Industrial setting
(% of TDI)
Exposure dose
Development setting
(% of TDI)
Adults
Children
Adults
Children
BS
1
0.080
0.14
0.42
0.90
LCS
70
1.3
2.5
6.5
17
There was a significant difference between exposure levels for the model
populations, which depend upon food consumption habits, body weights and the
fraction of locally produced food that are ingested (Table 19). The exposure levels
differ by one order of magnitude between the highest exposed group (children in
the Development setting) and the lowest exposed group (adults in the Industrial
setting).
Considering that the bioaccumulation in CalTOX might be underestimated at least
on order of magnitude, the dose of the highest exposed group might be significant
(~10% of TDI) already at 1 ng TEQ kg-1 in soil. For populations relying on locally
produced free-range eggs, this exposure route alone could then contribute to more
than 100% of TDI at 10-100 ng TEQ kg-1 in soil.
10.4.2
Ingestion of milk
Modelled concentrations for milk and meat in the BS and LCS are compiled in
Table 23. Since reference data from Peru is missing, the model outputs are
compared to selected data from the literature. The reference studies represent nonpolluted, background scenarios and local contamination scenarios with elevated
PCDD/F levels in soil (23 ng TEQ kg-1 in the UK study, 0.19-13 900 ng TEQ kg-1
in the vicinity of a pasture in Brazil, pasture soil concentrations were not reported).
There are few case studies where contamination of milk have been related to soil
concentration levels in the pasture, thus the reference studies are not necessarily
exact matches of the contamination levels in the modelling scenarios. However,
they do indicate that the modelled milk concentrations are realistic and
representative of generic non-polluted environments and local contamination cases.
In other evaluations of performance of CalTOX in contaminate site scenarios, it
was indicated that the model outputs for biotransfer into milks yield reliable
estimates as long as experimental BTFs are used (Wiberg et al., 2007, Åberg et al.,
69
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
in preparation). Thus, we believe that the exposure assessment is not significantly
biased for this exposure route.
Table 23. Modelled cow’s milk concentrations (pg TEQ g-1 w.w.) in the risk assessment
together with reference data from the literature. BS=Background scenario, LCS=local
contamination scenario.
Milk concentrations
(pg TEQ g-1 w.w.)
Model output, BS
0.027
Model output, LCS
0.41
Milk samples from food basket study, Spain
0.045a.e
Milk samples from rural sites, Switzerland
0.018a,d
Milk samples from polluted site, Brazil
0.25a,b
Milk samples from polluted soil site, UK
0.21a,c
a
assuming 5 % in whole milk, bBraga et al., 2002, cLake et al., 2005, dSchmid et al., 2003,
Fernandez et al., 2004
e
Modelled exposure doses via ingestion of locally produced milk in BS and LCS are
presented in Table 24. In a non-polluted environment, the high ingestion rates of
locally produced milk in the Development setting contributed to 8 % of TDI for
children, while the exposure of adults in the Industrial setting did not exceed 1% of
TDI. At 70 ng TEQ kg-1 soil, the exposure levels for children in the Development
setting exceeded TDI. Also the adults achieved high exposure doses, corresponding
to ~15% of TDI. Even for people in the Industrial setting, the exposure of children
was high (45% of TDI), while the exposure of adults were 7.5% of TDI.
Table 24. Modelled exposure doses (% of TDI) via ingestion of milk for adults and children
in the Industrial and Development settings.
Soil conc.
(ng TEQ kg-1)
Exposure dose
Industrial setting
(% of TDI)
Exposure dose
Development setting
(% of TDI)
Adults
Children
Adults
Children
BS
1
0.6
2.9
1.2
8
LCS
70
7.5
45
15
125
Similarly as for eggs, there are inherent uncertainties in modelling the
bioaccumulation. Site specific factors such as the magnitude and spatial
distribution of local PCDD/F contamination in soil, seasonal changes and feeding
conditions will also affect the contamination levels in the milk. However,
according to the initial evaluation, the estimates in Table 24 are considered as
reliable, but significant uncertainties exist in this estimation.
70
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
10.4.3
Ingestion of meat
Modelled outputs for meat are presented in Table 25. No reference studies were
available that allowed a full scenario comparison between modelled and measured
data since published beef concentrations are not always matched to soil
concentrations from pastures usually. The selected references used in Table 25
represent background concentrations in beef (Bergkvist et al., 2008), and situations
were a local contamination source was present (Stachel et al., 2006; Lindström et
al., 2005). Data from Lindström et al. originated from a site with similar TEQ soil
concentration (86 ng WHO-TEQ kg-1 d.w.) as for our local contamination
scenario. The comparison shows that the model outputs are representative of
generic background conditions as well as where local sources exist.
Table 25. Modelled beef concentrations (pg TEQ g-1 w.w.) in the risk assessment together
with reference data from the literature. BS=Background scenario, LCS=local contamination
scenario.
Meat concentrations
(pg TEQ g-1 w.w.)
a
Modell output, BS
0.016
Model output, LCS
0.17
Beef, background concentrations, food basket, Sweden
0.029a,d
Beef, flooding event with local contamination, Germany
0.16a.b
Sheep muscle, contaminated saw mill site, Sweden
0.22a,c
b
c
assuming 7 % fat in meat, Stachel et al., 2006 Lindström et al., 2005, dBergkvist et al., 2008
Modelled exposure doses for ingestion of meat at environmental background
concentrations, resulted in a maximum exposure dose of 5.4% of TDI for children
in the Development scenario (Table 26). At the higher contamination level, the
exposure dose of children increased to 80% of TDI, while exposure levels for
adults and children in the Industrial setting did not exceed 4.3% of TDI. Also
adults in the Development setting received a significant exposure dose at the higher
contamination level.
Table 26. Modelled exposure doses (% of TDI) via ingestion of meat for adults and children
in the Industrial and Development settings.
(ng TEQ kg-1)
Exposure dose
Industrial setting
(% of TDI)
Exposure dose
Development setting
(% of TDI)
Adults
Children
Adults
Children
BS
1
0.1
0.3
1.4
5.4
LCS
70
1.3
4.3
16
80
Soil conc.
71
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
10.4.4 Ingestion of leafy vegetables
Modelled outputs for exposed produce concentrations (leafy vegetables) are
presented in Table 27. Since this output is affected by soil particle adsorption on
the leaf surfaces, and the adsorption efficiency in reality depend on e.g. climate,
soil properties, leaf size, height above ground and leaf surfaces, it is difficult to
find matching reference data. Plant samples from Peru were therefore used as
reference values, even though they are not eatable vegetables. The plant samples
were also rinsed before analysis, thus they did not contain adsorbed particles as the
leafy vegetables do in the model simulation. Despite this, the modelled
contamination levels of exposed produce were low in comparison to the measured
levels of rinsed plants, up to a factor of 10 in both scenarios. This indicates that the
human exposure assessment might have yielded an under estimated exposure dose
in the simulation. However, it is important to stress that concentration data for
plant species that are consumed by humans are missing. The field data also
indicated species-specific variation of plant concentrations, which in turn were not
normalised to account for varying water content.
Table 27. Modelled plant concentrations (pg TEQ g-1 w.w.) in the risk assessment together
with reference data from Zapallal and Trapiche. BS=Background scenario, LCS=local
contamination scenario.
Vegetable concentrations
(pg TEQ g-1 w.w.)
Model output, BS
0.038
Model output, LCS
0.53
Plant samples 5-6, reference samples, Trapiche
0.33/0.58
Plant samples 1-4, waste site samples, Zapallal
0.01-5.2
At background concentrations, the exposure of the most exposed group was 6.5%
of TDI (Table 28), while the least exposure corresponded to only 0.25% of TDI. At
the high soil level, children in the Development setting received an exposure dose
constituting 90% of TDI. The exposure dose of the adults was 30% of TDI. The
maximum exposure in the Industrial setting was 5.5% of TDI.
Table 28. Modelled exposure doses (% of TDI) via ingestion of exposed produce for adults
and children in the Industrial and Development settings.
Exposure dose
Development setting
(% of TDI)
(ng TEQ kg-1)
Exposure dose
Industrial setting
(% of TDI)
Adults
Children
Adults
Children
BS
1
0.25
0.41
2.7
6.5
LCS
70
2.6
5.5
30
90
Soil conc.
For exposed produce, the model assumes that contaminated soil particles are
adsorbed to the leaf surfaces. Rinsing of the products will therefore decrease the
72
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
external dose. Since no reference data was available to evaluate the modelled
accumulation in the exposed produce, the precision of the model output is insecure.
10.4.5
Ingestion of soil
Since the model assumes that initial soil concentrations (i.e. BC and LCS
concentrations of 1 and 70 ng TEQ kg-1) decreases over time because of transport
and degradation processes, the soil ingestion exposure levels in Table 29 were
estimated for soil concentrations of 1 and 60 ng TEQ kg-1 d.w.
At the BS contamination level, ingestion of soil resulted in a maximum exposure
dose equal to 6.3% of TDI for children it the Developing setting. At 60 ng TEQ,
the exposure of this target group increased to 380% of TDI. The assumed soil
ingestion rates included in this scenario were not supported by e.g. experimental
data, so the assumption may be unrealistic. On the other hand, it is reasonable to
believe that people living at poor conditions will ingest more soil and other
particles, compared to people in industrialised countries. The modelling results
show that the external exposure via ingestion of soil is a potentially important
exposure route in the presence of local sources. In the current example, no
consideration was taken to the reduced availability of PCDD/Fs on soil particles for
absorption in the digestive system (Budinsky et al., 2008; Ruby et al., 2002;
Morinello et al., 2003). This approach may in turn lead to that the health risk
related to soil ingestion is exaggerated.
Table 29. Modelled exposure doses (% of TDI) via ingestion of surface soil for adults and
children in the Industrial and Development settings.
Soil Conc.
(ng TEQ kg-1)
Exposure dose Industrial
setting
(% of TDI)
Exposure dose
Developing setting
(% of TDI)
Adults
Children
Adults
Children
BC
1.0
0.03
0.4
0.4
6.3
LCS
62
2.0
25
23
380
At the highest input soil concentration (70 ng TEQ kg-1 soil), the estimated
exposure levels for single exposure routes of the most sensitive population
exceeded TDI by far. At the same environmental concentrations, the exposure
level of the most and least sensitive populations differed by one to two orders of
magnitude.
73
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
10.5 Critical soil concentration levels
Some general conclusions can be drawn from the exposure assessment, the
modelling exercises and the supporting field data; i) even at moderately elevated
soil concentrations (e.g. 50-100 ng TEQ kg-1) local food and soil ingestion
pathways may add significantly to recommended TDIs of local residents, ii) the
exposure levels differ by orders of magnitude depending on the environmental
concentrations and living conditions of the people.
Estimated exposure levels for populations in the Developing settings as functions
of increasing soil concentrations, are presented in Figure 13 a and b for illustrative
purposes. In these figures, the egg exposure routes were adjusted upwards by a
factor of 10 to compensate for that the model predicted lower levels than estimated
by soil-egg BTFs from the literature. The exposure estimates assume 100%
availability for internal absorption of contaminants in all matrices.
Critical soil concentrations that result in total exposure levels equal to 100% of
TDI, were 45 ng TEQ kg-1 (0.045 ppb) for the adults, and 7 ng TEQ kg-1 (0.007
ppb) for the children. The scenarios simulate that the target populations are selfsupporting when it comes to food, such as leafy vegetables, milk, meat and freerange-eggs. Additional exposure via inhalation, ingestion of fish and other food
products may exist but these was not taken into account, and nether was additional
exposure through ingestion of dl-PCBs.
74
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Figure 13. Summary of estimated exposure levels (ingestion of soil, total ingestion o food and
total exposure) for a) adults and b) children in the Development setting. Critical soil concentrations
that result in total exposure levels equal to 100% of TDI, were 45 ng TEQ kg-1(0.045 ppb) for the
adults, and 7 ng TEQ kg-1(0.007 ppb) for the children.
For children, almost 40% of the dose was related to ingestion of soil, an exposure
route which contains a high degree of uncertainty since soil ingestion rates differ
considerably between individuals and are difficult to determine (US EPA, 2003).
By excluding a correction factor that accounts for reduced absorption efficiency in
the digestive tract of soil-associated contaminants (corresponding to 20-60% of the
total concentration; Ruby et al., 2002), this exposure route may have been
overestimated by a factor of 2-5. Even in a “best case” scenario assuming 20%
availability, soil ingestion would have contributed to 100% of TDI for children in
the Development setting at soil concentrations close to 80 ng TEQ kg-1.
Considering that residues from thermal processes in general contain levels of
PCDD/Fs that exceed this concentration by far (Table 2), ingestion of soil/dust/ash
is an alarming risk scenario if local communities are exposed to concentrated waste
that are introduced into their surroundings.
Ingestion of soil may result in
high exposure levels for children
and adults. This exposure route
contains several uncertainties
and a reduced internal
bioaccessibility of solid matrices
is not always taken into account
in exposure assessments.
At soil concentrations of 80 ng
TEQ kg-1 (0.08 ppb), the
For adults, the tolerance level are higher, mostly
due to higher body weight and a behaviour that
in general prevent high soil ingestion rates.
Adults can, however, become exposed via
occupational activities that increase their soil
ingestion rates. They can also be subjected to
exposure of concentrated waste during handling
of concentrated waste.
75
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Table 30 illustrate soil ingestion exposure for adults in the Development setting at
different solid matrices concentrations, assuming an internal availability that ranges
20-100% of the total concentration. In the worst case scenario (assuming 100%
accessibility), 1 000 ng WHO-TEQ in the solid matrices resulted in 370% of TDI.
In a best case scenario (assuming 20% accessibility), a solid matrices concentration
of 1 000 ng WHO-TEQ still yielded a significant exposure corresponding to 74 %
of the TDI.
Table 30. Estimated adult soil ingestion exposure (% of TDI) for the Development setting at
different solid matrices concentrations (ng WHO-TEQ kg-1) assuming different internal
availabilities after exposure.
Solid conc.
(ng TEQ kg-1 d.w.)
100 % availability
50 % availability
20 % availability
1
0.4
0.2
0.1
62
23
11
4.6
1 000
370
190
74
If the soil ingestion rate for children was extremely exaggerated in the
Development setting, this exposure pathway can be excluded from the model
assessment for illustrative purposes. A certain amount of soil will still affect the
exposure, since soil particles contaminates the terrester food chains via pasture soil
and grass. By excluding soil ingestion exposure, the critical soil concentration that
corresponds to 100% of TDI increases to 12 ng TEQ kg-1 for children in the
Development setting. If the amount of ingested food is reduced by 50%, if e.g. the
food ingestion rates were overestimated by a factor of 2, or if only 50% of the total
consumption was locally produced, the critical soil concentration would be ~25 ng
TEQ kg-1. However, if all the original assumptions in the scenario are realistic, 25
ng TEQ kg-1 in soil corresponds to 300% of the TDI of the children.
The exposure assessment is
affected by several uncertainties
which are related to human
exposure parameters and
assumptions about population
behavior.
As illustrated above, there are a number of
assumptions that will affect the levels of the
critical soil concentrations. The exposure
assessment is therefore limited by the fact that
individual variations of food and soil ingestion
rates are not covered by the methodology we
used. Average intake rate values are not representative of consumption patterns that
usually are highly variable in true populations. As mentioned before, some of the
parameters were also defined using rough assumptions, even though they were
justified from expected population differences related to e.g. the degree of
industrialisation of different regions and living conditions (rural or urban). The fact
that little is known about current human exposure levels of populations in
developing countries makes it challenging to assess current baseline exposures in
non-polluted environments.
76
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Despite limited possibilities to take all variables and uncertainties in local
contamination scenarios into account, the assessment indicate that critical soil
concentrations of PCDD/Fs for sensitive target groups (such as children in selfsupporting and rural settings), are found in the range of 7 to 25 ng TEQ kg-1.
Estimated adult exposure at these levels will not exceed 20-70% of TDI, given that
the assumptions for this target group were realistic. However, it is important to
stress the fact that high ingestion rates of a single, locally produced food item (such
as free-range eggs), may result in a significant exposure level even at these soil
concentrations.
By using the sum of multiple exposure routes to identify critical soil
concentrations, one assumes that the target group is exposed via several routes
simultaneously. This assumption is not necessarily true, but represents a worst
case. Again, there is a significant uncertainty of how important different exposure
routes are for different individuals in a given population.
One clear limitation of this assessment was that dl-PCBs were not included. A
general assumption is that dl-PCB contributes to approximately 50% of the TEQ in
food, and that only 50% of TDI can be accounted for by PCDD/Fs. Thus, it is
reasonable to adjust the critical soil concentration downwards by a factor of two. It
then results in 3 to 13 ng TEQ kg-1 in soil for children with high ingestion rates of
locally produced food.
It is also important to stress that modelled soil concentrations represent average
levels in soil for a specified area that is simulated by the model. Thus, the highest,
tolerable level in soil has not been specified by the calculations.
77
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
11
Synthesis of the results
11.1 Risk scenarios
By reviewing the literature, only a few case studies showed or indicated that
management of PCDD/F contaminated waste has been a major, local source. The
contaminated waste materials in the most relevant case studies were impregnated
wood and incineration residues.
The review showed that a serious risk scenario is prevailing if waste wood
fractions are reused as bedding or construction material in animal food production
facilities. Considering that PCDD/F waste wood concentrations of 40-50 ng WHOTEQ kg-1 resulted in severe egg contamination (33-88 pg WHO-TEQ g-1 fat
(Diletti et al., 2005), the suggested LPCL of 15 000 ng TEQ kg-1 (15 ppb) is not
low enough for this waste fraction. Frequently occurring food contamination
incidents show that animal food production facilities are sensitive targets for
contaminants that are introduced via recycled/uncontrolled material, even though
the majority of the incidents were unintended. Contaminated waste wood fractions
can also enter biofuel incineration facilities, resulting in higher pollutant
concentrations in the residues.
For incinerations residues, several options for recycling and reuse seem to exist. A
serious risk scenario is prevailing if the material is used in areas close to animal
food production facilities or if the application allows direct contact with the waste
by local residents or workers. In the New-castle case study (Pless-Mulloli et al.,
2001), the highest measured PCDD/F concentration in recycled ash was 9 500 ng ITEQ kg-1 (9.5 ppb), while free range chicken eggs from the contaminated
recycling area contained 0.4-56 pg I-TEQ g-1 fat. Even though it was not possible
to establish a quantitative correlation between the PCDD/F egg and recycled ash
concentrations, the results shows that the suggested limit of 15 ppb for PCDD/F in
waste does not allow unrestricted reuse of ash that do not exceed this criteria. Since
moderately elevated environmental levels (e.g. 10-50 ng TEQ kg-1 in the ground)
are high enough to cause significant exposure levels of local residents living under
rural conditions and relying on locally produced food, the impact from highly
contaminated waste in certain areas can be detrimental if the waste is reused with
limited awareness of possible consequences. Experiments with ducks that were fed
with contaminated fly ash (containing 201 ng TEQ kg-1 or 0.2 ppb), showed that
the eggs became contaminated despite a restricted bioavailability of PCDD/Fs in
solid matrices and rather low ash concentrations (Shih, 2009).
In spite of an extensive record showing that management of solid and liquid waste
has historically been important as local pollution sources, the limited number of
recent contamination cases may indicate that improper management of PCDD/F
78
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
waste is not a common source for PCDD/F and PCB contamination of human food
chains or human exposure today, at least not in the developed part of the world. On
an international level, there are, however, indications that PCDD/F contaminated
waste is not always managed to avoid negative environmental or human health
effects. Open waste dump sites and rivers in developing countries are potential
targets for dumping of highly contaminated waste. In these countries, open
dumping can affect subpopulations that scavenge the waste fill for recyclable
materials. The resources to detect and measure such impacts are usually limited in
these countries. There is also an occupational hazard for people managing the
waste sites. Overall, open access to highly contaminated waste sites can affect
wildlife, since birds and other animals feeding on the sites accumulates the
pollutants (Watanabe et al., 2005). So far, it seems that human health effects
related to open dumping of PCDD/F contaminated waste is not well investigated.
The minor field studies in Peru and Thailand confirmed that highly contaminated
ashes are stored on open ground at sites where the waste is produced. In theory,
wind-blown distribution of ashes is a highly relevant contamination scenario that
can affect the surroundings. Our field study did, however, not allow distinction
between distribution of ash residues from other local sources, such as air emissions
and subsequent deposition from the recycling activities. It is important to keep in
mind that areas that are affected by multiple sources are even more sensitive for
additional pollution. Possible consequences of improper ash management strategies
can, in most cases, only be discussed from a theoretical point of view.
One special case where recycling of contaminated incineration residues may result
in high emissions of PCDD/Fs to the surroundings is when the Waelz process is
applied. This is a recycling technique that uses a thermal process to reclaim metals.
If POP contaminated ash is used in the process, efficient air pollution control
devices are needed to reduce the PCDD/F emissions from the flue gases. Compared
to incineration of waste, the emissions from recycled POP contaminated ash in the
Waelz process may be considerably higher. In the literature study, only one study
dealt with this issue. A more comprehensive investigation is probably needed to
conclude whether this recycling application is of special interest in the context of
this study.
Special cases where PCDD/F contaminated waste have caused severe impact of
local environments are management of chemical waste from e.g. organochlorine
production, but most existing cases seem to be legacies of the past. Since chemical
wastes contain a mixture of hazardous pollutants, they might be classified as POP
contaminated waste by other criteria than PCDD/F. Detected levels of PCDD/Fs in
recently produced chemicals from e.g. Asian countries indicate that waste streams
in chemical industries can be contaminated as well. A more thorough research into
this issue is needed before the importance of these waste streams can be
established.
79
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Another area with ongoing production of POP contaminated waste is e-waste
recycling. So far, most studies have focused on environmental impacts generated
during the recycling activities, and less focus has been put on the waste fractions. A
limited number of studies show that residues from incineration contain high levels
of PCDD/Fs, and that generated waste products have be dumped in the local
environment.
Via ingestion of locally produced food, humans get exposed of accumulated
contaminants and correlations between high body burdens and ingestion of locally
contaminated food have been observed. However, little is known about current
baseline exposure of people in developing regions, and it is not appropriate to
extrapolate data between different regions or cultures, since living conditions and
dietary habits differ.
11.2
Exposure assessment
The exposure assessment that were based on environmental concentrations from
the field study in Peru, identified adults and children, living under rural conditions
and are more or less self-supporting with food, as sensitive receptors for local
environmental pollution. A critical PCDD/F soil concentration of 7-25 ng TEQ kg1 was estimated for children. Within this range, it seems that a rural lifestyle with a
high proportion of ingested locally produced food probably can be maintained by
young children and adults without exceeding the TDI. However, this range
assumes that dl-PCBs do not contribute to the total risk, an assumption which
likely underestimates real case scenarios, as discussed earlier (and also later).
For direct exposure via ingestion of soil, the levels in waste/solid matrices should
probably not exceed 200-1 000 ng TEQ kg-1 for adults. This range is estimated
from exposure dose calculations using assumptions for adults that must be verified,
e.g. for occupational exposure scenarios. The estimated range is also dependent the
internal bioaccessibility of PCDD/Fs in solid matrices. Results from a number of
studies of soil show that if 100% internal accessibility is assumed, the exposure
dose via ingestion of soil is overestimated, since the accessibility usually ranges
20-60%. The accessibility of pollutants from ashes is not necessarily the same as in
soil, since ash has another physical and chemical composition.
It is important to stress that there are several assumptions underlying the
identification of the critical soil concentration, and many of these assumptions have
not been verified by e.g. experimental data for real target populations. There are
also inherent uncertainties in several steps of the assessment, and these
uncertainties affect the accuracy of the critical soil concentration. Major
uncertainties are i) to what extent the exposure routes will exist simultaneously or
alone, ii) the amount of ingested food that are locally produced, iii) food ingestion
rates, and iv) the amount of ingested soil. Since the assessments were based on
80
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
hypothetical populations, it was considered as more reasonable to identify an
interval of “critical soil concentrations” rather than one single value. The estimated
ranges for the critical soil concentrations were found by using “acceptable
exposure levels”, which here was 100% of TDI, since the scenario was assumed to
simulate self-supporting residents.
One major limitation of the exposure assessment was that dl-PCBs were not taken
into account, and this was because of theoretical limitations; experimental data
necessary to yield reliable modelling results was not easily available. Since the
currently suggested LPCL does not include dl-PCBs, the final risk related to
exposure of dioxin and dioxin-like compounds from solid matrices (e.g. ash or soil)
might be underestimated. Soil-to-egg BTFs from a selection of studies show that
dl-PCBs are more available, which might counteract the fact that dl-PCBs are
present in lower TEQ concentrations then PCDD/Fs in soil and ash. Field data from
Peru support this finding, since the TEQ fraction related to dl-PCBs were much
higher in biotic samples, compared to the abiotic matrices. If a risk scenario
includes only exposure via ingestion of soil or solid matrices (e.g. in an
occupational scenario), dl-PCBs might be of minor importance as long as their
internal bioaccessibility do not exceed the accessibility of PCDD/F. Since the TDI
includes both PCDD/Fs and dl-PCBs, a downward adjustment of the critical soil
concentrations to 3-13 ng TEQ kg-1 for PCDD/Fs may be justified to allow
additional exposure of dl-PCBs. In an exposure assessment where the accumulation
of PCDD/Fs and dl-PCBs are processed together, it is recommended to review and
adjust these limits.
Since typical background PCDD/F soil concentrations (0.14-4.1 ng TEQ kg-1 d.w.,
Rogowski & Yake, 2005; 0.62-1.6 ng WHO-TEQ kg-1 d.w., Matscheko et al.,
2002) that are only affected by atmospheric deposition or urban sources are close
to the critical limits calculated in this study, the margins until the soil may become
a significant source is small. Even soil concentrations at strictly regulated
hazardous landfills are close to the lower end of this interval (1.5-2.14 ng TEQ kg1 d.w.; Mari et al., 2009), and soil at unregulated open waste dump sites may
exceed the interval by far (0.02-1 700 ng TEQ kg-1 d.w.; Table 3, Minth et al.,
2003). However, some of the impact at open waste sites can be attributed to open
burning of waste. The fact that soil at regulated hazardous waste sites contain
higher PCDD/F concentrations than reference areas (Mari et al., 2009), indicates
that waste sites in general may contain elevated concentrations of PCDD/Fs that
originates from solid waste. The landfill investigated by Mari et al. (2009) has been
receiving PCDD/F contaminated waste for ~10 years only. The soil sampling at
Zapallal in Peru showed a gradient, with decreasing PCDD/F concentrations at
increasing distance from the waste site (Figure 6). Thus, possible exposure hazards
associated to elevated soil concentrations will have limited spatial distribution.
81
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Studies of POP body burdens for waste picking children at open waste sites have
shown that open dump site areas contribute to human exposure (Cuadra et al.,
2006). This conclusion was also drawn by Santos et al. (2003), who investigated
the exposure of organochlorine pesticides in residents at an open dump site area.
Even though PCDD/F or dl-PCB was not investigated, it is most possible that the
body burdens of these substances might have been elevated as well. Cuadra and coauthors found also a gradient with decreasing POP concentrations in non-working
children as the distance to the waste site increased. Kunisue et al. (2004) showed a
strong correlation between elevated TEQ concentrations in soil at Indian open
dump sites and high body burdens in human milk (Table 8). The exposure was
caused by buffaloes grazing at the polluted site and high ingestion of bovine milk.
For PCDD/F, most case studies have focused on scenarios that include dietary
exposure pathways (Chapter 6), but our exposure assessment show that ingestion of
solid matrices (soil or ash) may be significant contributors at solid matrices
concentration of 10-100 ng WHO-TEQ kg-1 d.w. (Figure 13). Results by TurrioBaldassari et al. (2008) indicate elevated TEQ serum concentrations in residents
exposed to contaminated soil, but no local dietary exposure, at an former industrial
area (15-1 034 ng WHO-TEQ kg-1 d.w., including both PCDD/F and dl-PCB;
Turrio-Baldassari et al., 2007, see also Figure 2). However, the serum
concentrations were not significantly higher than reference concentrations for less
exposed populations. Despite elevated soil concentrations at open dump sites
(Table 3; Minh et al., 2003), local residents were not subject to elevated exposure
as long as local food chains were not contaminated (Kunisue et al., 2004, see also
Table 8).
In summary, open waste sites (or other areas that receives PCDD/F contaminated
waste) may be a local source of PCDD/F and dl-PCBs, and soil concentrations may
exceed levels that are considered as “safe” for self-supporting populations. Few
investigations of PCDD/F and dl-PCB body burdens and exposure levels in local
residents at such sites have been performed. If local food chains become
contaminated, there is an obvious risk for elevated body burdens. If local dietary
exposure pathways are absent, the risk depends on the intensity of contact with
contaminated solid matrices, which in turn depend on human behaviour. Little is
known about possible effects associated to this exposure route.
82
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
11.3 Uncertainties in the results
In the following paragraph, uncertainties related to the results in this report are
briefly discussed.
11.3.1
Identifying risk scenarios related to improper management
of PCDD/F contaminated waste
This task was formulated from a very broad perspective, but was limited by a
vague opinion of the kind of waste categories that actually were of importance.
Focus was therefore put on incineration residues, since they globally are produced
in huge volumes and are of contemporary and future relevance. Furthermore, they
were treated by the BIPRO report. Contaminated waste wood fractions were added,
since the literature study identified several relevant case studies related to the
purpose of the project. This fraction is generated during demolition of old buildings
and wood constructions where chlorophenol impregnated wood have been used.
Chemical waste and residues from e-waste recycling were included since results
from other studies indicate that these on-going activities may generate “new” types
of PCDD/F contaminated waste. Other recently produced PCDD/F contaminated
waste types may of course exist, but they have neither been directly or indirectly
identified in the literature search.
Production waste from organochlorine industry can contain high levels PCDD/Fs
and other unintentionally produced POPs (Weber et al. 2008). While such chemical
waste in industrial countries are incinerated in dedicated hazardous waste
incinerators, such facilities are lacking in developing and transition countries still
today. Therefore, it will be important to control such wastes in these countries.
The literature search was made using the scientific data base Web of Science. It
covers a broad range of scientific journals with topics related to environmental
science. However, chemical abstracts, technical reports and conference
proceedings are not included in this data base. Relevant information that was not
identified in our literature search may therefore exist. Technical reports and
conference proceedings that have been cited in this report was either found as
references of cited journal articles, or they were known by participants in this
project.
The identified risk scenarios are mostly based on empirical evidence to show that
they are relevant, even if the likelihood that they will occur depend on factors that
could not be assessed by this project. Other risk scenarios, which so far have not
resulted in site investigations or other measurable impacts of the environment or
human health, may exist as well.
A compilation of internationally reported data for PCDD/F in different waste
categories was made. It does not claim to give a complete picture of contamination
83
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
levels in waste, but was compared to the suggested Low POP Content Limit to
investigate residue levels in relation to the LPCL. Limited information exists for
dl-PCBs in waste. It is therefore difficult to quantify the total risk in scenarios that
include transfer of dioxins and dioxin-like compounds into food chains. In the
exposure assessment, it was assumed that dl-PCBs will constitute 50% of the total
exposure.
11.3.2
Correlating environmental levels to human food chain
contamination
This is an extensive research area. The cited references were selected since they
illustrate consequences of local contamination scenarios. Food chain contamination
at background conditions were of limited interest. Since site-specific circumstances
will influence the bio-transfer of pollutants, it is difficult to describe the impact of
local contamination scenarios in general terms. However, a quite large number of
studies were cited, and they are consistent in that they show that local sources are
of great importance for local food chain contamination. The difficulties arise when
this impact must be described quantitatively. Field data is usually presented in
different ways and for different purposes, and there are a limited number of studies
where data can be used to address the biotransfer variability related to different
field conditions.
In this report, the variability for transfer into free-range eggs was described
quantitatively by calculating soil-to-egg concentrations ratios and analysing their
statistical distributions. The same could not be made for beef or milk transfer due
to lack of data. The biotransfer variability is a high source of uncertainty in risk
assessments that rarely is taken into account. It could not be fully incorporated in
the exposure assessment in this report either, even though it was used to evaluate
assumptions in the risk assessment by BIPRO and the reported exposure
assessment. Since uncertainties exist in all stages of a risk assessment, the most
comprehensive way to handle them is to use probabilistic approaches, but this was
beyond the scope of this project. By excluding the uncertainty related to biotransfer
variability, a full understanding of how the risk is distributed within a population is
never gained and the final risk estimate can be overestimated as well as
underestimated.
11.3.3
Correlating environmental levels to improper management
of waste in the field studies
One of the largest uncertainties related to the scope of this report is probably how
to quantify possible impacts from contaminated waste on environmental
concentrations. This correlation does not only depend on pollutant concentrations
in waste, but also on the amount of waste that is distributed into the environment,
how the waste is managed/recycled and the spatial distribution of the waste in
affected areas.
84
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Even though a number of studies show that the presence of local pollution sources
may affect human food chains, it is difficult to empirically show that improper
management of waste will affect local environmental concentrations. To be able to
plan a field study that fulfils its purposes, good knowledge about the sampling sites
and some knowledge about local environmental concentrations are usually
necessary. The field studies that were performed within this project were the first at
the selected study sites. In the initial planning stage, information about the sites
was compiled by local NGOs, and their information was later used to set up a
sampling scheme. Existing measurements of environmental concentrations did not
seem to exist, so the sampling was planned from theoretical expectations about
pollution sources and the fate of contaminants in the environment. Even though the
results showed that highly contaminated ash was managed at the sites and that the
surroundings were affected by the activities at the sites, it was not possible to
distinguish between ash distribution and other local sources. The fact that air
emissions from the recycling/incineration activities probably are additional sources
complicated the evaluation of the results. Since air and flue gas measurements were
not performed, the field study was not designed to be able to separate the impact of
the two sources (air emissions and contaminated ash). Overall, sampling and
measurements of flue gas and air are difficult to perform to get representative
results. Considering the improved knowledge about fate and distribution of
pollutants at the study sites, it might be possible to follow-up the first sampling to
further investigate and separate the impact of the different sources, if necessary.
11.3.4
Human exposure assessment
Overall, the major uncertainties in the exposure assessment are probably related to
human behaviour, and if exposure will result in elevated body burden or not.
Exposure doses and elevated body burdens related to PCDD/F contaminated solid
matrices in the environment are not addressed as often as dietary exposure
pathways. Some additional data may exist for occupational exposure scenarios,
where the exposure pathways are different compared to local residents.
Considering that the Low POP Content Limits are applicable to solid matrices, this
exposure route should be investigated more carefully to improve our understanding
of how PCDD/F contaminated waste may affect human health.
Sparse pollution data exist for waste site scenarios, which are believed to be
relevant for the purpose of this project. Existing studies represent either regulated
hazardous waste sites that operates according to European principles, or nonregulated open waste sites in developing countries where burning of waste also is
performed. Between these two “extremes”, there are probably other representative
waste site scenarios, which perhaps never have been investigated. It would
therefore be desirable to identify waste sites (or other sites that receives PCDD/F
contaminated waste) that are operated at different conditions, and to perform risk
assessments at the sites to get more information about contamination levels in the
85
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
waste and the surroundings, as well as body burdens of people that reside or work
in the area.
The model populations in the exposure assessment were parameterised using
empirical data that represents “average persons”. In some cases, rough assumptions
were made from a theoretical point of view, and these assumptions were not
supported by field data. The strong impact of different human behaviour was
illustrated by the human exposure outputs, which ranged over one to two orders of
magnitude for the model populations. By using averages, the exposure of parts of
populations is underestimated, while 90th or 95th percentile point estimate values
can overestimate the exposure. Again, a probabilistic approach is more suitable to
illustrate ranges of human exposure levels taking intra-population variability into
account. It is likely that deterministic risk assessments exaggerate the risk.
To be able to correlate environmental levels to human exposure, a multimedia
modelling approach was applied. The advantage of the method is that multiple fate
and exposure routes can be investigated in different scenarios for a range of
environmental levels. The disadvantage of modelling is that it relies on numerous
assumptions and simplifications that cannot always be supported by empirical data
or by site specific knowledge. For the purpose of this report, the model was applied
for generic local contamination scenarios, where field data from one of the case
studies was used as input to define the environmental concentrations.
By using empirical field soil concentrations as input, a realistic contamination
scenario was assessed. The soil input data was characteristic for incineration
sources, and the congener patterns showed high levels of lower chlorinated PCDFs.
Theoretically, pollution by sources exhibiting incineration congener composition
constitutes high risk scenarios, since the lower chlorinated congeners are more
mobile and bioavailable and will more easily be transferred into food chains.
Some of the model uncertainty derives from the applied BTFs. Methods where
BTFs can be estimated for super-hydrophobic compounds, are associated with a
high degree of uncertainty. This uncertainty will exist for all model calculations
that rely on BTFs.
To improve the confidence in the model outputs, field data from the current project
and other field studies were used to evaluate the performance. This approach
contributed to reduce some of the uncertainty related to uncertainties described
above. In most cases, the model outputs were found reliable, and adjustments were
only justified for transfer into eggs, where a comprehensive set of empirical soil-toegg concentrations ratios were used to calculate reference data. The evaluation was
limited by the fact that few case studies have been performed at the same
environmental concentrations as in the modelling scenarios, and it was not always
possible to relate reported concentrations in biotic matrices to soil concentrations in
the reference studies. Since the selected model has been applied and evaluated for
PCDD/F in other scenarios that were not part of this project, earlier gained
86
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
experience in evaluating and interpreting the model outputs were valuable. Since
the model was applied using a deterministic approach, parameter uncertainties
were not included. The deterministic approach conflicts the empirical evidence that
biotransfer into human food chains is highly variable. Thus, deterministic results
can unconsciously result in misleading feelings of “safe and easy decisions”.
11.3.5
Estimated critical soil concentrations
The estimated critical soil concentrations are affected by previously discussed
uncertainties. Additional uncertainty arise when multiple exposure routes are
summed to a total exposure level, which then was used to identify critical soil
concentrations where people can live without exceeding a certain portion of the
TDI. If one supposes that target populations should be able to live without
limitations on a contaminated site, this approach might be justified. By using the
sum of multiple exposure routes, the total risk is, however, easily (although not
always intended so) exaggerated since point estimates usually include some safety
margins and these are added when the exposure routes are combined. It can also be
questioned how likely it is that the behaviour of a population are characterised by
“worst case behaviour” for all exposure routes. It does not have to be likely that
people rely on getting or buying food produced at a local site to 100%. In
identifying critical soil concentrations or any other limit values, one must define an
acceptable exposure level, which can be TDI or a portion of TDI, depending on the
human exposure scenario and the context it simulates.
Finally, anyone should be aware of that modelled soil concentrations represent
average levels in soil for a specified area that is represented by the model
landscape. Average, tolerable soil concentration level allows variable soil
concentrations where the highest, tolerable level actually has not been specified.
Again, the spatial distribution of soil concentrations and activities related to human
behaviour is of importance for the final risk and the modelling results should not be
misinterpreted as a maximum allowable soil concentration.
11.3.6
Degree of protection with current Low POP Content Limits
The ultimate aim of the project was to investigate whether the suggested Low POP
Content Limits for PCDD/Fs is low enough to prevent human health risk. Even
though empirical evidence is limited to a few case studies, and there still exist
knowledge gaps that limits the understanding of how contaminants in waste will
affect humans, the combined results using a range of methods points toward a “no”
as an answer of the question. In relation to the concentrations that are found in
waste, local environments cannot contain those high levels while keeping safety
margins for human health.
Still, the main uncertainty related to this task is related the one that was discussed
in paragraph 3: what are the possibilities that improper management of
contaminated waste will cause serious environmental contamination? Under what
87
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
circumstances will such scenarios come true? To what extent can environmental
levels become affected by the waste?
Since this project focused on human health risks, no efforts have been made to
identify the risk related to fate and distribution of PCDD/Fs from an ecological
point of view. Studies have identified open dump sites as sources for PCDD/F in
wild birds. Another issue that has not been discussed in this report is long term
consequences for the society if POP contaminated wastes are recycled and
pollutants are reintroduced into the environment.
88
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
12 Conclusions
• There exist several cases that illustrate large negative impacts related to
direct emissions of waste and waste water into the environment, although
only a few of them represent current incidents and most of them are related
to chemical production. Recent incidents have occurred in Europe and
illustrate how improper recycling of ash and impregnated wood may
contaminate human food chains. Empirical results from actual cases
indicate that the currently suggested LPCL for PCDD/F is not low enough
to prevent serious contamination of human food chains.
• Considering the high concentrations of PCDD/Fs in different waste
fractions, direct exposure via ingestion of soil/solid matrices are of great
concern. The importance of this exposure route is less thoroughly
investigated compared to dietary pathways for scenarios with elevated
levels of PCCD/Fs and dl-PCBs in soil. Exposure calculations for
PCDD/Fs and studies of human POP body burdens at open waste sites
indicate that PCDD/F contaminated waste may be a risk for populations
with intense and regular contact with the waste is intense.
• Dietary exposure assessments show that exposure levels of people in many
countries are close to or exceed the recommended TDI. Limited data exist
for populations in developing countries. For most populations, this means
that an allowable incremental exposure related to waste can only account
for a minor part of the TDI.
• Limited data exist for dl-PCB concentrations in waste. Even though
existing data indicate that dl-PCB account for a minor fraction of the total
TEQ, the higher accessibility of this compound group may lead to a
significant contribution to total TEQ if the waste is introduced into the
environment and its pollution enter food chains. So far, the impact of dlPCBs in waste has not been fully investigated.
• A critical soil concentration of 7-25 ng WHO-TEQ kg-1 (0.007-0.025 ppb)
for PCDD/Fs was identified for children in rural and self-supporting
settings. The criterion was that the total exposure summed for multiple
exposure routes should not exceed TDI. If additional exposure from dlPCBs is assumed to account for 50% of TDI, this limit should be adjusted
downwards to 3-13 ng WHO-TEQ kg-1 (0.003-0.013 ppb). A number of
uncertainties were identified that affect the accuracy and the span of the
range. The critical soil concentrations represent only average levels in soil
and not the maximum tolerable levels. Still, the range is far below the
suggested Low POP Content Limit of 15 ppb, and suggests a high risk for
89
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
scenarios where PCDD/F contaminated waste contaminate the
environment.
• For adults, ingestion of soil or ash can become an important exposure route
during e.g. occupational exposure. Ingestion of soil/solid matrices is also
important for children in residential scenarios. Critical solid matrices
concentrations for adults can probably be found in the range of 200-1 000
ng WHO-TEQ kg-1 (0.2-1 ppb) depending on the assumed internal
bioaccessibility of solid matrices, the soil ingestion rate and what fraction
of TDI that is considered as an acceptable exposure dose. This range is far
below the suggested Low POP Content Limit of 15 ppb.
• Existing data show that the internal bioaccessibility of PCDD/F in soil is
strongly reduced. No data was found for PCDD/F in waste matrices,
neither for dl-PCBs in soil or waste matrices. By assuming 100%
bioaccessibility in exposure calculations, the risk related to ingestion of
soil/solid matrices is exaggerated.
• Results from the field studies in Peru and Thailand showed that the open
waste sites are local sources to the environment and that highly
contaminated ash was stored open. However, it was not possible to
determine the relative impact of management of PCDD/ contaminated
solid waste from local air emissions.
90
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
13 Recommendations for future
work
The results in this report was a first approach to investigate human health risks
associated to PCDD/Fs and dl-PCBs in waste and waste management practices in
the society. The issue is complex and is not easily handled, since it involves
environmental and toxicological sciences as well as political, technical and
economical perspectives. Therefore, the aim of this report was not to suggest new
Low POP Content Limits for PCDD/Fs (or dl-PCBs) in waste. The results highlight
some issues that are important from a human health perspective and that parties
involved in the process of setting Low POP Content Limits should consider.
Our recommendations for future work in this issue are:
• To discuss consequences of including or excluding dl-PCBs in the Low
POP Content Limits. This task might require more information about
expected levels in waste, consequences for the exposure assessment,
discussion about economical, technical and political consequences, etc.
• To consider how to deal with the wide range of uncertainties that are
incorporated in all risk assessments. It is more advantageous to apply a
probabilistic approach that incorporates data uncertainty and variability
than to rely on point estimates. To avoid speculations and “best guesses”,
it is preferable if relevant and realistic waste management scenarios can be
identified. Empirical data can then be collected for known cases, and the
data can thereafter underlie the development of scientifically based limit
values. Exposure to solid matrices is a risk factor due to extremely high
concentrations in some waste products. The contact intensity to solid waste
varies among different exposure groups and the soil/dust ingestion
parameter is usually associated with a high uncertainty. Considering the
high TEQ levels in solid waste, it is possible that airborne exposure may
be of concern for some occupational indoor environments. Handling of
PCDD/F contaminated waste close to areas with animal food production is
another important risk scenario.
• To consider if the international perspective continues to be of importance.
If so, more information should be found out about exposure routes and
body burdens of people that belong to risk scenarios in developing
countries (e.g. waste pickers at open waste dump sites or people that are
working with POP contaminated waste). This is probably a major task that
requires identification of suitable sites, knowledge of emissions and
environmental levels and sampling of human serum for exposed people
and control groups.
91
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Appendix A
Preliminary study of the waste site Zapallal, Peru
Emission and Pollution Problem by dioxin
in Peru
(Luis Gomero Osorio)
Introduction
The Action Network in Alternative Agriculture (RAAA) joined with Japan
Offspring Fund (JOF) and worked in a coordinate way in 2001. It was in order to
analyse samples of urban residue incinerators and this work involved many
countries in the Asia – Pacific Region. The results of this study showed a high level
of dioxin emission in Peru.
The sample of Zapallal landfill gave a result higher than the permitted limits (3 ng
– TEQ/g according to WHO). This landfill is located in the Carabayllo district in
the north of Lima city. The analysis of ash residues showed the presence of dioxin
14 ng-TEQ/g; it represented a 466 % more than the permitted limits.
Moreover, two samples were taken in other places, one of them was taken from the
Cockroach landfill (nowadays has been closed) and the other was taken from the
COR-PAC incinerator (located in the International Jorge Chavez Airport,
nowadays the incinerator has not worked). The levels of dioxin for both samples
were 0.19 and 0.36 TEQ/g respectively. The values are lower than the permitted
limits by WHO.
In 2006, the Project PNI – COP determined the emissions of PCDD/PCDF
estimated by Peru. In order to get it, the reference that was used were the data for
2003 year as a base, belonging to the incineration category of waste; the total
emission was 21 g TEQ/a by air way and was 17 TEQ/a by waste way of
PCDD/PCDF.
According to the regional distribution of the emissions of PCDD/PCF into the air,
it has been determined that the Lima city has a great emission of it; it is higher than
10 TEQ/ year. It happens because of the difficulties for management and the final
disposal of the solid waste. The reason of this situation is because of open field
burning of solid and dangerous waste.
Moreover, according to the inventory of dioxin and furan of solid waste of
municipalities in Peru, the emission into the air is approximately 0.09 g TEQ/year.
The reason of this is because of open field burning.
92
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
The inventory in its conclusions mentions that the process of open field burning
represents 61% of the emissions of dioxin and furan into the air and it is followed
by the production of ferrous metals and no ferrous metals with 20% and the
incineration of residues with 11%.
DIGESA did a monitoring of air quality in the study zone of the Zapallal landfill in
2008; it was specifically in the Lomas the Carabayllo Human Settlement. The
monitoring stations were located within a radius of about one km in relation to the
landfill. This public institution concluded that there were different sources of
pollution in the zone, such as smelting enterprises, recycle of lead and aluminium,
accumulated solid residues, removal of land surrounding the quarries, recycle of
garbage and burning organic waste, animal husbandry (pork), landfill, unpaved
roads and hills without vegetation. The monitoring determined that the mean of
concentrations of particulate material by 24 hours was lower than 10 microns
PM10. The other three stations showed values higher than the National Standard
(of 150 µg/m3). This situation is an evidence of the air pollution in this zone and
the population is exposed to a great health risk.
The pollution produced by open field burning is permanent especially in the urban
zone where there are final disposal of solid waste or landfill. In addition, there are
some complementary activities that are developed near the landfill. They contribute
with emissions of toxic gases and pollutants as dioxin and furan. Therefore, it is
very important monitoring the air quality with frequency in order to take corrective
actions.
Objectives
To evaluate possible levels of exposure and risks in places where the polluted
residues with PCDD /F are stored or they are reused.
To collect detailed information about selected places, all of them are in order to
have a plan of sampling and identify the possible places of taking sample.
Methodology
To elaborate the present report, the first step was to get actualised information
about the emissions of dioxin and furan in the country. The information was taken
from institutions as DIGESA – Health Ministry, Carabayllo Municipality and
Callao – DISA. The information was collected and it was used as a technical
support of the present report.
In addition, the influence zone was visited by the researchers and they went around
all the area of the Zapallal landfill, moreover, the smelting enterprises and the
storage of segregated material were visited. It had been taken photos of the actual
situation of this place and it was done a meeting with the leaders of the base
organisations and the technician of the Municipality. Moreover, there was a
93
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
directly communication with the technicians of the sanitary area of the
International Jorge Chavez Airport.
I.
The Zapallal Landfill
Location of Zapallal Landfill
The Zapallal landfill is located in the right side of the Chillon River between the
Campana and Cabrera hills. It belongs to the Carabayllo district, province and
department of Lima. The landfill has a surface of 440 hectares of which 60% (260
ha) is used for landfill and the other 40% of this area is not appropriate for this
activity.
In the first part of the Project, an area of approximately 11 ha was included in
which it has been distributed the platforms of final disposal of urban waste.
Moreover, there were special areas for final disposal and/or confinement of
hospital and industrial residues. The estimated minimum lifetime is 30 years.
The ecosystem that is part of the Zapallal landfill is conformed by a sub tropical –
desert zone, clay soils, and it is extremely dry. There are not enough flora and
wildlife. There are arachnids and lizards. The flora is limited and is composed by
cactus. It happens because of different factors such as lack of water and extreme
aridity.
The pluvial precipitation is low and is limited to drizzle in winter; the monthly
rainfall goes to 0 a 6 mm. The monthly mean temperature goes to 17 to 25 ºC, the
94
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
mean annual relative humidity is 80 a 90% and the predominant direction of the
wind is for the southeast. The superficial and subterranean waters are absent.
Description of the storage places of waste and residues
LANDFILL
Approximately 600 Ton/day of solid waste that came from household activities is
disposed in this place, and almost 3 Ton/day of waste that comes from the health
centres is disposed there, too; therefore, there are special cells to confine this
dangerous waste by security. A significant number of poor people have been
established near the landfill. The population of this area faces up the typical
problems of the peri–urban zones such as the lack of water and the sanitation;
moreover, the incipient level of urban consolidation, the high incidence of
transmissible illnesses, and others problems.
GARBAGE DUMP
The garbage dump is almost 30 years. Therefore, it means that it is a high
infectious focus not only for the bacteria that are common in the solid waste, but
also for the process of burning of organic residues accumulated by long time. All
of these produce emissions of noxious gases that go into the air of the zone. The
garbage dump is surrounded by approximately 350 families. In addition, the
garbage dump has 300 thousand cubic meters of accumulated waste; actually there
are not mechanisms to eradicate it. It is important to mention that this garbage
dump is located to 1500 m from the Zapallal landfill. This garbage dump is not
used for final disposal these days.
ILLEGAL SMELTING ACTIVITIES
There are illegal smelting activities in
the zone, 10 of these places have been
identified, but nowadays only three are
working and they smelt metals such
aluminium and copper. Moreover,
asphalt is produced in an artisanal way,
batteries are recycled to get lead, and
some minerals are milled. Noils that are
produced by residues of hydrocarbon
and used oils that comes from other
places. All of these materials are using for generating energy. In addition, smelting
activities are doing in an artisanal way and they are using plastic materials for
incineration.
95
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
STORAGE OF SEGREGATED PRODUCTS
The recyclers take materials from the landfill and they stored them in these places.
This activity is not legal and it is prohibit doing inside the landfill. However, the
population located near the zone puts in dangerous situation its life and health
because they enter to collect the materials so that they can have the opportunity to
sell them in the market. The waste that has not been sold is burned in an open field
near closed yard. Children and teenage participate of this activity to burn waste.
It is important to mention that the municipal waste of the landfill that was burning
in open field has diminished according to the estimated number in 2001 when the
evaluation of dioxin was done. The management is better these days. Nowadays the
burning is been doing in the properties that are totally closed.
Types of identified residues
RESIDUES OF THE ILLEGAL AND ARTISANAL SMELTING ACTIVITIES
Ten smelting enterprises were identified in this place. However, nowadays only
three are working and are producing emissions of toxic substances into the air
because of the materials that are used to generate energy; these are based in
hydrocarbon residues (noils) (see Table 1). This residue is the most used in all of
the smelting activities that have been identified.
Pollutant
R=100
R=20
ROQ (ppm)
19320
19960
Sulfides (ppm)
206
215
Phenols (ppm)
231
244
Mercaptans (ppm)
26070
28960
Oils and fats (ppm)
13080
19200
The plastic segregated of the landfill and residues of oils are using to generate
energy too, a great quantity of ash is generated and accumulated in this process;
each owner has a piece of land that is closed in which the ash are stored.
96
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
DIGESA has identified and registered people that work in this activity and they are
mentioned in the followed table5:
Owner
Activity
Julio Cesar Salas Abanto
Produce chemical substances: Zinc sulphate and
copper sulphate
Edwar Sixto Berrospi
Production of blue based in asphalt
José Luis Silva
Milling of minerals
Ventura Meneses Fidencio
Smelting activity
Carmelo Fernández
Smelting activity
Abanto Justo Ponciano
non ferrous smelting activity
This activity has been identified in the industrial zone of Lomas de Carabayllo that
is near the landfill. The smelting activity and the incinerators permanently operate
and others operate temporally. The residues are stored in the same place for long
time (see photos).
Therefore, this zone could be vulnerable; the population of this zone claim to
authorities to close the landfill and to eradicate the illegal smelting activities. For
that reason some environmental studies have been done by DIGESA in order to
know about the concentration of particulate material or to do the evaluation of lead
level in the population.
The 100% of residues come from the same place where different materials are
burning. The used oil is the material more used for burning; acid noils are used,
too. The acid noils are based in hydrocarbon residues that come from the Conchan
refinery. Moreover, batteries are burning in order to recover lead. It is important to
mention that the technology that is used in this zone is artisanal and it does not
have any security measure.
____________________________
5 The Information was taken to the Act of inspection of Civil Defence that was done by February 2007,
and other information come from the fiscal Act to notify the presence of these smelting activities that
was done by June 2007.
97
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Storage of residues
The residues or ashes of the incinerators are stored in yards and these residues are
exposed to the wind. This is one of the reasons that the ashes are spread by the
wind to different communities near the influence zone, and it affects the health of
population. Layers of ashes were evidence when the researchers visited the study
zone. These layers of ash were located near the artisanal incinerators. The
management of these ashes has not been done yet and these materials are in a
process of accumulation. The material that is removed when the owner cleans the
local is disposed in the garbage dump and in other cases these materials go into the
nearest river in this case the Chillon River.
As it was mentioned the zone is too arid; there are not superficial and subterranean
waters. The wind is one of the factors that spread the ashes and dangerous
particles; it happens because wind is very strong and intense. People that are
working in the smelting activity are very distrustful; they do not allow people enter
into their locals especially if people are strangers in the zone. Therefore, the
supervisions have to be done by the competent authority.
The main activities in the area of influence of the landfill and waste identified
The photo shows in a general way
the main activities that are
carried out around the Zapallal
landfill. The landfill is
surrounded by human
settlement, artisanal smelting
enterprises, and non metallic
mining activities. The zone has
54 consolidated urban
allotments and it is possible
that 30 thousand people could be affected by environmental problems. The distance
that separates the landfill from the population is approximately 800 meters.
98
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Access to the landfill and the surrounding
To enter into the landfill in an official way it is necessary to have a permission of
the Relima enterprise. This enterprise has the concession of the area and it is the
responsible of integral management of the landfill. However, there is not
surveillance in the area; there is only surveillance in the main entrance for that
reason is possible that people enter without any problems by other zones of the
landfill. In addition, not all the area has been closed. The enterprise has fulfilled the
commitment to establish a life fence, and a barbed wire fence was established to
separate the landfill from the population located near. This situation gives
opportunity that informal segregators enter into the landfill without any problem.
If it is necessary to take samples of ashes, these have to be done in an official way
for that reason it is important to request permission to the competent authority such
as the Municipality, DIGESA, the prosecution or the organised community. As it
was mentioned, there is a serious problem related to the incineration. Therefore, it
is important to evaluate the pollutants (dioxin and furan). It is necessary the support
of the Carabayllo Municipality and the prosecution for entering into the smelting
places of the zone. It is recommended that official samples have to be collected in
front of witnesses so that the results can be recognised by all involved people.
It possible to say that there are not obstacles for taking samples, but it is necessary
to do a bureaucratic process. Moreover, it is necessary to have the presence of
competent authorities, and local community to get them. This study has allowed to
have actualised information. Moreover, it has been possible to evaluate the actual
situation, and it showed that is important to support the local authorities with
technical information about the emission problem of pollutants such as dioxin and
furan.
II. The Cockroach
landfill
This landfill was abandoned by
2001; none enterprise managed
this place. However, emissions of
toxic gases were eliminated into
the air and the burning appeared
in a spontaneous way. Therefore,
samples of ashes of this place
were taken to be analysed. There
was presence of dioxin in the
results; it was 0.19 ng-TEQ/g. This landfill is located in the left side of the Chillon
River. Nowadays, it has been closed and it does not have any activity of final
disposal of solid waste. Moreover, it is not accessible and it is surrounded for
human settlements that are very poor.
99
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
III. The Corpac
Incinerator
The Corpac incinerator was located in the
north of the international Jorge Chavez
airport. A; all of different kinds of waste
generated in the airport and the sanitary
products seized have been burned until
2001. The incinerator does not operate these
days. The process of incineration of waste
had to be undergone by 300 ºC. After this
process the ashes went to the landfill. For that reason, samples of this place were
taken to analyse; the results showed the presence of 0.36 ng -TEQ/g.
According to the health department of the airport and the DISA – Callao, the
process of incineration is not carried out in the Corpac incinerator. Nowadays, the
waste generated in the airport is previously recycled, then an autoclave is using to
sterilise and the residues are milling. Finally the waste of this process goes to the
landfill. Therefore, there are not ashes with this kind of process.
Acknowledgment
My thanks to Mr. Carlos Ascarza that belongs to the promoter group of the
association of the concentrated development plan of Lomas de Carabayllo and to
engineer Kathia Fuertes Espinoza of the Municipal Agency of Lomas de
Carabayllo for the supporting for the elaboration of this report.
References
PNI-COP PROJECT, 2006: National Inventory of the sources and emissions of
dioxin and furan, executed by CONAM, SENASA, DIGESA and sponsored by
GEF/PNUMA
CESIP, 2004: Child working in Lomas of Carabayllo: looking at the situation of
children working in the recycling of garbage, sponsored by Terre des Hommes Netherlands.
Health Ministry – DIGESA, 2008. Report Nº 001551-2008/DEPAAPCCA/DIGESA: Monitoring air quality in the human settlement of Lomas de
Carabayllo.
Fiscal Act, 2007: Authorization for the Carabayllo Municipality to closed and to
eradicate the smelting activities, according to the Art 49 of the LOM No 27972 and
the material law.
100
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Civil Defence, 2007: Visiting Act for inspection of Civil Defence to different
illegal places dedicated to smelt and recycle materials.
Gomero L y Velásquez H, 2001: Dioxin evaluation in samples of ashes of
incinerators and landfills of urban waste. Executed by RAAA and sponsored by
Japan Offspring Fund (JOF)
Carrasco M., Ore J.: Treatment of acid noils produced in the manufacture of
lubricating base type LCT at the Talara refinery.
101
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Appendix B
Map of Zapallal and sampling points
102
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
103
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
104
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Appendix C
Photos from the field study at Zapallal, Peru
(taken by Viktor Sjöblom, SLU, Umeå, Sweden)
Picture 1. Welcome to Zapallal.
105
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Picture 2. Arid climate at Zapallal, it is windy and lots of dust in the air.
Picture 3. Within the waste site, there are at least 100 industrial allotments. Most of the
activities involve recycling. Other activities are production of chemicals and zinc powder and
burning. Burning of waste took place at one of the four allotments that were visited during
the field sam-pling.
106
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Picture 4. The area is quite large, and there were even official and non official burning of
waste outside the area. The main area (the hot spot) was ~1 km2, even though burning did
not take place everywhere.
Picture 5. Recycling of copper from copper cable. Ash sample 1.
107
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Picture 6. This road started where the industrial allotments ended. Soil samples 1-3 and
plant samples 1-4 were taken along the road.
Picture 7. This part of a small village is situated 1.5 km east of Zapallal. Soil and plant
samples 5.
108
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Picture 8. This area is situated 4 km east of Zapallal. There are some agricultural activities
here (cultivation of plants and vegetables) Soil and plant samples 6.
Picture 9. Cable burning for recycling of cupper.
109
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Picture 10. Furnace for cable burning.
110
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Picture 11. Ash from cable burning. Ash sample 1.
Picture 12. Area for burning of plastic film for recycling of cellulose. Ash sample 2. People are
living here, and the area with the industrial allotments begins in the background. Egg sample 3
was taken downside this place.
111
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Picture 13. Ash from burning of lead batteries. Ash sample 3.
112
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Picture 14. Sediment sampling in Chillon river, 2-3 km south of Zapallal. Sediment 1. The
wet season is between October and April, but water is not necessarily flowing in the River
the whole rainy season. During the visit it was completely dry.
113
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Picture 15. Daily disposal of waste in Chillon River. During the visit we saw traces from dumping
of ash.
Picture 16. Sediment sampling at the reference site at Trapiche, some 20-30 km upstream
sediment sample 1. Sediment sample 2.
114
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Picture 17. Area with free range chickens. Egg sample 1.
115
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Picture 18. Area with free range ducks. Egg sample 2.
Picture 19. Aloe Vera, plant sample 1:1,1:2 and 1:4.
116
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Picture 20. Plant sample 2.
117
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Picture 21. Plant sample 3.
118
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Picture 22. Plant sample 4.
Picture 23. Site of reference soil sample Soil 7.
119
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Picture 24. Site of reference soil sample Soil 7.
Picture 25. Site of reference sample Soil 9
120
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Appendix D
Photos from field study at the incinerator plant in Phuket, Thailand
(taken by Lars Lundmark, Umeå University, Sweden)
Picture 1. Ash sampling from open area.
Picture 2. Ash deposit at pond.
121
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Picture 3. Bottom ash sampling.
Picture 4. Untreated waste deposit.
122
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Picture 5. Water sampling.
Picture 6. Waste water sampling (out to channel).
Picture 7. Pond outside plant.
123
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Picture 8. Sediment ash store.
Picture 9. Grey ash without graphite injection.
Picture 10. Some part of the ash store was covered by a thick layer of some
plastic material.
124
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Picture 11. Sediment from pond (fisherman).
Picture 12. Fisherman on the other side.
Picture 13. Buying fish samples.
125
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Picture 14. Reference sample (Paton Beach town).
Picture 15. Soil sample (Reference).
126
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
References
Alcock, R. E., Sweetman, A. J., Anderson, D. R., Fisher, R., Jennings, R. A., and
Jones, K. C, 2002. Using PCDD/F congener patterns to determine the source of
elevated TEQ concentrations in cow’s milk: A case study. Chemosphere,
46:383-391
Arisawa, K., Uemura, H., Hiyoshi, M., Satoh, H., Sumiyoshi, Y., Morinaga, K.,
Kodama, K., Suzuki, T. I., Nagai, M., and Suzuki, T., 2008. Dietary intake of
PCDDs/PCDFs and coplanar PCBs among the Japanese population estimated by
duplicate portion analysis: A low proportion of adults exceed the tolerable daily
intake. Environmental Research, 108:252-259
Aristizabal, B., Cobo, M., Hoyos, A., de Correa, C. M., Abalos, M., Martinez, K.,
Abad, E., and Rivera, J., 2008. Baseline levels of dioxin and furan emissions from
waste thermal treatment in Colombia. Chemosphere, 73:S171-S175
Asari, M., Takatsuki, H., Yamazaki, M., Azuma, T., Takigami, H., and Sakai, S. I.,
2004. Waste wood recycling as animal bedding and development of bio-monitoring
tool using the CALUX assay. Environment International, 30:639-649
Asmus, C. I. R. F., Alonzo, H. G. A., Palacios, M., da Silva, A. P., Filhote, M. I. D.,
Buosi, D., and Camara, V. D., 2008. Assessment of human health risk from
organochlorine pesticide residues in Cidade dos Meninos, Duque de Caxias, Rio de
Janeiro, Bra-zil. Cadernos de Saude Publica, 24:755-766
Baars, A. J., Bakker, M. I., Baumann, R. A., Boon, P. E., Freijer, J. I.,
Hoogenboom, L. A. P., Hoogerbrugge, R., van Klaveren, J. D., Liem, A. K. D.,
Traag, W. A., and de Vries, J., 2004. Dioxins, dioxin-like PCBs and non-dioxinlike PCBs in foodstuffs: occurrence and dietary intake in The Netherlands.
Toxicology Letters, 151:51-61
Bergkvist, C., Oberg, M., Appelgren, M., Becker, W., Aune, M., Ankarberg, E. H.,
Berglund, M., and Hakansson, H., 2008. Exposure to dioxin-like pollutants via
different food commodities in Swedish children and young adults. Food and
Chemical Toxicology, 46:3360-3367
Bernard, A., Broeckaert, F., De Poorter, G., De Cock, A., Hermans, C., Saegerman,
C., and Houins, G., 2002. The Belgian PCB/dioxin incident: Analysis of the food
chain contamination and health risk evaluation. Environmental Research, 88:1-18
127
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Bilau, M., Sioen, I., Matthys, C., De Vocht, A., Goemans, G., Belpaire, C.,
Willems, J. L., and De Henauw, S., 2007. Probabilistic approach to polychlorinated
biphenyl (PCB) exposure through eel consumption in recreational fishermen vs. the
general population. Food Additives and Contaminants, 24:1386-1393
BIPRO, 2005. Study to facilitate the implementation of certain waste related
provisions of the Regulation on Persistent Organic Pollutants (POPs).
ENV.A.2/ETU/2004/0044 Final report August 2005. European Comission
Birch, G. F., Harrington, C., Symons, R. K., and Hunt, J. W., 2007. The source and
distribution of polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofurans
in sedi-ments of Port Jackson, Australia. Marine Pollution Bulletin 54:295-308
Bopp, R. F., Gross, M. L., Tong, H., Simpson, H. J., Monson, S. J., Deck, B. L.,
and Moser, F. C., 1991. A Major Incident of Dioxin Contamination - Sediments of
New-Jersey Estuaries. Environmental Science & Technology, 25:951-956
Braga, A. M. C. B., Krauss, T., dos Santos, C. R. R., and de Souza, P. M., 2002.
PCDD/F-contamination in a hexachlorocyclohexane waste site in Rio de Janeiro,
Brazil. Chemosphere, 46:1329-1333
Brambilla, G., Fochi, I., De Filippis, S. P., Iacovella, N., and di Domenico, A.,
2009. Pentachlorophenol, polychlorodibenzodioxin and polychlorodibenzofuran in
eggs from hens exposed to contaminated wood shavings. Food Additives and
Contaminants Part A-Chemistry Analysis Control Exposure & Risk Assessment,
26:258-264
Bruckmeier, B. F. A., Juttner, I., Schramm, K. W., Winkler, R., Steinberg, C. E. W.,
and Kettrup, A., 1997. PCBs and PCDD/Fs in lake sediments of Grosser Arbersee,
Bavarian Forest, south Germany. Environmental pollution, 95:19-25
Budinsky, R. A., Rowlands, J. C., Casteel, S., Fent, G., Cushing, C. A., Newsted,
J., Giesy, J. P., Ruby, M. V., and Aylward, L. L., 2008. A pilot study of oral
bioavailability of dioxins and furans from contaminated soils: Impact of differential
hepatic enzyme activity and species differences. Chemosphere, 70:1774-1786
Castro-Jimenez, J., Mariani, G., Eisenreich, S. J., Christoph, E. H., Hanke, G.,
Canuti, E., Skejo, H., and Umlauf, G., 2008. Atmospheric input of POPs into Lake
Maggiore (Northern Italy): PCDD/F and dioxin-like PCB profiles and fluxes in the
atmosphere and aquatic system. Chemosphere, 73:S122-S130
128
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Cerna, M., Kratenova, J., Zejglicova, K., Brabec, M., Maly, M., Smid, J., Crhova, S.,
Grabic, R., and Volf, J., 2007. Levels of PCDDs, PCDFs, and PCBs in the blood of
the non-occupationally exposed residents living in the vicinity of a chemical plant in
the Czech Republic. Chemosphere, 67:S238-S246
Chan, J. K. Y., Xing, G. H., Xu, Y., Liang, Y., Chen, L. X., Wu, S. C.,
Wong, C. K. C., Leung, C. K. M., and Wong, M. H., 2007. Body loadings and
health risk assessment of polychlorinated dibenzo-p-dioxins and dibenzofurans at
an intensive electronic waste recycling site in China. Environmental Science &
Technology, 41:7668-7674
Chen, H. L., Lee, C. C., Liao, P. C., Guo, Y. L., Chen, C. H., and Su, H. J., 2003.
Associations between dietary intake and serum polychlorinated dibenzo-p-dioxin
and dibenzofuran (PCDD/F) levels in Taiwanese. Environmental Research,
91:172-178
Chen, H. L., Su, H. J., Hsu, J. F., Liao, P. C., and Lee, C. C., 2008. High variation
of PCDDs, PCDFs, and dioxin-like PCBs ratio in cooked food from the first total
diet survey in Taiwan. Chemosphere, 70:673-681
Chen, H.-L., Su, H.-J., and Lee, C.-C., 2006a. Patterns of serum PCDD/Fs affected
by vegetarian regime and consumption of local food for residents living near
municipal waste incinerators from Taiwan. Environment International, 32: 650-655
Chen, J. W., Wang, S. L., Yu, H. Y., Liao, P. C., and Lee, C. C., 2006b. Body
burden of dioxins and dioxin-like polychlorinated biphenyls in pregnant women
residing in a contaminated area. Chemosphere, 65:1667-1677
Chi, K. H., Chang, S. H., and Chang, M. B., 2006. Characteristics of PCDD/F
distributions in vapor and solid phases and emissions from the Waelz process.
Environmental Science & Technology, 40:1770-1775
Chi, K. H., Chang, S. H., and Chang, M. B., 2008. Reduction of dioxin-like
compound emissions from a Waelz plant with adsorbent injection and a dual
baghouse filter system. Environmental Science & Technology 42: 2111-2117
Costera, A., Feidt, C., Marchand, P., Le Bizec, B., and Rychen, G., 2006. PCDD/F
and PCB transfer to milk in goats exposed to a long-term intake of contaminated
hay. Chemosphere, 64:650-657
Cuadra, S. N., Linderholm, L., Athanasiadou, M., and Jakobsson, K., 2006.
Persistent or-ganochlorine pollutants in children working at a waste-disposal site
and in young females with high fish consumption in Managua, Nicaragua. AMBIO
35:109-116
129
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Diletti, G., Ceci, R., Conte, A.-M., De Benedictis, A., Migliorati, G., and
Scortichini, G., 2008. Contamination from dioxins in Italy: Source identification
and intervention strategies. Eds. Mehmetli, E. and Koumanova, B: The Fate of
Persistent Organic Pollutants in the Environment, 301-314 (Springer)
Diletti, G., Ceci, R., De Massis, M. R., Scortichini, G., and Migliorati, G., 2005.
A case of eggs contamination by PCDD/Fs in Italy:analytical levels and
contamination source identification. Organohalogen Compounds, 67:1460-1461
Donato, F., Magoni, M., BergonZi, R., Scarcella, C., Indelicato, A., Carasi, S., and
Apostoli, P., 2006. Exposure to polychlorinated biphenyls in residents near a
chemical factory in Italy: The food chain as main source of contamination.
Chemosphere, 64:1562-1572
Engwall, M. and Hjelm, K., 2000. Uptake of dioxin-like compounds from sewage
sludge into various plant species - assessment of levels using a sensitive bioassay.
Chemosphere, 40:1189-1195
Esposito, M., Cavallo, S., Serpe, F. P., D'ambrosio, R., Gallo, P., Colarusso, G.,
Pellicano, R., Baldi, L., Guarino, A., and Serpe, L., 2009. Levels and congener
profiles of poly-chlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and
dioxin-like polychlorinated biphenyls in cow's milk collected in Campania, Italy.
Chemos-phere 77:1212-1216
European Commission, 1999. Compilation of EU dioxin exposure and health data.
AEAT/EEQC/0016, European Comission
European Commission, 2000. Opinion of the Scientific Comittee on Animal
Nutrition: Dioxin contamination of feedingstuffs and their contribution to the
contamination of food of animal origin. European Comission
European Commission, 2006. Commission regulation setting maximum levels for
certain contaminants in foodstuffs. EC No 1881/2006
Fattore, E., Fanelli, R., Turrini, A., and di Domenico, A., 2006. Current dietary
exposure to polychlorodibenzo-p-dioxins, polychlorodibenzofurans, and dioxinlike polychlorobiphenyls in Italy. Molecular Nutrition & Food Research, 50:915921
Fernandez, M. A., Gomara, B., Bordajandi, L. R., Herrero, L., Abad, E., Abalos, M.,
Rivera, J., and Gonzalez, M. J., 2004. Dietary intakes of polychlorinated dibenzo-pdioxins, dibenzofurans and dioxin-like polychlorinated biphenyls in Spain. Food
Additives and Contaminants 21:983-991
130
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Ferreira, C., Ribeiro, A., and Ottosen, L., 2003. Possible applications for municipal
solid waste fly ash. Journal of Hazardous Materials, 96:201-216
Fierens, S., Mairesse, H., Hermans, C., Bernard, A., Eppe, G., Focant, J. F., and
De Pauw, E., 2003. Dioxin accumulation in residents around incinerators. Journal
of Toxicology and Environmental Health-Part A, 66:1287-1293
Fries, G. F., Feil, V. J., Zaylskie, R. G., Bialek, K. M., and Rice, C. P., 2002.
Treated wood in livestock facilities: relationships among residues of
pentachlorophenol, dioxins and furans in wood and beef. Environmental pollution,
116:301-307
Fürst, P., 2009. Plenary lecture Dioxin Conference 2009
Goldman, L. R., Harnly, M., Flattery, J., Patterson, D. G., and Needham, L. J.,
2000. Serum polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans
among people eating contaminated home-produced eggs and beef. Environmental
Health Perspectives, 108:13-19
Gullett, B. K., Linak, W. P., Touati, A., Wasson, S. J., Gatica, S., and King, C. J.,
2007. Characterization of air emissions and residual ash from open burning of
electronic wastes during simulated rudimentary recycling operations. Journal of
Material Cycles and Waste Management, 9:69-79
Harnly, M. E., Petreas, M. X., Flattery, J., and Goldman, L. R., 2000.
Polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran contamination
in soil and home-produced chicken eggs near pentachlorophenol sources.
Environmental Science & Technology, 34:1143-1149
Harris, S. A. and Jones, J. L., 2008. Fish consumption and PCB-associated health
risks in recreational fishermen on the James River, Virginia. Environmental
Research, 107:254-263
Holt, E., Weber, R., W., Stevenson, G., and Gaus, C., 2010. Polychlorinated
dibenzo-p-dioxin and dibenzofuran (PCDD/F) impurities in pesticides: a neglected
source of contemporary relevance. Environmental Science and Technology, In
Press
Hoogenboom, L. A. P., Kan, C. A., Zeilmaker, M. J., Van Eijkeren, J., and
Traag, W. A., 2006. Carry-over of dioxins and PCBs from feed and soil to eggs at
low contamination levels - influence of mycotoxin binders on the carry-over from
feed to eggs. Food Additives and Contaminants, 23:518-527
131
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Hoogenboom, R., Heres, L., Urlings, B., Herbes, R., and Traag, W., 2009.
Increased levels of dioxins in Irish pig meat; the Dutch connection. Organohalogen
Compounds, 71:2197-2201
Hoogenboom, Ron, Bovee, Toine, Portier, Liza, Bor, Gerrit, van der Weg, Guido,
Onstenk, Constant, and Traag, Wim, 2004. The German bakery waste incident; use
of a combined approach of screening and confirmation for dioxins in feed and
food. Talanta, 63:1249-1253
Hsu, M. S., Hsu, K. Y., Wang, S. M., Chou, U., Chen, S. Y., Huang, N. C.,
Liao, C. Y., Yu, T. P., and Ling, Y. C., 2007. A total diet study to estimate
PCDD/Fs and dioxin-like PCBs intake from food in Taiwan. Chemosphere,
67:S65-S70
Hülster, A. and Marschner, H., 1993. Transfer of PCDD/PCDF from contaminated
soils to food and crop plants. Chemosphere, 27:439-446
Huwe, J. K., Davison, K., Feil, V. J., Larsen, G., Lorentzsen, M., Zaylskie, R., and
Tiernan, T. O., 2004. Levels of polychlorinated dibenzo-p-dioxins and
dibenzofurans in cattle raised at agricultural research facilities across the USA and
the influence of pentachlorophenol-treated wood. Food Additives and
Contaminants, 21:182-194
Huwe, J. K. and Smith, D. J., 2005. Laboratory and on-fram studies on the
bioaccumulation and elimination of dioxins from a contaminated mineral
supplement fed to dairy cows. Journal of Agriculture and food chemsitry,
53:2362-2370
IPEN, 2005. The egg report: contamination of chicken eggs from 17 countries by
dioxins, PCBs and hexachlorobenzene. The International POPs Elimination
Network
Isosaari, P., Kankaanpaa, H., Mattila, J., Kiviranta, H., Verta, M., Salo, S., and
Vartiainen, T., 2002. Spatial distribution and temporal accumulation of
polychlorinated dibenzo-p-dioxins, dihenzofurans, and Biphenyls in the Gulf of
Finland. Environmental Science & Technology, 36:2560-2565
Isosaari, P., Kohonen, T., Kiviranta, H., Tuomisto, J., and Vartianinen, T., 2000.
Assessment of levels, distribution, and risks of polychlorinated dibenzo-p-dioxins
and dibenzofurans in the vicinity of a vinyl chloride monomer production plant.
Environmental Science & Technology, 34:2684-2689
132
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Kao, W. Y., Ma, H. W., Wang, L. C., and Chang-Chien, G. P., 2007. Site-specific
health risk assessment of dioxins and furans in an industrial region with numerous
emission sources. Journal of Hazardous Materials, 145:471-481
Kiviranta, H., Ovaskainen, M. A. L., and Vartiainen, T., 2004. Market basket study
on dietary intake of PCDD/Fs, PCBs, and PBDEs in Finland. Environment
International, 30:923-932
Kiviranta, H., Vartiainen, T., and Tuomisto, J., 2002. Polychlorinated dibenzo-pdioxins, dibenzofurans, and biphenyls in fishermen in Finland. Environmental
Health Perspectives, 110:355-361
Knutzen, J., Bjerkeng, B., Naes, K., and Schlabach, M., 2003. Polychlorinated
dibenzofurans/dibenzo-p-dioxins (PCDF/PCDDs) and other dioxin-like substances
in marine organisms from the Grenland fjords, S. Norway, 1975-2001: present
contamination levels, trends and species specific accumulation of PCDF/PCDD
congeners. Chemosphere, 52:745-760
Kunisue, T., Watanabe, M., Iwata, H., Subramanian, A., Monirith, I., Minh, T. B.,
Baburajendran, R., Tana, T. S., Viet, P. H., Prudente, M., and Tanabe, S., 2004.
Dioxins and related compounds in human breast milk collected around open
dumping sites in Asian developing countries: Bovine milk as a potential source.
Archives of Environmental Contamination and Toxicology, 47:414-426
Lake, I. R., Foxall, C. D., Lovett, A. A., Fernandes, A., Dowding, A., White, S.,
and Rose, M., 2005. Effects of river flooding on PCDD/F and PCB levels in cows'
milk, soil, and grass. Environmental Science & Technology, 39:9033-9038
Lee, C. C., Guo, Y. L., Kuei, C. H., Chang, H. Y., Hsu, J. F., Wang, S. T., and
Liao, P. C., 2006a. Human PCDD/PCDF levels near a pentachlorophenol
contamination site in Tainan, Taiwan. Chemosphere, 65:436-448
Lee, C. C., Lin, W. T., Liao, P. C., Su, H. J., and Chen, H. L., 2006b. High average
daily intake of PCDD/Fs and serum levels in residents living near a deserted
factory producing pentachlorophenol (PCP) in Taiwan: Influence of contaminated
fish consumption. Environmental pollution, 141:381-386
Lee, K. T., Lee, J. H., Lee, J. S., Park, K. H., Kim, S. K., Shim, W. J., Hong, S. H.,
Im, U. H., Giesy, J. P., and Oh, J. R., 2007. Human exposure to dioxin-like
compounds in fish and shellfish consumed in south Korea. Human and Ecological
Risk Assessment, 13:223-235
Lee, W. J., Shih, S. I., Li, H. W., Lin, L. F., Yu, K. M., Lu, K., Wang, L. C.,
Chang-Chien, G. P., Fang, K., and Lin, M., 2009. Assessment of polychlorinated
133
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
dibenzo-p-dioxins and dibenzofurans contribution from different media to
surrounding duck farms. Journal of Hazardous Materials 163:1185-1193
Leung, A. O. W., Luksemburg, W. J., Wong, A. S., and Wong, M. H., 2007.
Spatial distribution of polybrominated diphenyl ethers and polychlorinated
dibenzo-p-dioxins and dibenzofurans in soil and combusted residue at Guiyu, an
electronic waste recy-cling site in southeast China. Environmental Science &
Technology 41:2730-2737
Li, J. G., Wu, Y. N., Zhang, L., and Zhao, Y. F., 2007. Dietary intake of
polychlorinated dioxins, furans and dioxin-like polychlorinated biphenyls from
foods of animal origin in China. Food Additives and Contaminants, 24:186-193
Linderholm, L., Athanasiadou, M., Norrgren, H., Bergman, Å., and Jakobsson, K.,
2009. Assessment of persistent organic pollutants (POPs) in serum from GuineaBissau, Western Africa - A time trend study. Organohalogen Compounds,
71:2041-2043
Lindström, G., Henriksson, S., Hagberg, J., Björnfoth, H., and van Bavel, B., 2005.
Uptake of PCDDs, PCDFs an non-ortho PCBs in sheep from PCP contaminated
sawmill soil. Organohalogen Compounds, 67:1387-1389
Llerena, J. J., Abad, E., Caixach, J., and Rivera, J., 2003. An episode of dioxin
contamination in feedingstuff: the choline chloride case. Chemosphere, 53:679-683
Loutfy, N., Fuerhacker, M., Tundo, P., Raccanelli, S., El Dien, A. G., and
Ahmed, M. T., 2006. Dietary intake of dioxins and dioxin-like PCBs, due to the
consumption of dairy products, fish/seafood and meat from Ismailia city, Egypt.
Science of the Total Environment, 370:1-8
Luksemburg, W. J., Mitzel, R. S., Peterson, R. G., Hedin, J. M., Maier, M. M.,
Schuld, M., Zhou, H. D., and Wong, A. S., 2002. Polychlorinated dibenzodioxins
and dibenzofurans (PCDDs/PCDFs) levels in environmental and human hair
samples around an electronic waste processing site in Guiyu, Guangdong Province,
China. Organohalogen Compounds, 55:347-349
Ma, J., Kannan, K., Cheng, J., Hori, Y., Wu, Q., and Wang, W., 2008.
Concentrations, Profiles, And Estimated Human Exposures for Polychlorinated
Dibenzo-p-Dioxins and Dibenzofurans from Electronic Waste Recycling Facilities
and a Chemical Industrial Complex in Eastern China. Environmental Science &
Technology, 42:8252-8259
Malisch, R., 2000. Increase of the PCDD/F-contamination of milk, butter and meat
samples by use of contaminated citrus pulp. Chemosphere, 40:1041-1053
134
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Malve, O., Salo, S., Verta, M., and Forsius, J., 2003. Modeling the transport of
PCDD/F compounds in a contaminated river and the possible influence of
restoration dredging on calculated fluxes. Environmental Science & Technology,
37:3413-3421
Mari, M., Nadal, M., Schuhmacher, M., and Domingo, J. L., 2009. Exposure to
heavy metals and PCDD/Fs by the population living in the vicinity of a hazardous
waste landfill in Catalonia, Spain: Health risk assessment. Environment
International 35: 1034-1039
Martinez, M. A., Sanz, P., Ruiz, M. L., Fabrellas, B., Abad, E., and Rivera, J.,
2008. Evaluation of the Spanish hot dip galvanising sector as a source of
polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans.
Chemosphere, 71:1127-1134
Marvin, C., Williams, D., Kuntz, K., Klawunn, P., Backus, S., Kolic, T., Lucaciu, C.,
MacPherson, K., and Reiner, E., 2007. Temporal trends in polychlorinated dibenzop-dioxins and dibenzofurans, dioxin-like PCBs, and polybrominated diphenyl ethers
in Niagara river suspended sediments. Chemosphere, 67:1808-1815
Masunaga, S., Takasuga, T., and Nakanishi, J., 2001. Dioxin and dioxin-like PCB
impurities in some Japanese agrochemical formulations. Chemosphere, 44:873-885
Mato, Y., Suzuki, N., Katatani, N., Kadokami, K., Nakano, T., Nakayama, S.,
Sekii, H., Komoto, S., Miyake, S., and Morita, M., 2007. Human intake of PCDDs,
PCDFs, and dioxin like PCBs in Japan, 2001 and 2002. Chemosphere,
67:S247-S255
Matscheko, N., Tysklind, M., de Wit, C., Bergek, S., Andersson, R., and Sellstrom,
U., 2002. Application of sewage sludge to arable land-soil concentrations of
polybrominated diphenyl ethers and polychorinated dibenzo-p-dioxins,
dibenzofurans, and biphenyls, and their accumulation in earthworms.
Environmental Toxicology and Chemistry, 21:2515-2525
Mbuligwe, S. E. and Kaseva, M. E., 2006. Assessment of industrial solid waste
management and resource recovery practices in Tanzania. Resources Conservation
and Recycling, 47:260-276
McLachlan, M., Thorna, H., Reissinger, M., and Hutzinger, O., 1990. PCDD/F in
an agricultural food chain. Part 1: PCDD/F mass balance of lactating cow.
Chemosphere, 20:1013-1020
135
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Micheletti, C., Critto, A., and Marcomini, A., 2007. Assessment of ecological risk
from bioaccumulation of PCDD/Fs and dioxin-like PCBs in a coastal lagoon.
Environment International, 33:45-55
Minh, N. H., Minh, T. B., Kajiwara, N., Kunisue, T., Subramanian, A., Iwata, H.,
Tana, T. S., Baburajendran, R., Karuppiah, S., Viet, P. H., Tuyen, B. C., and
Tanabe, S., 2006. Contamination by persistent organic pollutants in dumping sites
of Asian developing countries: Implication of emerging pollution sources. Archives
of Environmental Contamination and Toxicology, 50:474-481
Minh, N. H., Minh, T. B., Watanabe, M., Kunisue, T., Monirith, I., Tanabe, S.,
Sakai, S., Subramanian, A., Sasikumar, K., Viet, P. H., Tuyen, B. C., Tana, T. S.,
and Prudente, M. S., 2003. Open dumping site in Asian developing countries:
A potential source of polychlorinated dibenzo-p-dioxins and polychlorinated
dibenzofurans. Environmental Science & Technology, 37:1493-1502
Moon, H.-B. and Choi, H.-G., 2009. Human exposure to PCDDs, PCDFs and
dioxin-like PCBs associated with seafood consumption in Korea from 2005 to
2007. Environment International 35: 279-284
Morinello, E. J., Warmerdam, J. M., and Finley, B. L., 2006. The oral
bioavailability of polychlorinated dibenzo-p-dioxins/dibenzofurans in soil: Review
of the state of art of science. Organohalogen Compounds, 68:1581-1584
Muller, J. F., Gaus, C., Prange, J. A., Papke, O., Poon, K. F., Lam, M. H. W., and
Lam, P. K. S., 2002. Polychlorinated dibenzo-p-dioxins and polychlorinated
dibenzofurans in sediments from Hong Kong. Marine Pollution Bulletin
45:372-378
Nakagawa, R., Hori, T., Tobiishi, K., Iida, T., Tsutsumi, T., Sasaki, K., and
Toyoda, M., 2002. Levels and tissue-dependent distribution of dioxin in Japanese
domestic leafy vegetables - from the 1999 national investigation. Chemosphere,
48:247-256
SEPA, 2009. Betydelse av pentaklorfenolbehandlat trä för spridning av dioxin i
miljön. Rapport 5911, The Swedish Environmental Protection Agency (In
Swedish)
NFA, 2003. Riksmaten Barn 2003. Livsmedels och näringsintag bland barn i
Sverige. The Na-tional Food Administation (In Swedish)
NFA, 2002. Riksmaten 1997-1998. Kostvanor och Näringsintag i Sverige. The
National Food Administration (In Swedish)
136
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Oehme, M. and Muller, M. D., 1995. Levels and Congener Patterns of
Polychlorinated Dibenzo-P-Dioxins and Dibenzofurans in Solid Residues from
Wood-Fired Boilers - Influence of Combustion Conditions and Fuel Type.
Chemosphere, 30:1527-1539
Omran, A. and Gavrilescu, M., 2008. Municipal Solid Waste Management in
Developing Countries: A Perspective on Vietnam. Environmental Engineering and
Management Journal, 7:469-478
Pasquini, M. W., 2006. The use of town refuse ash in urban agriculture around Jos,
Nigeria: health and environmental risks. Science of the Total Environment,
354:43-59
Pirard, C., Eppe, G., Massart, A. C., Fierens, S., De Pauw, E., and Focant, J. F.,
2005. Environmental and human impact of an old-timer incinerator in terms of
dioxin and PCB level: A case study. Environmental Science & Technology,
39:4721-4728
Pless-Mulloli, T., Edwards, R., Howel, D., Wood, R., Paepke, O., and Herrmann, T.,
2005. Does long term residency near industry have an impact on the body burden of
polychlorinated dibenzo-p-dioxins, furans, and polychlorinated biphenyls in older
women? Occupational and Environmental Medicine, 62:895-901
Pless-Mulloli, T., Edwards, R., Päpke, O., and Schilling, B., 2001. Full technical
report PCDD/F and heavy metals in soil and egg samples from Newcastle
allotments: Assessment of the role of ash from Byker incinerator. University of
Newcastle
Prange, J. A., Gaus, C., Papke, O., and Muller, J. F., 2002. Investigations into the
PCDD con-tamination of topsoil, river sediments and kaolinite clay in Queensland,
Australia. Chemosphere 46:1335-1342
Pussemier, L., Mohimont, L., Huyghebaert, A., and Goeyens, L., 2004. Enhanced
levels of dioxins in eggs from free range hens; a fast evaluation approach. Talanta,
63:1273-1276
Rogowski, D. L. and Yake, W., 2005. Typical dioxin concentrations in agriculture
soils of Wash-ington state and potential sources. Environmental Science &
Technology 39:5170-5176
Ruby, M. V., Fehling, K. A., Paustenbach, D. J., Landenberger, B. D., and
Holsapple, M. P., 2002. Oral bioaccessibility of dioxins/furans at low
concentrations (50-350 ppt toxicity equivalent) in soil. Environmental Science &
Technology, 36:4905-4911
137
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Ryan, J. J., Dewailly, E., Gilman, A., Laliberte, C., Ayotte, P., and Rodrigue, J.,
1997. Dioxin-like compounds in fishing people from the Lower North Shore of the
St. Lawrence River, Quebec, Canada. Archives of Environmental Health,
52:309-316
Sakurai, T., Weber, R., Ueno, S., Nishino, J., and Tanaka, M., 2003. Relevance of
coplanar PCBs for TEQ emission of fluidized bed incineration and impact of
emission con-trol devices. Chemosphere 53:619-625
Santillo, D., Fernandes, A., Stringer, R., Alcock, R., Rose, M., White, S., Jones, K.,
and Johnston, P., 2003. Butter as an indicator of regional persistent organic
pollutant contamination: further development of the approach using
polychlorinated dioxins and furans (PCDD/Fs), and dioxin-like polychlorinated
biphenyls (PCBs). Food Additives and Contaminants, 20:281-290
Santos, E., Silva, R. D., Barretto, H. H. C., Inomata, O. N. K., Lemes, V. R. R.,
Kussumi, T. A., and Rocha, S. O. B., 2003. Levels of exposure to organochlorine
pesticides in open-air dump dwellers. Revista de Saude Publica 37:515-522
SCF, 2000. Opinion of the SCF on the risk assessment of dioxins and dioxin-like
PCBs in food. SCF/CS/CNTM/DIOXIN/8 Final, European Comission, Scientific
Committee on Food
Schecter, A., Cramer, P., Boggess, K., Stanley, J., Papke, O., Olson, J., Silver, A.,
and Schmitz, M., 2001. Intake of dioxins and related compounds from food in the
US population. Journal of Toxicology and Environmental Health-Part A, 63:1-18
Schmid, P., Gujer, E., Zennegg, M., and Studer, C., 2003. Temporal and local
trends of PCDD/F levels in cow´s milk in Switzerland. Chemosphere 53: 129-136
Schoeters, G. and Hoogenboom, R., 2006. Contamination of free-range chicken
eggs with dioxins and dioxin-like polychlorinated biphenyls. Molecular Nutrition
& Food Research, 50: 908-914
Schuler, F., Schmid, P., and Schlatter, C., 1997. The transfer of polychlorinated
dibenzo-p-dioxins and dibenzofurans from soil into eggs of foraging chicken.
Chemosphere, 34:711-718
Schulz, A. J., Wiesmuller, T., Appuhn, H., Stehr, D., Severin, K., Landmann, D.,
and Kamphues, J., 2005. Dioxin concentration in milk and tissues of cows and
sheep related to feed and soil contamination. Journal of Animal Physiology and
Animal Nutrition, 89:72-78
138
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Sepúlveda, A., Schluep, M., Renaud, F. G., Streicher, M., Kuehr, R., Hagelüken,
C., and Gerecke, A. C., 2009. A review of the environmental fate and effects of
hazardous substances released from electrical and electronic equipments during
recycling: Examples from China and India. Environmental Impact Assessment
Review, In Press
Shen, L., Gewurtz, S. B., Reiner, E. J., MacPherson, K. A., Kolic, T. M., Helm, P. A.,
Brindle, I. D., and Marvin, C. H., 2008. Patterns and sources of polychlorinated
dibenzo-p-dioxins and polychlorinated dibenzofurans in surficial sediments of Lakes
Erie and Ontario. Environmental pollution, 156:515-525
Shen, L., Gewurtz, S. B., Reiner, E. J., MacPherson, K. A., Kolic, T. M., Khurana, V.,
Helm, P. A., Howell, E. T., Burniston, D. A., Brindle, I. D., and Marvin, C. H., 2009.
Occurrence and sources of polychlorinated dibenzo-p-dioxins, dibenzofurans and
dioxin-like polychlorinated biphenyls in surficial sediments of Lakes Superior and
Huron. Environmental pollution, 157:1210-1218
Shih, S. I., Wang, I. C., Wu, K. Y., Li, H. W., Wang, L. C., and Chang-Chien, G. P.,
2009. Uptake of polychlorinated dibenzo-p-dioxins and dibenzofurans in laying
ducks. Journal of Environmental Science and Health Part A-Toxic/Hazardous
Substances & Environmental Engineering, 44:799-807
Shih, S. I., Wang, Y. F., Chang, J. E., Jang, J. S., Kuo, F. L., Wang, L. C., and
Chang-Chien, G. P., 2006. Comparisons of levels of polychlorinated dibenzo-pdioxins/dibenzofurans in the surrounding environment and workplace of two municipal solid waste incinerators. Journal of Hazardous Materials 137: 1817-1830
Sonak, S., Sonak, M., and Giriyan, A., 2008. Shipping hazardous waste:
implications for economically developing countries. International Environmental
Agreements-Politics Law and Economics, 8:143-159
SP Swedish National Testing and Research Institute, 2005. Analysis of fire debris
after tyre fires and fires in electrical and electronic waste. SP Report 2005:44, SP
Swedish National Testing and Research Institute
Stachel, B., Christoph, E. H., Götz, R., Herrmann, T., Kruger, F., Kuhn, T., Lay, J.,
Löffler, J., Päpke, O., Reincke, H., Schröter-Kermani, C., Scwartz, R., Steeg, E.,
Stehr, D., Uhlig, S., and Umlauf, G., 2006. Contamination of the alluvial plain,
feeding-stuffs and foodstuffs with polychlorinated dibenzo-p-dioxins,
polychlorinated dibenzofurans (PCDD/Fs), dioxin-like polychlorinated biphenyls
(DL-PCBs) and mercury from the river Elbe in the light of the flood event in
August 2002. The Science of the Total Environment 364: 96-112
139
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Suarez, M. P., Rifai, H. S., Palachek, R. M., Dean, K. E., and Koenig, L., 2005.
Polychlorinated dibenzo-p-dioxins and dibenzofurans in Houston Ship Channel
tissue and sediment. Environmental Engineering Science, 22:891-906
Sun, S. J., Zhao, J. H., Koga, M., Ma, Y. X., Liu, D. W., Nakamura, M., Liu, H. J.,
Horiguchi, H., Clark, G. C., and Kayama, F., 2005. Persistent organic pollutants in
human milk in women from urban and rural areas in northern China.
Environmental Research, 99:285-293
Sun, S. J., Zhao, J. H., Liu, H. J., Liu, D. W., Ma, Y. X., Li, L., Horiguchi, H.,
Uno, H., Iida, T., Koga, M., Kiyonari, Y., Nakamura, M., Sasaki, S., Fukatu, H.,
Clark, G. C., and Kayama, F., 2006. Dioxin concentration in human milk in Hebei
province in China and Tokyo, Japan: Potential dietary risk factors and
determination of possible sources. Chemosphere, 62:1879-1888
Svenska Renhållningsverksföreningen, 2001. Förbränning av avfall. En
kunskapssammanställning om dioxiner. Svenska Renhållningsverksföreningen
(In Swedish)
Thomas, G. O., Sweetman, A. J., and Jones, K. C., 1999a. Input-output balance of
polychlorinated biphenyls in a long-term study of lactating daily cows.
Environmental Science & Technology, 33:104-112
Thomas, G. O., Sweetman, A. J., and Jones, K. C., 1999b. Metabolism and bodyburden of PCBs in lactating dairy cows. Chemosphere, 39:1533-1544
Turrio-Baldassarri, L., Abate, V., Alivernini, S., Battistelli, C. L., Carasi, S.,
Casella, M., Iacovella, N., Iamiceli, A. L., Indelicato, A., Scarcella, C., and La
Rocca, C., 2007. A study on PCB, PCDD/PCDF industrial contamination in a
mixed urban-agricultural area significantly affecting the food chain and the human
exposure. Part I: Soil and feed. Chemosphere, 67:1822-1830
Turrio-Baldassarri, L., Abate, V., Battistelli, C. L., Carasi, S., Casella, M.,
Iacovella, N., Indelicato, A., La Rocca, C., Scarcella, C., and Alivernini, S., 2008.
PCDD/F and PCB in human serum of differently exposed population groups of an
Italian city. Chemosphere, 73:S228-S234
Undemann, E., Brown, T. N., McLachlan, M. S., and Wania, F, 2009. The role of
models in comparing the behavior of different organic contaminants in different
food chains and ecosystem. Presented at the 12th EuCheMS ICCE 2009,
International Confer-ence on Chemicals in the Environment, Stockholm, Sweden,
June 14-17, 2009
140
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
UNEP, 2001. Thailand Dioxin Sampling and Analysis Program. United Nations
Environment Program
US EPA, 2003. Exposure Factors Handbook. Volume I of III - General factors.
Update to Expo-sure Factors Handbook EPA/600/8-89/043 - May 1989.
EPA/600/P-95/002Ba. SAB Review Draft. 1996. Office of Research and
Development, National Center for Environmental Assessment, U.S. Environmental
Protection Agency
Van den Berg, M, Birnbaum, L., Denison, M., De Vito, M., Farland, W., Feeley, M.,
Fiedler, H., Hakansson, H., Hanberg, A., Haws, L., Rose, M., Safe, S., Schrenk, D.,
Tohyama, C., Tritscher, A., Tuomisto, J., Tysklind, M., Walker, N., and Peterson, R E,
2006. The 2005 World Health Organization re-evaluation of human and mammalian
Toxic Equivalency Factors for Dioxins and Dioxin-like Compounds. Toxicological
Sciences, 93:223-241
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., Peterson, R. E.,
Poellinger, L., Safe, S., Schrenk, D., Tillitt, D., Tysklind, M., Younes, M., Waern, F.,
and Zacharewski, T., 1998. Toxic equivalency factors (TEFs) for PCBs, PCDDs,
PCDFs for humans and wildlife. Environmental Health Perspectives, 106: 775-792
Van Overmeire, I., Pussemier, L., Waegeneers, N., Hanot, V., Windal, I., Boxus, L.,
Covaci, A., Eppe, G., Scippo, M. L., Sioen, I., Bilau, M., Gellynck, X., De Steur, H.,
Tangni, E. K., and Goeyens, L., 2009a. Assessment of the chemical contamination in
home-produced eggs in Belgium: General overview of the CONTEGG study.
Science of the Total Environment, 407:4403-4410
Van Overmeire, I., Waegeneers, N., Sioen, I., Bilau, M., De Henauw, S., Goeyens, L.,
Pussemier, L., and Eppe, G., 2009b. PCDD/Fs and dioxin-like PCBs in homeproduced eggs from Belgium: Levels, contamination sources and health risks. Science
of the Total Environment, 407:4419-4429
Vehlow, J., Bergfeldt, B., and Hunsinger, H., 2006. PCDD/F and related
compounds in solid residues from municipal solid waste incineration - a literature
review. Waste Management & Research, 24:404-420
Wang, I. C., Wu, Y. L., Lin, L. F., and Chang-Chien, G. P., 2009. Human dietary
exposure to polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans
in Taiwan. Journal of Hazardous Materials 164: 621-626
141
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Watanabe, M., Iwata, H., Watanabe, M., Tanabe, S., Subramanian, A., Yoneda, K.,
and Hashi-moto, T., 2005. Bioaccumulation of organochlorines in crows from an
Indian open waste dumping site: Evidence for direct transfer of dioxin-like
congeners from the contaminated soil. Environmental Science and Technology
39: 4421-4430
Weber, R., Gaus, C., Tysklind, M., Johnston, P., Forter, M., Hollert, H., Heinisch, E.,
Holoubek, I., Lloyd-Smith, M., Masunaga, S., Moccarelli, P., Santillo, D., Seike, N.,
Symons, R., Torres, J. P. M., Verta, M., Varbelow, G., Vijgen, J., Watson, A.,
Costner, P., Woelz, J., Wycisk, P., and Zennegg, M., 2008. Dioxin- and POPcontaminated sites-contemporary and future relevance and challenges. Environmental
Science and Pollution Research, 15:363-393
Weintraub, M. and Birnbaum, L. S., 2008. Catfish consumption as a contributor to
elevated PCB levels in a non-Hispanic black subpopulation. Environmental
Research, 107:412-417
Wiberg, K, Åberg, A., McKone, T. E., Tysklind, M., Hanberg, A., and Macleod,
M., 2007. Model selection and evaluation for risk assessment of dioxin
contaminated sites. AMBIO, 36: 458-466
Wittsiepe, J., Erlenkämper, B., Welge, P., Hack, A., and Wilhelm, M., 2007.
Bioavailability of PCDD/F from contaminated soil in young Goettingen minipigs.
Chemosphere, 67: S355-S364
WHO, 2000. Consultation in assessment of the health risk of dioxins; re-evaluation
of the toler-able daily intake (TDI). Food Additives & Contaminants 17: 223-369
Wu, W. Z., Schramm, K. W., and Kettrup, A., 2001. Bioaccumulation of
polychlorinated dibenzo-p-dioxins and dibenzofurans in the foodweb of Ya-Er
Lake area, China. Water Research, 35:1141-1148
Yive, N. S. C. K. and Tiroumalechetty, M., 2008. Dioxin levels in fly ash coming
from the combustion of bagasse. Journal of Hazardous Materials, 155:179-182
Yousif, D. F. and Scott, S., 2007. Governing solid waste management in
Mazatenango, Guatemala. International Development Planning Review,
29:433-450
Zhang, Jianqing, Jiang, Yousheng, Zhou, Jian, Fang, Daokui, Jiang, Jie, Liu,
Guihua, Zhang, Hongyu, Xie, Jianbin, Huang, Wei, Zhang, Jinzhou, Li, Hui,
Wang, Zhou, and Pan, Liubo, 2008. Concentrations of PCDD/PCDFs and PCBs in
retail foods and an assessment of dietary intake for local population of Shenzhen in
China. Environment International, 34:799-803
142
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
REPORT 6418 • Low POP Content Limit for PCDD/Fs
Zhang, Q. H., Xu, Y., Wu, W. Z., Schramm, K. W., and Kettrup, A., 2002.
Reduction of polychlorinated dibenzo-p-dioxins and dibenzofurans levels in
chloranil from China. Bulletin of Environmental Contamination and Toxicology,
69:459-462
Zhang, S. K., Peng, P. A., Huang, W. L., Li, X. M., and Zhang, G., 2009.
PCDD/PCDF pollution in soils and sediments from the Pearl River Delta of China.
Chemosphere, 75:1186-1195
Zhao, G. F., Xu, Y., Han, G. G., and Ling, B., 2006. Biotransfer of persistent
organic pollutants from a large site in China used for the disassembly of electronic
and electrical waste. Environmental Geochemistry and Health, 28:341-351
Zhu, J. X., Hirai, Y., Yu, G., and Sakai, S., 2008. Levels of polychlorinated
dibenzo-p-dioxins and dibenzofurans in China and chemometric analysis of
potential emission sources. Chemosphere, 70:703-711
Åberg, A., Tysklind, M., Nilsson, T., Macleod, M., Hanberg, A., Andersson, R.,
Bergek, S., Lindberg, R., and Wiberg, K., 2010. Exposure assessment at a PCDD/F
contaminated site in Sweden-field measurements of exposure media and blood
serum analysis. Environmental Science and Pollution Research, 17:26-39
143
Low POP Content Limit
OF PCDD/F in Waste
rEport 6418
SWEDISH EPA
isbn 978-91-620-6418-1
issn 0282-7298
Evaluation of human health risks
Persistent and toxic organic pollutants such as dioxins
and dioxin-like PCBs are found in high levels in different
waste fractions. Consequently, the management of such
waste is of major concern considering its potential toxic
impact on the environment and human health.
In this report a science-based Low POP Content Limit
for PCDD/F in waste is developed based on case studies
including improper waste management resulting in
contamination of soil and human food chains. Direct
contact with contaminated waste is also of great concern
from a human health risk perspective.
Setting of Low POP Content Limits is a complex
issue and involves political, technical and economic
perspectives as well. It should however always be focused
on finding a limit value that protects the environment and
human health.
Swedish EPA SE-106 48 Stockholm. Visiting address: Stockholm - Valhallavägen 195, Östersund - Forskarens väg 5 hus Ub, Kiruna - Kaserngatan 14.
Tel: +46 8-698 10 00, fax: +46 8-20 29 25, e-mail: [email protected] Internet: www.naturvardsverket.se Orders Ordertel: +46 8-505 933 40,
orderfax: +46 8-505 933 99, e-mail: [email protected] Address: CM Gruppen, Box 110 93, SE-161 11 Bromma. Internet: www.naturvardsverket.se/bokhandeln