Journal of Environmental Science and Health Part A, 41:2127–2162, 2006
C Taylor & Francis Group, LLC
Copyright ISSN: 1093-4529 (Print); 1532-4117 (Online)
DOI: 10.1080/10934520600872433
Some Chemical Contaminant
of Surface Sediments at the
Baltic Sea Coastal Region with
Special Emphasis on
Androgenic and
Anti-Androgenic Compounds
J. Falandysz,1 T. Albanis,2 J. Bachmann,3 R. Bettinetti,4
I. Bochentin,1 V. Boti,2 S. Bristeau,5 B. Daehne,6 T. Dagnac,5
S. Galassi,7 R. Jeannot,5 J. Oehlmann,3 A. Orlikowska,1
V. Sakkas,2 R. Szczerski,1 V. Valsamaki,2 and
U. Schulte-Oehlmann2
1
Department of Environmental Chemistry & Ecotoxicology, University of Gdańsk,
Gdańsk, Poland
2
Department of Chemistry, University of Ioannina, Ioannina, Greece
3
Department of Ecology and Evolution, J.W. Goethe University, Frankfurt, Germany
4
Department of Chemistry and Environmental Sciences, University of Insubria, Como,
Italy
5
Bureau de Recherches Geologiques et Minieres, Orleans, France
6
Limnomar, Laboratory for Aquatic Research and Comparative Pathology,
Hamburg/Norderney, Germany
7
Department of Biology, University of Milan, Milano, Italy
Androgenic and anti-androgenic compounds including p,p -DDE, Diuron, Linuron,
Fenarimol, Vinclozolin, 1-(3,4-dichlorophenyl) urea (DCPU), 1-(3,4-dichlorophenyl)-3methylurea, (DCPMU), tributyltin (TBT) and triphenyltin (TPT) and their metabolites
(DBT, MBT, DPT, MPT) as well as metallic elements (Ni, Cu, Zn, As, Cd, Pb, Co, Tl,
Cr, Fe, Mn, Al, K, Mg, Na, Ca, Ba, Ti, Sn), PAHs (16 indicator compounds), DDTs and
PCBs have been quantified in top layer (0–10 cm) of up to 37 surface sediment samples
collected from several sites in costal zone of the Gulf of Gdańsk, an inland freshwater
Received January 18, 2006.
Address correspondence to Jerzy Falandysz, Department of Environmental Chemistry
and Ecotoxicology, University of Gdańsk, 18 Sobieskiego Str., PL 80-952, Gdańsk,
Poland; E-mail: [email protected]
2127
2128
Falandysz et al.
area of Brdyujście in Poland and the tidal flats of the Norderney Island, Wadden Sea
in 2002–2003. These sites differed in the degree of anthropogenic activities, including
chemical pollution and related impact on biota. Especially in sediments near shipyards,
ship repair facilities, harbours, other industrial activities or close to municipal sewage
treatment plant outlets butyltins, PAHs and some metallic elements were found at high
concentrations. Diuron, Linuron and DCPMU were detected at a few sites, Fenarimol
only once, while Vinclozolin and DCPU were not detected. DDT concentrations in the
sediments from the Gdańsk and Gdynia region of the Gulf show a stepwise decrease
following the ban for production and use, while diffusion of PCBs at some industrial
sites seems to continue. Elevated PAH concentrations in sediments seem to be mainly
due to pyrogenic and less to mixed pyrogenic and petrogenic sources, while for a few
sites rather petrogenic sources dominated. The reference sites in the Norderney Island,
Wadden Sea showed similar or slightly higher loads of DDTs, BTs, PAHs, PCBs and
metallic elements when compared to sediments from the least contaminated sites in
the coastal Gulf of Gdańsk area, while phenyltins were not detected at both spatially
distant European areas.
Key Words: Diuron; Endocrine disrupters, Fenarimol; Heavy metals; Linuron; Organotins; PAHs; PCBs; Pesticides; Vinclozolin.
INTRODUCTION
Since decades, the Baltic Sea and especially the surrounding–its coastal
regions are impacted by many anthropogenic factors, including discharged
chemicals, which disturb the quality of water and sediments, influence the
composition of the aquatic biocenosis, the survival of biota and may eventually
bio-accumulate in the food-chain.[1,2] Because of these unsolved environmental
problems the Baltic Sea is considered as an area of high scientific interest.
Nevertheless, scientific data concerning its pollution by some noxious organic
or organo-metallic compounds such as phenylurea herbicides, Fenarimol,
Vinclozolin or triphenyltin (TPT), which exhibit androgenic or anti-androgenic
activity, are scare or even non-existing.
The aim of this study was to assess the environmental exposure to
androgenic and anti-androgenic compounds (AACs) in two European areas
with different environmental pollution history. Surface sediment samples were
collected in autumn 2002 and winter 2002–2003 to assess their androgenic
and anti-androgenic potential both analytically and biologically. The selected
sampling points included the near shore region of the Gulf of Gdańsk located
in the neighbourhood of the cities of Gdańsk and Gdynia, inland sites of
the Brdyujście area in the vicinity of the city of Bydgoszcz as well as two
reference sites in Northern Germany (Norderney Island). The collected
sediment samples were analyzed for the occurrence of AACs and a range of
further environmental contaminants. The target analytes included pesticides
and their metabolites (p,p-DDT, p,p-DDD, p,p-DDE, Diuron, Linuron, DCPU,
DCPMU, Fenarimol, Vinclozolin, tributyltin, dibutyltin, monobutyltin,
Surface Sediment Contamination at the the Baltic Sea Coastal Region
2129
Figure 1: Location of the sediment sampling sites in the Gulf of Gdańsk.
triphenyltin, diphenyltin and monophenyltin), polychlorinated biphenyls
(PCBs), polycyclic aromatic hydrocarbons (PAHs: naphthalene, acenaphthylene, acenaphthalene, fluorene, phenanthrene, anthracene, fluoranthene,
pyrene, benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, dibenzo(ah)anthracene, benzo(ghi)perylene and
indeno(123cd)-pyrene), and metallic elements (As, Al, Ba, Ca, Cd, Co, Cr, Cu,
Fe, K, Mg, Mn, Na, Ni, Pb, Sn, Ti, Tl and Zn).
2130
Falandysz et al.
Figure 2: Location of the sediment sampling sites in inland Poland.
MATERIALS AND METHODS
Study Areas
The coastal zone of the Gulf of Gdańsk is the main area of this study. Few
sediment samples were also collected from the Brdyujście site of inland Poland
as well as two reference sites from Northern Germany (Norderney island),
respectively (Figs. 1–3). The Gulf of Gdańsk is part of the Gdańsk Basin which
is a southward extension of the Eastern Gotland Basin. This area—frequently
treated as a separate natural region because of its maximum depth of
118 m—acts as a sink for suspended matter carried by the Vistula River, the
largest river draining into the Baltic proper.[1]
The Gulf of Gdańsk is known to be also under the direct impact of an
intensively urbanized and industrialized region due to the Trójmiasto agglomeration with two large cities, Gdańsk and Gdynia, as well as numerous small
towns, villages and settlements. Some local industrial activities are situated
along its southern, western and north-western (Hel Peninsula) coastline. The
southwestern region of the coastal zone of the Gulf of Gdańsk is considered as
a region of high anthropogenic activity. This is due to a long history of port
activity, shipyard and ship repair industry, navy, chemical industry (fertilizer
production, petroleum refinery), fishery industry, agriculture, residential and
communal heating as well as transport and city run-offs.
Surface Sediment Contamination at the the Baltic Sea Coastal Region
2131
Figure 3: Location of the reference sediment sampling sites in the tidal flats of the island
Norderney (Lower Saxonian Wadden Sea, Germany).
The Brdyujście area in the vicinity of the city of Bydgoszcz is situated about
180 km south of the Gulf of Gdańsk in inland Poland (Fig. 2). At the Brdyujście
sites (nos. 50 and 51/52) sewage was dumped, in recent years largely purified,
coming from the city of Bydgoszcz with its large chemical industries. The Brda
River in the Brdyujście site flows into the Vistula River which enters finally
the Gulf of Gdańsk.
The two reference sites in Germany (nos. R1 and R2) are situated in
the tidal flats of Norderney, an island in the Lower Saxonian Wadden Sea.
These two selected sites were routinely tested within the German Federal
Environmental Monitoring programme and represent the lower level of contamination with xenobiotics in this area (Fig. 3).
Sediment Collection and Processing
Thirty seven surface (0–10 cm) sediment samples with a mass of
∼15 kg each were collected in the Gulf of Gdańsk region using an Eckman grab
sampler. Sampling sites were selected to obtain a good coverage of different
kinds of pollution sources both from fresh and brackish waters in the coastal
zone in the Gulf as well as to establish transects from point sources whenever
it was relevant and possible in autumn 2002 and winter 2002/03 (Fig. 1). At the
same time sediments were collected also in inland Poland (Fig. 2) and at the
2132
Falandysz et al.
two reference samples in the tidal flats of the East Frisian island Norderney
(Germany) at low tide (Fig. 3).
Each wet sediment sample from a particular site was well mixed, divided
into aliquots of ∼2 kg and packed into polyethylene bags. The bags were
wrapped with aluminium foil and kept deep-frozen until chemical analysis
was completed. A ∼2 kg sediment sub-sample from each site was further
lyophilized under dark condition. After being dried at 40◦ C sediment subsamples were initially sieved at 2 mm, followed by crushing and sieving at
250 µm, and further divided into several portions and packed into precleaned high or low density sealed polyethylene containers, depending on
further chemical analysis. Dry sediment subjected to butyltins and phenyltins
analyses were cold stored in brown-coloured containers. The organic matter
content of the sediments was determined by weight-loss-on-ignition at 550 ◦ C.
FENARIMOL, VINCLOZOLIN, DIURON, LINURON, DCPU AND DCPMU
QUANTIFICATION
Chemicals
Analytical grade standards of Diuron (1-(3, 4-dichlorophenyl)-3, 3-dimethylurea), Linuron (3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea), Fenarimol and Vinclozolin were obtained from Riedel-de-Häen, (Seelze-Hannover,
Germany), respectively. The common metabolites of phenylurea pesticides,
1-(3,4-dichlorophenyl) urea (DCPU) and 1-(3,4-dichlorophenyl)-3-methylurea
(DCPMU) were purchased from Dr. Ehrenstorfer GmbH (Augsburg, Germany)
and were used without further purification (minimum percent purity greater
than 98%). Stock standard solutions were prepared at 2 g/L in methanol for
Fenarimol and Vinclozolin and in acetonitrile HPLC grade for the rest analytes. Secondary and working calibration standards were prepared at various
concentrations by serial dilution in methanol and acetonitrile, respectively.
Empore extraction disks of 47 mm diameter containing SDB (styrenedivinylbenzene) copolymer were purchased from 3M (Saint Paul, MN, USA).
The SDB disks comprised 10% fibrillated PTFE and 90% 15 µm (particle
diameter) SDB adsorbent material. Particles in the SDB disks had an average
pore size of 80 Å and a 350 m2 /g surface area. Filter Aid FA 400 was purchased
from 3M (Saint Paul, MN, USA) and copper powder (150 mesh, 99.5%) was
supplied by Aldrich (Milwaukee, WI, USA).
Methanol, dichloromethane, acetone, ethyl acetate, hexane, isooctane and
toluene, were trace analysis grade from Pestiscan (Labscan Ltd., Dublin,
Ireland). HPLC-grade solvents acetonitrile, dichloromethane, acetone,
methanol and water as well as hydrochloric acid and anhydrous sodium
sulphate were purchased from Merck (Darmstadt, Germany).
Surface Sediment Contamination at the the Baltic Sea Coastal Region
2133
Extraction and Quantification
A different extraction methodology was developed for the extraction of
the target analytes. A 5 g aliquot of sediment material (freeze-dried) was
consequently extracted 3 times using 7 mL each time of the following solvents:
acetone, dichloromethane and hexane for Fenarimol and Vinclozolin, while
acetone, methanol and dichloromethane were used as the extraction solvents
of phenylurea herbicides as well as their metabolites, respectively.
Both extracts were combined separately and centrifuged at 5000 rpm for
5 min. Afterwards the supernatants were collected and evaporated to dryness
under a gentle stream of nitrogen. The residue for the analysis of Diuron,
Linuron and their metabolites was then reconstituted in acetonitrile:water
(50:50) up to a final volume of 0.05 mL prior to HPLC-UV/DAD analysis.
Further centrifugation or filtration through PTFE membranes was carried out
when particulate matter interfered the analysis.
Regarding Fenarimol and Vinclozolin analysis, the residue was redissolved in 0.5 mL of methanol, and diluted with distilled water to a final
volume of 100 mL. Then the pH was adjusted to 3 and subjected to SPE
procedure (clean up step). Isolation of the AACs was performed off-line using
a standard SPE-system from Supelco (Bellefonte, PA, USA) connected to a
vacuum pump. SDB disks were first activated by wetting with 5 mL acetone.
Then, they were washed with 2 × 5 mL ethyl acetate: dichloromethane
(50:50 v/v) and were vacuum dried. Methanol (5 mL) was then percolated
through the disks and without letting the disk become dry, the diluted extract
(100 mL) was applied to a speed of 10 mL/min. Next the disks were dried
under vacuum for 10 min. The analytes were eluted in the opposite way
to the sample application (back flush desorption) with 2 × 5 mL of a ethyl
acetate-dichloromethane mixture (50:50 v/v). The extract was dried over anhydrous sodium sulphate and concentrated under a gentle nitrogen stream to
0.2 mL. Additional clean-up with activated copper powder was mandatory for
the elimination of elemental sulphur that causes problems in the chromatographic analysis. The activation of copper powder was performed by washing
under sonication (3 minutes) three times each with 20% HCl, water, acetone
and toluene. After this procedure, copper remains active for at least 3 months
when stored immersed in toluene or cyclohexane. The elimination of sulphur
was done in situ by adding into the vials containing the concentrated sediment
extract (0.2 mL) about 200 mg of activated copper powder. The mixture (extract
and activated copper) was subjected to sonication for 20 minutes, and it was
allowed to stand overnight in the refrigerator to let copper complex with free
sulphur in the sediment extract.
The HPLC system consisted of a Shimadzu (Kyoto, Japan) Model LC10ADVp pump associated with a valve with a 20 µL loop and a Shimadzu
Model SPD-10AVp UV-vis diode-array detector connected to a Shimadzu Model
2134
Falandysz et al.
Class VP 5 integrator. The analytes were separated by means of a Discovery
C18 (250 × 4.6 mm ID: 5 µm) analytical column from Supelco (Bellefonte, PA,
USA) that was fitted with a guard column cartridge of the same composition.
The detector was set at 252 and 250 nm.
Gradient elution was performed by increasing the percentage of acetonitrile in water from 10 to 70% over the first 20 minutes and then to 100% over a
2-minute period. This composition was maintained for 2 minutes, after which
time the initial solvent conditions were restored using a linear ramp over a
3-minute period. The column was equilibrated for an additional 5 min before
the next sample injection. Flow rate was 1 mL min−1 and the volume injected
was 20 µL. The oven temperature was set to 40◦ C.
Chromatographic analysis of Fenarimol and Vinclozolin was performed
using a Shimadzu 14A capillary gas chromatograph equipped with a 63 Ni
electron capture detector (ECD) at 300◦ C. Analytes were separated with a DB1 column (J & W. Scientific, Folsom, CA, USA), 30 m × 0.32 mm I.D., containing
dimethylpolysiloxane with a phase thickness of 0.25 µm. The temperature
program used for the analysis was: from 55◦ C (2 minutes) to 210◦ C (15
minutes) at 5◦ C/min and to 270◦ C at 10◦ C/min. The injector was set to 240◦ C in
the splitless mode. Helium was used as the carrier at 1.5 mL/min. and nitrogen
was used as the make-up gas at 35 ml/min according to the optimization
results of the instrument given by the manufacturer. Identification of peaks
was based on the comparison of the retention times of compounds in the
standard solutions. Quantification of the analyzed compounds was performed
using the method of the internal standard.
Confirmation of the presence of Fenarimol and Vinclozolin was carried
out using a QP 5000 Shimadzu instrument, equipped with a capillary column
DB-5-MS, 30 × 0.25 mm, 0.25 µm, containing 5% phenyl-methylpolysiloxane
(J & W Scientific) at the following chromatographic conditions: from 50◦ C
(1 min) to 140◦ C (2 min) at 30◦ C/min and to 280◦ C at 5◦ C/min (12 min).
Helium was used as the carrier gas at a flow-rate of 1 mL/min. The ion source
and transfer were kept at 290◦ C and 240◦ C, respectively. Electron impact
ionization mode, with 70 eV electron energy, was selected. The splitless mode
was used for injection with the valve opened for 30 s. The screening analysis
was performed in the SIM mode, monitoring at least two characteristic ions
for each compound. In some experiments and for confirmation purposes, scan
acquisition mode (m/z 50–450) was used. The ion traces were divided into four
groups that were recorded sequentially during the injection, on the basis of the
retention times of the single substances. In this way we avoid false positives
due to the occurrence of other compounds which give common fragment ions
but belong to a different retention time group.
Surface Sediment Contamination at the the Baltic Sea Coastal Region
2135
Phenylurea Herbicides and Metabolites
Sediment samples were spiked at a concentration range of 5–100 µg/kg of
the target AACs and extracted using sonication bath coupled to HPLC/UVDAD to check recoveries, method linearity and detection limits in natural
matrices. Linearity was evaluated by the calculation of linear plot based on
linear regression and the correlation coefficient R2 . All analytes exhibited a
linear range from 5–100 µg/kg and an average correlation coefficient above
or equal to 0.994 was observed. Replicate analysis of spiked sediments
(n = 5) revealed satisfactory recovery values ranged from 66% to 92% for the
two herbicides and their metabolites. The limit of detection varied between 0.6
and 0.9 µg/kg for all analytes.
Fenarimol and Vinclozolin
Replicate analysis of spiked sediments with Fenarimol and Vinclozolin at
25 µg/kg (n = 5) revealed sufficient recovery values of 75% for Fenarimol and
74% for Vinclozolin. Relative standard deviation values were 14% and 11% for
Fenarimol and Vinclozolin, respectively. Both compounds had a linear range
from 25–400 µg/kg and an average correlation coefficient R2 ≥ 0.995. The limit
of detection was 5 µg/kg, to both analytes.
Intra-day (repeatability) and inter-day (reproducibility) precision experiments by analyzing three samples spiked at 25 µg/kg of each compound showed
excellent results with RSDs less than 12% in all cases.
DDTs AND PCBs QUANTIFICATION
Extraction and Cleanup
Soxhlet extraction of dried sediment (2–3 g) was performed for 8 hours
with n-hexane (100 mL). After solvent evaporation under reduced pressure,
extractable organic matter (EOM) content was determined gravimetrically.
Organic matter was then destroyed with H2 SO4 (98%) and chlorinated hydrocarbons were recovered by shaking with several portions of n-hexane. Next,
combined n-hexane extracts were further concentrated down to about 2 mL
and passed through a Florisil column (4 × 0.7 cm I.D.) with Cu powder
(0.1 g) on the top. Cu powder was previously activated by HCl (18.5%) and
washed with water, acetone and n-hexane. The Florisil column was eluted with
25 mL of n-hexane and the eluate was concentrated to exactly 0.5 mL.
Quantification and AQ/AC
The purified extracts were introduced by on-column injection into a gas
chromatograph Termo-Finnigan TOP 8000 equipped with a fused silica column
2136
Falandysz et al.
(CP-Sil 8 CB, Chrompack, 50 m × 0.25 mm × 0.25 mm I.D., film thickness
0.25 µm). A Carlo Erba ECD 80 was used as electron capture detector heated
at 320◦ C. p,p -DDE, p,p -DDD (Dr. Ehrenstorfer, Germany) and p,p -DDT Pestanal (Riedel-de Haen, Germany) were reference standards used at the final
concentration of 10 µg/L in iso-octane. The technical polychlorinated biphenyls
(PCBs) formulation of Aroclor 1260 (10 mg/L in iso-octane, Dr. Ehrenstorfer,
Germany) was used as reference standard for PCBs quantification. Single PCB
congeners were identified and quantified both by reference-pure PCBs (BCR,
Brussels, Belgium) and published data.[3]
Recovery efficiency was tested on reference sediment previously used in an
intercalibration exercise.[4,5] Recoveries for p,p -DDE and PCBs were within
60–80% and for p,p -DDT and p,p -DDE around 50%.
PAHs Quantification
Sediments were analysed for their contents of PAH (naphtaline, acenaphthylene, acenaphtene, fluorene, phenanthrene, anthracene, fluoranthene,
pyrene, benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, dibenz(ah)anthracene, benzo(ghi)perylene and
indenol(1,2,3-cd)pyrene) according to DIN 38414 S 21 (DIN 1996) by means
of HPLC (high performance liquid chromatography).[6] Samples were freeze
dried and milled, followed by an accelerated solvent extraction (ASE).
Cyclohexane served as extractant. Analysis parameters for the extraction
were as follows: extractin pressure was 10 MPa; extraction temperature
was 100◦ C; heating time was 5 min; static extraction was 3 × 5 minutes;
rinsing with solvent (60% of cell volume) and rinsing with nitrogen (1 MPa for
150 seconds). The sample volume was reduced to 1.0 ml and cleaned over
2.8 ml cartridges with 0.5 g silica gel filling (SPE column). The cleaned extract
was transferred into an acetonitrile phase and prepared for HPLC analysis.
In deviation from the guideline, the separation was achieved by means of a
gradient elution, with parameters as follows: injection volume was 20 µL;
column temperature was 20◦ C; flow rate was 0.9 ml/min: at elution time
0–20 minutes acetonitryle in deionized water (50:50; eluent A) was used; at
elution time 20–35 minutes acetonitryle (eluent B) was used; at elution time
35–40 minutes, again eluent A was used.
For the detection of organic hydrocarbons, both fluorescence detectors
and photodiode-array detectors may be used. In order to obtain optimal
results, both detector types were used for this study. For quality assurance
and control, a standard reference material was analysed (harbour sediment
CRM 104, Resource Technology Corporation, USA). The obtained results for
these analyses showed concentrations in the certified range. The reported
PAH concentrations are mean values of three measurements, each of three
digestions of a sediment sample.
Surface Sediment Contamination at the the Baltic Sea Coastal Region
2137
ORGANOTINS QUANTIFICATION
Chemicals
The standards of tributyltin (TBT), dibutyltin (DBT), monobutyltin (MBT),
triphenyltin (TPT), diphenyltin (DPT) and monophenyltin (MPT) were purchased from STREAM Chemicals (Bischheim, France). 2,2,4-trimethylpentane
(VWR, France), methanol (HPLC) (JT Baker, France), tropolone (99%), acetic
acid glacial (99%), ammonium acetate (98%; Lancaster, Bischheim, France),
and sodium tetrahydroborate (min. 98%; STREM Chemicals, Bischheim,
France) all were of analytical grade.
Extraction, Quantification and AQ/AC
Organotins were extracted from dried sediment samples by using Pressurized Liquid Extraction (PLE). The following conditions were used for the
PFE: temperature 80◦ C, pressure at 100 bars, extraction time 5 minutes and
number of cycles was 5. Then, 1 to 10 mg of each sample was extracted
with 30 mL of acetic acid 0.5 M in methanol (3/97 v/v) containing 0.2% of
tropolone. After extraction, 5 mL of extract were mixed with 2 to 5 mL of
2,2,4-trimethylpentane, internal standard mixture and 2 mL of NaBEt4 (2%)
at pH 4.8 (100 mL of acetate buffer 0.6 to 1 M). The 2,2,4-trimethylpentane,
which contained the organotin compounds, was recovered and concentrated
down to 1 mL under gentle stream of nitrogen. The extract was analyzed by
gas chromatography tandem mass spectrometry (GC-MS/MS).
GC/MS/MS analyses were performed using a Thermoquest (Les Ulis,
France) system consisting of a Trace GC 2000 GC equipped with a PTV
split-splitless temperature injector, an AS 2000 autosampler and a POLARIS
Q ion-trap mass spectrometer (Thermofinnigan, Les Ulis, France). For data
processing, Excalibur software from Thermofinnigan was used. The injector
was equipped with a 12 cm × 2 mm I.D. Silcoseeve liner (Thermofinnigan).
They 2 µL of extract was injected onto the PTV injector in constant flow
mode set at 1 mL/min and with an injection rate of 1 µL/s. The split flow
was set at 50 mL/min. The temperature of the injector was initially set at
85◦ C then increased to 300◦ C at a rate of 10◦ C/s where it was maintained for
12 minutes. The PTV split/splitless valve was operating in splitless mode until
the temperature of 300◦ C was achieved.
Once the temperature stabilized, it was maintained for a period of 1.5
minutes, then changed to split mode. Compounds were separated on a 30 m
× 0.25 mm I.D. column, coated with 0.25 µm of 65% dimethyl-35% phenyl
polysiloxane phase (BPX-35, SGE, Courtaboeuf, France). The temperature of
the column was initially set at 85◦ C for a period of 1 minute, and then increased
at different rates to 280◦ C. Helium was the carrier gas at a constant flow of
2138
Falandysz et al.
Table 1: Interlaboratory round robin for organotin compounds in sediments.
Butyltin species concentration (ng/g)
MBT
DBT
TBT
SED 1 (mean value)
Measured value
SED 2 (mean value)
Measured value
111.2 (34%)
126.6
124.7 (50.5%)
93.7
165.3 (19.6%)
168.3
205.3 (19.8%)
247.2
319.2 (13%)
310.3
28.5 (24%)
24.4
1 mL/min. The transfer line was set at 300◦ C with the external ion source
at 280◦ C. The ions in EI for the target species were selected and fragmented
with helium gas CID in the ion trap. The second-order mass spectra resulting
from the most intense fragment were scanned from m/z ion 50 to the mass
of the selected ions. The concentrations were calculated using the calibration
curves established for each compound in internal standardisation mode with
tripropyltin and diheptyltin as internal standards.
Organotin compound recoveries for certified reference material (sediment
CRM 462 and CRM 646) were in the range of 120–130% for TBT, 90–112% for
DBT, 70–89% for MBT, 54–125% for TPT, 77–119% for DPT and 75–100% for
MPT. The results of an intercalibration exercise are presented in Table 1.
Metallic Elements Quantification and AQ/AC
Sediments were analysed for their contents of the elements Ag, Al, As,
Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sn, Tl and Zn according to guideline DIN
38406 E 29 (DIN 1996) by means of ICP-MS (inductively coupled plasma
mass spectrometry, Perkin Elmer Elan 6000 or Finnigan PQ3 for tin) and
ICP-OES (inductively coupled plasma optical emission spectroscopy, Perkin
Elmer Optima 3000).[7]
Therefore, 250 mg of the sediment sample were freeze dried (Alpha
1–4, Christ, Osterode/Harz, Germany), and 6 mL HNO3 (65% subboiled),
2 mL H2 O2 and 1 mL HF (suprapure) were added. Sediments were digested
in teflon tubes in a High Performance Microwave Digestion Unit MLS
1200 mega (Microwave Lab Systems GmbH, Leutkirch, Germany), combined
with a EM-45/A unit for used air. A rhodium solution (50 µL of a 10 mg/L stock
solution each) served as internal standard for ICP-MS analysis.
Analytical performance of element quantification was checked by analysis
of two standard reference material (SRM)—river sediment 1407–1 and sediment GBW 08301. The obtained results for these analyses showed concentrations in the certified range (Table 2). Instruments were optimised by means of a
manganese standard (Kraft, Duisburg, Germany) and subsequent calibration
was achieved by ICP multielement standard VI (Merck, Darmstadt, Germany).
Surface Sediment Contamination at the the Baltic Sea Coastal Region
2139
Table 2: Metallic element data of sediment GBW 08301(µg/g dry matter).
Element
Ni
Cu
Zn
As
Cd
Pb
Co
Mn
Cr
Certified value
Measured value
32
53 ± 6
251
56 ± 10
2.4 ± 0.3
79 ± 12
16.5 ± 1.5
975 ± 34
90 ± 8
32
51
235
53
2.4
88
14
958
86
Instruments were rinsed with 3% HNO3 (subboiled). Analysis parameters for
ICP-MS were as follows: CEM voltage, 3.72 V; plasma 1000 W; argon pressure,
4.4 bar; nebulizer gas flow, 0.93 L/min; plasma gas flow, 0.8 L/min. Analysis
parameters for ICP-OES were as follows: plasma, 1200 W; argon pressure,
4–5 bar; argon flow 15 L/min; nebulizer gas flow, 0.7–0.9 L/min; plasma gas
flow, 0.8 L/min.
Al, Fe and Mn concentrations were determined by ICP-OES. The reported
metal concentrations are mean values of four measurements, each of two
digestions of a sediment sample.
RESULTS AND DISCUSSION
Overview
The sediment collected from the sampling sites in the region of the Gulf
of Gdańsk had various texture. The sediments ranged from sandy material at
sites 8, 9, 12, 20–22, 30–33, 40–44, 60, 61, 70, 80, and 81 to muddy sediments
relatively rich in organic matter (> 2%) at sites 1–7, 11, 13–15, 50, 51/52, 82,
83, R1 and R2 (Figs. 1–3, Table 3).
Some bulk data on concentrations of butyltins (BTs), DDTs (p,p -DDE;
p,p -DDT and p,p -DDD), PCBs and PAHs but also some individual compounds such as tin (Sn), Diuron, Linuron, (DCPU), (DCPMU), Fenarimol
and Vinclozolin in sediment from the sites investigated are summarized in
Table 3. Generally, amongst organic contaminants PAH concentrations were
greater than those of PCBs, DDTs or phenylurea herbicides. As expected,
sediments from shipyard and other industrial sites are characterized by high
concentrations of tributyltin and its metabolites. In addition, PCBs, some
parent PAHs as well as heavy metals were quantified at elevated concentration
at some of the sites sampled (Tables 3, 5, 7 and 8). No live benthic fauna
2140
1
2
3
4
5
6
7
8
9
11
12
13
14
15
20
21
22
Site
no.
3.8
10
7.5
8.5
4.9
5.1
2.7
0.4
0.5
11.5
0.5
2.2
7.5
3.9
1.8
1.5
1.7
OM
(%)
30
7.2
4.1
2.8
0.64
0.53
0.18
ND
ND
ND
ND
ND
0.063
ND
ND
ND
ND
BTs
µg/g
d.m.∗
38
5.8
5.3
4.2
3.1
2.7
3.2
3.6
0.9
0.3
0.2
0.5
0.9
0.3
0.3
0.4
0.2
Sn
µg/g
d.m.
34
27
5.4
7.1
6.8
30
0.87
0.16
0.08
0.41
0.17
0.11
0.12
0.09
0.14
0.16
0.26
DDTs
ng/g
d.m.
420
230
21
52
<0.5
1.0
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
PCBs
ng/g
d.m.
NA
52
12
5.9
5.7
18
0.73
0.2
NA
2.3
NA
NA
2.3
NA
NA
NA
NA
PAHs
µg/g
d.m.
25
ND
25
ND
ND
ND
ND
NQ
NQ
21
ND
ND
ND
ND
ND
ND
ND
Diuron
ng/g
d.m.
ND
ND
20
ND
ND
ND
ND
21
NQ
3.8
NQ
NQ
2.7
NQ
ND
ND
ND
Linuron
ng/g
d.m.
NQ
ND
ND
ND
ND
ND
ND
ND
ND
NQ
ND
ND
ND
ND
ND
ND
ND
DCPU
ng/g
d.m.
ND
ND
19
ND
ND
ND
ND
8.5
NQ
8.5
ND
NQ
ND
ND
ND
ND
ND
DCPMU
ng/g
d.m.
NQ
18
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NQ
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Fenarimol Vinclozolin
ng/g
ng/g
d.m.
d.m.
Table 3: Concentration of organic matters (%), total butyltins, tin, DDTs, PCBs, 16 PAHs, Diuron, Linuron, Fenarimol and
Vinclozolin in surface sediments at selected sites in coastal region of the Gulf of Gdańsk, inland Poland and the Wadden Sea at
the German North Sea coast (for the sites localization see Figs. 1–3).
2141
1.7
0.5
0.4
0.6
0.3
1.4
1.7
0.3
0.3
15.6
6.2
0.7
0.5
0.6
0.4
1.6
2.6
2.7
5.5
4.1
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.082
0.10
ND
ND
ND
ND
0.35
0.55
0.63
ND
ND
0.3
0.3
0.4
0.2
0.3
0.5
0.3
0.2
0.3
1.4
4.0
0.4
0.3
0.6
0.4
1.5
2.0
1.9
NA
NA
<0.5
0.16
0.14
<0.5
0.08
0.37
0.33
<0.5
<0.5
24
4.7
0.43
0.35
0.18
0.16
4.0
4.2
3.5
0.65
0.41
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
15
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
42
<0.5
<0.5
<0.5
NA
170
NA
NA
0.45
NA
NA
0.22
NA
8.8
9.4
NA
NA
NA
0.25
1.3
2.1
2.1
0.50
0.29
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
5.1
ND
ND
ND
NA
NA
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
NA
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NQ
ND
ND
ND
NA
NA
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NQ
ND
ND
ND
NA
NA
NQ
NQ
NQ
NQ
NQ
ND
ND
ND
ND
NA
32
ND
ND
ND
ND
ND
ND
ND
NA
NA
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
ND
ND
ND
ND
ND
ND
ND
ND
NA
NA
cation; NA (not analyzed); ND (not detected): DCPU < 0.9 ng/g d.m., DCPMU < 0.7 ng/g d.m., Diuron < 0.7 ng/g d.m., Linuron
< 0.6 ng/g d.m., Fenarimol and Vinclozolin < 5.0 ng/g d.m.; NQ (not quantified): DCPU < 2.7 ng/g d.m., DCPMU and Diuron < 2.1 ng/g d.m.,
Linuron < 1.8 ng/g d.m., Fenarimol and Vinclozolin < 15.0 ng/g d.m.
∗ Butyltin
30
31
32
33
40
41
42
43
44
50
51/52
60
61
70
80
81
82
83
R1
R2
2142
Falandysz et al.
(molluscs, crustacean, juvenile fishes) was found at the time of sediment
collection at sites 1–6, 11, 14, 50, 51/52, 81, 82 and 83 (Figs. 1 and 2).
Sediments were found to be much less polluted and with abundant benthic
animals at sites outside of the industrial/shipyard zone, the sewage/waste
water outfall area with a long history of suspended matter sedimentation or
at sites relatively away of the cities.
Diuron, Linuron, Vinclozolin DCPU, DCPMU and Fenarimol
From the target analytes examined, Diuron, Linuron and their metabolite
DCPMU were found in sediments at sites that were mostly under influence
of industrial impacts and at a single site receiving more municipal and
agricultural impacts rather than industrial discharges. In detail, four positive
detections were observed for Diuron and Linuron at concentration ranging
from 5.1 to 25 and 2.7 to 20 ng/g dry matter, respectively (sites nos. 3, 8,
11, 14 or 80, respectively). DCPMU was detected at three of these sites with
concentrations from 8.5 to 19 ng/g dry matter, while DCPU was not detected at
all. Diuron, Linuron and DCPMU were detected at two sites, which are related
to some degree of industrial, shipyard, ship repair and municipal impacts (sites
nos. 3 and 11). Site no. 3 receives effluents from the sewage treatment plant
“Zaspa” in Gdańsk and the Kaszubski Canal in Nowy Port and site no. 11
is influenced by the Reda River. On the other side, at a single coastal site
(no. 8) receiving discharges of the Motława River, including also runoff storm
water and treated municipal effluents of the city of Gdańsk, both Linuron
and DCPMU were detected. At two other sites only Diuron was detected—at
shipyard site and sea port—while Linuron was found nearby to the Reda River
outlet (sites nos. 1 and 80, Table 3).
Fenarimol was only detected once in sediment from the Dead Vistula River
Canal nearby to the shipyard canal at Ostrów Island in Gdańsk (no. 2). DCPU,
the common metabolite of Diuron and Linuron herbicides as well as Vinclozolin
was not found at any site examined (Table 3). There are no previous records
on environmental occurrence either of Diuron, Linuron and their metabolites
as well as of Fenarimol and Vinclozolin in the Gdańsk region or other areas in
the northern part of Poland or in the southern coastal part of the Baltic Sea.
Diuron could be additionally applied as active anti-boosting agent in marine
paints apart from its agricultural use.[8]
DDTs and PCBs
p,p –DDE is an impurity in technical DDT formulations (up to ∼4%)
but its main origin in the environment is as a metabolite of the
pesticide p,p–DDT [1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane] by various
biota (mammals, birds, insects).[9] The acaricide Dicofol [1,1-dichloro-2,2-bis
Surface Sediment Contamination at the the Baltic Sea Coastal Region
2143
(4-chlorophenyl)ethane; TDE or p,p –DDD] usually contains some amount of
by-side p,p –DDT.
The insecticide DDT was intensively used in Poland in the 1950s to the
1970s. Also in the former Eastern Germany, technical DDT was used up to
the 1980s.[10] To combat malaria in subtropical and tropical region countries
technical DDT is continuously manufactured and used at some amount.[11]
p,p –DDE is thermodynamically more persistent when compared to p,p DDT and p,p–DDD, and both p,p–DDT and p,p–DDE can persist for long when
bound to soil particles.[10,11] Due to intensive use of DDT in the Polish agriculture in the past soil and soil run-off are considered as a main but decreasingly
important source of DDTs (DDT and analogues) for the environment of the
Gulf of Gdańsk. To some degree also a long-range trans-boundary tropospheric
transport and subsequent aerial deposition could be considered as a source of
DDTs to the Gdańsk region.[10,12–16]
In earlier studies, sandy surface sediments collected at the northern region
of Puck Bay in the Gulf of Gdańsk in 1990 contained DDTs in concentration
from 0.039 to 0.35 ng/g d.m., while muddy sediment from the Vistula River
at Kiezmark site (near Gdańsk) and from the Gdańsk Depth in the Gulf
of Gdańsk colleted in 1992 contained DDTs at concentration of 77 and
15 ng/g d.m., respectively.[17,18] In the same decade a wider range of DDT
concentrations was noted in surface freshwater sediments collected in the
costal area of Gulf of Gdańsk with mean values ± standard deviations (and
ranges) for p,p –DDE at 2.3±4.1 (0.013–14) ng/g d.m., p,p–DDT at 4.9±12
(0.022–51) ng/g d.m., DDTs (p,p- and o,p-DDT, -DDD and -DDE) at 24±41
(0.1–150) ng/g d.m.[19] These concentrations are comparable or even lower
when compared to the most contaminated sites impacted by industrial plants
and/or sewage outfalls in this study (Table 3). This finding implies a stepwise
decreasing pollution trend following cessation of manufacture and ban on
usage. However, the DDT concentrations in Gulf of Gdańsk sediments are at a
number of the analysed sites in the same range or even lower when compared
to the reference sites in the Wadden Sea (Table 3).
From the European perspective, DDTs were noted at higher concentrations
than for the non-industrial sites in this study at non-industrial sites in
the Rhone delta in France (5–15 ng/g d.m.), estuaries in Northern Greece
(0.3–60 ng/g d.m.), in Lake Maggiore in Italy (44–140 ng/g d.m.) and in Cyprus
(19–699 ng/g d..m.).[20–23]
PCB concentrations in sediments at shipyard/industrial sites in the
Gdańsk region (nos. 1–4 and 6) or Gdynia Shipyard area (no. 82) generally
exceed DDT levels (Table 3). In an earlier study the muddy sediment from the
Vistula River at Kiezmark site (near Gdańsk) and from the Gdańsk Depth
in the Gulf of Gdańsk, which were collected in 1992, contained PCBs at
5.6 and 1.2 ng/g d.m., respectively.[18] In parallel, for several coastal freshwater
sites near the cities of Gdańsk and Gdynia investigated in 1994 sediment PCB
2144
Falandysz et al.
concentrations were 110±160 ng/g d.m.[19] When compared to these historical
records the findings in our present study imply a continuous leakage and
diffusion of PCBs from local sites (Table 3). No PCBs were found in the
sediments from the two reference sties in the Wadden Sea (Tables 3 and 4)
suggesting a higher prevalence of DDTs diffusion than that of PCBs in the
southern region of the North Sea.
PAHs
Concentrations of the 16 US-EPA priority PAHs varied between 0.20 and
52 µg/g in 16 selected sediments from the Gulf of Gdańsk region, between
8.8 and 9.4 µg/g in sediments for 2 adjacent sites at Brdyujście in inland
Poland, and between 0.29 and 0.50 µg/g for the two German reference
sites. PAHs concentrations were not uniformly distributed in sediments along
the southwestern coastline of the Gulf of Gdańsk. Sediments near the the
harbours of Gdańsk (nos. 2–6) and Gdynia (nos. 82 and 83) were generally
highly contaminated (Fig. 1, Table 5). Indeno(12cd)-pyrene was found at
the Mechelinki site—a former municipal sewage pipe outlet (dumping) site
for the city of Gdynia—at a relatively high concentration of 170 µg/g dry
matter. The Mechelinki site is localized at the shore of the Gulf and originally
was the outlet of the Zagórska Struga creak (site no. 31, Fig. 1). Sediment
at the other sites, when compared to the Mechelinki site, were much less
contaminated with indeno(12cd)-pyrene, i.e., contained this compound at
<0.008 to 1.6 µg/g dry matter. Actually sewage from the city of Gdynia after
is further transported by
passing the sewage treatment plant in Debogórze
pipe and waste water is dumped 1.5 km off-shore in the Gulf. Apart from
indeno(123cd)-pyrene, the concentrations of the other fifteen US-EPA PAHs
was low at the Mechelinki site, i.e., from <0.009 to 0.047 µg/g dry matters
(Table 5).
A particularly high total PAH concentration reaching 52 µg/g dry matters
was noted at the site close to the vessel bunkering point in the Ostrów Canal,
which is a part of the Dead Vistula River Channel with shipyards and some
other facilities localized nearby.
A high total PAH concentration of 18 µg/g dry matters was also found
in sediment collected close to the outlet of the sewage pipe of the Zaspa
sewage treatment plant in the city of Gdańsk (site no. 6). A study of untreated
(raw) and treated (after clarification) sewage sludge collected from that
same plant in 1998 revealed predomination of 4-ring and higher molecular
weight congeners and total PAHs at concentration of 12 (8.0–16) µg/g and 14
(9.4–18) µg/g, respectively.[24] The outlet of the waste water pipe is pointed
near bottom at the western site of the canal of the Port of Gdańsk. PAH
concentrations in sediments collected at the dumping site of waste water
and sewage from the city of Bydgoszcz (sites nos. 50 and 51/52) were in the
2145
95
101
110
151
149
153
132
138
187
183
128
174
177
156
180
170
201
203
195
194
206
PCBs
CB congener no.
27
14
<0.005
<0.005
120
65
3.3
75
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
38
17
18
17
0.00
12
13
420
1
17
25
<0.005
<0.005
36
32
<0.005
35
14
<0.005
<0.005
13
<0.005
<0.005
31
12
9.8
<0.005
0.24
5.0
2.6
230
2
1.2
0.29
<0.005
1.2
3.2
3.3
<0.005
3.6
1.2
0.59
<0.005
<0.005
0.65
<0.005
2.9
1.6
0.41
0.54
0.22
0.50
0.11
21
3
6
0.11
0.08
<0.005
<0.005
0.31
0.36
<0.005
<0.005
0.18
0.16
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
1.2
4
<0.005
5.2
<0.005
5.7
18
2.2
<0.005
7.3
1.8
1.1
<0.005
1.8
0.92
<0.005
3.8
2.0
0.63
0.72
<0.005
0.50
0.19
52
4.3
1.8
<0.005
2.0
<0.005
1.6
<0.005
2.3
0.43
0.55
<0.005
0.34
<0.005
<0.005
0.57
0.43
<0.005
0.15
<0.005
0.22
<0.005
15
50
Sampling site no.
4.6
1.4
<0.005
2.1
12
6.6
1.1
7.3
1.9
0.76
<0.005
1.7
0.96
<0.005
2.7
1.8
0.82
0.88
0.37
0.76
<0.005
47
82
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.05
R1
Table 4: Chlorobiphenyl (CB) congener and total chlorobiphenyls content of the sediments at selected sites examined
(ng/g d.m.).
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.05
R2
2146
2
3
4
5
6
7
8
11
14
31
40
43
50
51–52
80
81
82
83
R1
R2
Site no.∗
0.26
<0.013
<0.013
<0.013
<0.013
<0.013
<0.013
<0.013
<0.013
<0.013
<0.013
<0.013
0.030
0.26
<0.013
<0.013
<0.013
0.022
<0.013
<0.013
Naphthalene
0.042
0.025
<0.012
<0.012
<0.012
<0.012
<0.012
<0.012
<0.012
<0.012
<0.012
<0.012
<0.012
1.2
<0.012
<0.012
<0.012
<0.012
<0.012
<0.012
Acenaphthylene
1.7
0.015
0.025
0.025
0.14
<0.012
<0.012
<0.012
<0.012
<0.012
<0.012
<0.012
<0.012
<0.012
<0.012
<0.012
<0.012
0.020
<0.012
0.014
Acenaphthalene
2.5
0.023
0.027
0.032
0.34
0.020
<0.010
0.034
0.027
<0.010
<0.010
<0.010
0.17
0.032
<0.010
0.065
0.028
0.074
0.011
0.012
Fluorene
7.1
<0.018
0.75
0.060
3.0
0.032
<0.018
0.14
0.10
<0.018
<0.018
<0.018
<0.018
0.29
<0.018
0.035
0.13
0.14
<0.018
<0.018
Phenanthrene
1.8
0.047
0.094
0.091
0.88
0.031
0.025
0.030
0.027
0.047
0.029
0.086
0.086
3.6
0.056
0.026
0.024
0.032
0.026
0.028
Anthracene
18
0.56
1.4
0.82
4.0
0.19
0.11
0.88
0.96
0.014
0.019
<0.010
0.96
2.7
0.049
0.38
0.60
0.54
0.20
0.042
Fluoranthene
0.22
9.0
0.61
0.55
2.1
0.11
0.008
0.39
0.26
0.032
0.12
0.022
0.54
0.12
0.062
0.18
0.22
0.36
0.12
0.021
Pyrene
Table 5: Concentrations of 16 individual PAHs in surface sediments (µg/g dry matter) at selected sites in coastal region of the
Gulf of Gdańsk, inland Poland and the Wadden Sea at the German North Sea coast (for the sites localization see Figs. 1–3).
2147
∗ For
4.8
0.35
0.38
0.49
1.7
0.038
<0.016
0.12
0.13
<0.016
0.12
0.021
0.54
0.059
<0.016
0.063
0.13
0.11
0.026
<0.016
6.6
0.57
0.90
1.0
2.1
0.032
<0.016
0.19
0.14
<0.016
0.099
0.017
1.0
0.13
<0.016
0.17
0.18
0.17
0.019
0.040
the sites localization see Figs. 1–3.
2
3
4
5
6
7
8
11
14
31
40
43
50
51–52
80
81
82
83
R1
R2
2.1
0.29
0.46
0.52
0.81
0.035
<0.010
0.10
0.13
<0.010
<0.010
<0.010
1.3
0.13
<0.010
0.064
0.17
0.13
<0.010
0.014
1.2
0.20
0.29
0.34
0.67
0.022
<0.012
0.062
0.072
<0.012
<0.012
<0.012
0.67
0.048
<0.012
0.034
0.091
0.068
<0.012
<0.012
3.0
0.53
0.62
0.79
1.4
0.059
<0.009
0.15
0.20
<0.009
<0.009
<0.009
1.4
0.19
0.011
0.095
0.23
0.18
0.012
0.028
0.41
0.093
0.18
0.15
0.16
<0.009
<0.009
0.022
0.035
<0.009
<0.009
<0.009
0.35
<0.009
<0.009
0.017
0.048
0.028
0.018
0.021
1.0
0.20
0.32
0.38
0.42
0.097
<0.016
0.067
0.099
<0.016
<0.016
<0.016
0.83
0.47
<0.016
0.061
0.13
0.11
0.029
0.024
1.6
0.25
0.37
0.47
0.53
0.049
<0.008
0.071
0.089
170
<0.008
<0.008
0.94
0.16
0.008
0.055
0.15
0.12
<0.008
0.015
2148
Falandysz et al.
Table 6: Parent PAH concentration quotients in the sediment examined.
Parent PAH concentration quotient
Site no.∗
2
3
4
5
6
7
8
11
14
31
40
43
50
51–52
80
81
82
83
R1
R2
Phe/Anth
Pyrogenic < 10–15
Petrogenic > 10–15
3.9
0.19
8.0
0.66
3.4
1.0
0.36
4.7
3.7
0.19
0.31
0.10
0.10
0.081
0.16
1.3
5.4
4.4
0.35
0.32
Flu/Pyr
Pyrogenic >1
Petrogenic <1
82
0.062
2.3
1.5
1.9
1.7
14
2.3
3.7
0.43
0.16
0.23
1.8
23
0.79
2.1
2.7
1.5
1.7
2.0
Lmw/Hmw
Pyrogenic< 1
Petrogenic > 1
6.7
0.02
1.1
0.08
0.35
3.2
1.1
0.36
0.3
0.28
<0.01
0.16
0.03
20
0.15
0.19
0.59
0.39
0.08
1.3
Naph/Phen
Pyrogenic < 1
Petrogenic > 1
0.04
∼1
0.008
0.1
0.02
0.18
∼1
0.04
0.06
∼1
∼1
∼1
∼3
0.9
∼1
0.17
0.05
0.16
∼1
∼1
∗ For the sites localization see Figs. 1–3; A half of method limit of quantification value was used to
calculate a particular parent PAHs concentration quotients for some sampling sites; Lmw/Hmw
[concentration quotient of phenanthrene to pyrene relative to benzo(a )anthracene to
benzo(ghi )perylene] [27] .
range from 8.8 to 9.4 µg/g dry matter. These PAH concentrations are higher
when compared to riverine sediments collected along the Odra River and its
tributaries in summer 1998 with measured values between 0.15 and 19 µg/g
(6.5 µg/g, on the average).[24]
Known sources of PAHs for the aquatic environment are industrial discharges, petroleum spills, combustion of fossil fuels, wood, municipal and
industrial waste materials, automobile exhausts and non-point discharges
such as urban runoff and deposition via the atmosphere.[25–27] These sources
can be considered as contributing to the measured PAHs loads in the coastal
zone of the Gulf of Gdańsk but at a local scale and when related to the regional
topography single or few sources seem to dominate nowadays. Due to the
domination of some individual compounds, two main sources of environmental
pollution with PAHs can be distinguished.[26, 28–33]
Phenanthrene (Phe) is a thermodynamically more stable tricyclic aromatic congener than anthracene. Hence, petroleum contains more phenanthrene when compared to anthracene (Phe/Ant > 5). On the contrary, hightemperature processes such as incomplete combustion of fossil fuel (e.g.,
lignite or coal) can result in low Phe/Ant ratios (Phe/Ant <15).[28] Similarly,
Surface Sediment Contamination at the the Baltic Sea Coastal Region
2149
fluoranthene (Flu) to pyrene (Py) ratios greater than 1 are attributed to
pyrolitic sources, whereas ratios below 1 are related to petrogenic sources, with
few exceptions.[26–31] Another diagnostic tool to identify dominant source of
PAHs in environmental matrices is the predominance of low molecular weight
over higher molecular weight congeners (concentration ratio > 1), which
suggest petrogenic origin release.[29,33] Similarly, predominance of alkylated
and 2–3-ring over 4–6-ring PAHs suggests petrogenic origin pollution and
vice versa is for pyrolytic sources.[26,33] Fresh and unweathered petroleum is
characterized by naphthalene to phenanthrene concentration quotient greater
than 1.[33]
The Phe/Anth concentration ratio is <10–15 for all analysed sediments
implying largely pyrogenic origin of PAHs. Nevertheless, there is a wide
span for this parameter ranging from 0.086 to 1.3 for eleven and from 3.7
to 8.0 for seven further sites in Poland (Table 6). The Flu/Pyr concentration
quotient is >1 for 13 Polish sites and this roughly confirms the pyrogenic
origin of PAHs already shown by the low Phe/Anth concentration quotient.
However, at five sites (nos. 3, 31, 40, 43 and 80) the ratio is from 0.062
to 0.79 implying a petrogenic source of PAHs in spite of the low Phe/Anth
concentration quotient ranging from 0.10 to 0.31 (Table 6). The low molecular
weight PAHs predominated (Lmw/Hmw > 1) evidently at three sites (nos. 2,
7 and 51/52) suggesting a petrogenic origin of PAHs but at the same time
values of Phe/Anth and Flu/Pyr concentration quotients showed an opposite
pyrogenic source, which was especially evident for the sites 2 and 51/52
(Table 6).
Apart from the single inland site no 50 with a Naph/Phen ratio around 3
implying petrogenic source, for most other Polish sites the values of Naph/Phen
concentration quotients were below 1, thus supporting the suggestion of
pyrogenic origin of PAHs in agreement with the other above mentioned
parameters. Due to very low concentration of naphthalene or phenanthrene at
some sites (Table 5) no exact value of Napth/Phen concentration quotient could
be calculated with a quotient reaching ∼1 for the sites 3, 8, 31, 40, 43 and 80.
Since all sediment samples in this study could be considered as being more or
less influenced by pyrogenic PAHs sources due to the widespread combustion of
gasoline as well as hard coal, it is clear that petrogenic sources have only minor
significance for most of the investigated sites (Fig. 1). For the two German
reference sediments a pyrogenic source of PAHs predominated (Table 6), while
individual and total PAH concentrations were relatively low and in the range
of some sites from the coast of the Gulf of Gdańsk.
For the evaluation of the contamination of aquatic systems by PAH,
there are legally established quality objectives in the regulations of the
German Bundesländer for the implementation of EU regulation 76/464.
When converted to suspended matter and sediments, resulting values
range between 400 µg/kg d.w. for benzo(a)pyrene and 1000 µg/kg for
2150
Falandysz et al.
benzo(b)fluoranthene, benzo(ghi)perylene, benzo(k)fluoranthene, fluoranthene
and indeno(1,2,3-cd)pyrene. In this study however, the more stringent limit
values conceived by the Institute for Environmental Chemistry Bremen (1984)
were applied.[34] This assessment schema is based on a three-stage model
and defines benzo(a)pyrene and fluoranthene, which are known to be highly
environmentally harmful, as key substances:
benzo(a)pyrene (µg/kg d.m.)
fluoranthene (µg/kg d.m.)
Class 1
Class 2
Class 3
<180
<250
<1800
<2500
>1800
>2500
In class 1, “ecotoxicological effects are not expected”, in class 2, “ecotoxicological effects are likely at prolonged exposure, especially for sensitive
organisms”, and in class 3 concentrations are reached which “make adverse
effects on aquatic organisms, e.g. changes in species diversity, probable at
long-term exposure.”[34]
According to these criteria some sediment are highly contaminated with
PAHs and assigned to quality class 3 (sites 2, 6 from Ostrów Island/Dead Vistula River Canal; site 51/52 from Brdyujście). A number of further sediments
fall into class 2 (sites 3 and 4 from Ostrów Island, sites 11 and 14 at the
outlet of Płutnica River, site 50 from the Brdyujście/Vistula River area, and
sites. 81, 82 and 83 in the Gdynia Shipyard and Port of Gdynia region) and
a lower number into class 1 (sites 7 and 8 from Brzeźno and North Port, site
31 near Mechelinki although—as pointed out earlier—a high contamination
with indeno(123cd)pyrene is apparent, site 80 at Skwer Kościuszki, and sites
40 and 43 near the outlet of the Vistula River).
Butyltins and Phenyltins
A number of sediment samples collected at some locations in the coastal
zone of the Gulf of Gdańsk are apparently highly contaminated with butyltins
and total with concentrations ranging from ND to 30 and from ND to 38 µg/
kg d.m., respectively (Table 3). Amongst the numerous synthetic organotin
compounds used by man the salts of tri- and dibutyltin and tri- and diphenyltin
are important chemicals.[35] No triphenyltin, diphenyltin or monophenyltin
could be found at concentrations above the method limit of quantification in
surface sediment at any site investigated both in Poland and Germany. On
the contrary, tributyltin, dibutyltin and monobutyltin were detected at highly
relevant concentrations at the selected sites in the coastal zone of the Gulf of
Gdańsk. At the same time the compounds were detected at low concentrations
in some further sediment samples from the same region and from inland
Surface Sediment Contamination at the the Baltic Sea Coastal Region
2151
Poland or the butyltins remained below the limit of quantification for the
applied method (Table 7). In the most contaminated sediments (sites 1–4), the
sum of butyltin species reached a high proportion of the total tin concentration,
hereby underlining a relatively recent contamination. At the two investigated
reference sites in Germany neither phenyltins not butyltins were detected
(Table 3).
Tributyltin and triphenyltin are widely used biocides, which among other
found appliance as an effective antifouling agent released from marine paint
formulations directly into the water column. Especially this application leads
to a contamination of water, sediments and biota as well as to a damage of
many organisms and aquatic animal populations.[36–40] In this study, the sites
in the coastal zone of the Gulf of Gdańsk were found to be highly contaminated
with BTs, largely due to the continuous release of TBT from nearby shipyards,
ports and navy facilities. Potential sources and measured contamination levels
in the region are the same as indicated in sediments more than a decade ago
(Table 7).
The tributyltin content in highly contaminated sediment may decrease
relatively rapidly under aerobic conditions due to biodegradation by sediment
microorganisms, while the compound is much more persistent under anaerobic
conditions.[41,42] The continuous presence of TBT and its degradation products
at almost identical concentrations from the 1990s until today of muddy sediments from the Ostrrów Island shipyards, Gdynia Port and its shipyards area
highlight the lack of any serious recent control measures. These conditions are
highly unfavourable to aquatic life.
Metallic Elements
The bulk concentrations of As, Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg,
Mn, Na, Ni, Pb, Sn, Ti, Tl and Zn in analysed surface sediments are given
in Tables 3 and 8, respectively. Concentration varied from site to site for Pb,
Ni, Cu, Zn, Cd, Cr and to a lesser extent for As, Co, Cr, Sn, and Fe, while
only little variability was observed for the other elements. Ni, Cu, Zn, Cd, Pb
and Fe concentrations in sediments from the industrial area of Gdańsk and
Gdynia with its harbours were elevated when compared to the reference sites
from Norderney in the German Wadden Sea. Measured values for the same
elements were comparable or even lower than in the reference sediments at
the sites from inland Poland and in more sandy sediments collected near the
outlet of the Vistula and Reda Rivers (Table 8).
For most of the metallic elements quantified in this study concentrations
were higher when compared with results for related sites from the inner part
in the Gulf of Gdańsk and Puck Bay by other authors.[47–50] In accordance
with our findings, these authors also noted that surface sediments at station
2 in the inner part of the Gulf of Gdańsk show elevated levels of Cd, Cu, Pb
2152
Hel port, outer part, 1993
Mechelinki site, pipe outlet, 2002 (30)
Mechelinki site, 100 m off the pipe
outlet (31)
Mechelinki site, 300 m off the pipe
outlet (32)
Mechelinki site, 600 m off the pipe
outlet (33)
Puck, small river outlet site,
2002 (11)∗∗
Puck, Mechanical Works site,
2002 (12)
Puck, at the port site, 2002 (13)
Puck, at the marina site, 2002 (14)
Puck, 500 m east off the marina, 2002
(15)
Rewa River, outlet region, 2002 (20)
Rewa River, 200 m off the outlet, 2002
(21)
Rewa River, 500 m off the outlet, 2002
(22)
Gulf of Gdańsk, open part, 1994
Hel port, inner part, 1993
ND
ND
0.015
ND
ND
ND
ND
0.026
0.17 (0.17–0.17)
1
1
1
1
1
1
1
1
2
0.027
ND
ND
ND
ND
1
1
1
1
1
1
0.020 ± 0.003
(0.015–10.024)
ND
0.012 ± 0.017
(<0.0006–0.035)
MBT
11
5
Baltic Sea, southern part
Baltic Sea, southern part–open area,
1994
Gulf of Gdańsk
Puck Bay Various sites, 1995
n
Site and year
ND
ND
<0.0008
ND
ND
0.0043
0.055 (0.006–0.10)
ND
ND
ND
ND
0.02
ND
ND
0.011 ± 0.013
(<0.0008–0.0043)
ND
0.006 ± 0.008
(<0.0008–0.016)
DBT
ND
ND
ND
0.031
0.28 (0.18–
0.37)
0.028
ND
ND
<0.0010
0.051
(<0.0010–0.10)
0.024
ND
ND
ND
ND
ND
ND
ND
0.14
ND
ND
ND
0.10)
0.028
BTs
ND
ND
ND
ND
0.10
ND
ND
0.068 ± 0.032
(0.023–0.11)
ND
0.010 ± 0.017
(<0.010–0.039)
TBT
This work
This work
[43]
This work
This work
[43]
[43]
This work
This work
This work
This work
This work
This work
This work
This work
[43]
[43]
Reference
Table 7: Butyltins (BTs) content of surface sediments (mg butyltin cation/kg dry matters) from the southern part of the Baltic Sea
and inland Poland.
2153
0.69
0.33
24 ± 21 (4.6–46)
1
1
3
1
3
8
Ostrów Island area, GSR, 2002 (1)
Ostrów Island area, 1997
Ostrów island area, 1997
0.72
1.0
29 ± 18 (8.0–42)
0.16
7.9 ± 5.7 (2.0–17)
0.052
1
0.059
8.6 ± 7.7 (1.2–23)
0.01
1
ND
ND
ND
9.0
9.3 ± 2.8 (6.5–12)
ND
ND
ND
1
5
2
0.13
0.12
0.20
ND
ND
3.0
11 ± 3 (9.0–14)
0.059
0.089
0.074
ND
ND
1
1
1
1
1
—
—
0.77 ± 0.26
1.8 ± 2.7 (0.61–4.3)
(0.56–0.95)
1
3.0
5.1
21 1.4 ± 1.8 (0.17–8.4)
1.4 ± 2.7
(0.020–9.8)
1
ND
ND
3
3
Gdynia, Skwer Kościuszki site, 2002
(80)
Gdynia, Gdynia Shipyard, 2002 (81)
Gdynia, Passenger ships terminal (82)
Gdynia, Nauta Shipyard, 2002 (83)
Kacza River, outlet, 2002 (60)
Kacza River. 100 m off the outlet,
2002 (61)
Jelitkowski Creak, outlet, 2002 (70)
Vistula River, outlet (40–44)
Sea/Vistula Channel interface, 2002
(8–9)
Coastal inland region
Dead Vistula River Channel
Port Gdańsk canal, 500 m off the
sewage treatment plant pipe outlet,
2002 (7)
Port Gdańsk canal, close to the
sewage treatment plant pipe outlet,
2002 (6)
Kaszubski canal, Wisłoujście, 1993
Kaszubski canal, Nowy Port, 2000 (3)
Ostrów Island area, GSR, 1997
Gdynia marina, 1993
Gdynia marina, 1998
Gdynia seaport, 1993
Gdynia seaport, 1993
1.2
0.40
ND
ND
ND
0.77
1.2
1.5
ND
ND
ND
17
6.0
1.8–2.9
5.8
This work
This work
This work
This work
This work
This work
This work
This work
This work
This work
This work
[43]
[45]
[44]
[43]
2.6
[46]
9.6
This work
84 ± 51
[46]
(30–130)
57
69
This work
19 ± 5 (13–29)
40 ± 10
[46]
(29–48)
16 ± 12 (2.8–38)
33 ± 27
[46]
(5.8–80)
(Continued on next page)
1.2
8.3
31 ± 12 (18–40)
0.99
0.33
ND
ND
ND
0.58
1.0
1.2
ND
ND
8.5
3.2 ± 5.9
(0.024–23)
ND
—
3.2 ± 3.4 (1.2–7.3)
2154
0.0036
0.011
0.00050
0.012
0.048
0.0021
0.0033
0.0083
0.034
0.024
1
1
1
1
1
1
1
1
1
1
0.12
0.17
0.036
0.072
0.15
0.19
< 0.073
ND
0.003
0.12
0.14
0.001
This work
This work
[46]
[46]
[46]
[46]
[46]
[46]
[46]
[46]
[45]
0.93
0.019
0.048
This work
This work
This work
[46]
[45]
[45]
Reference
17
5.9
1.4
0.14
11
3.9
BTs
0.023
0.041
<0.0010
<0.0008
0.010
0.023
0.051
0.024
0.12
<0.0010
<0.0008
0.0061
0.015
0.027
<0.0008
0.0096
14
3.8
0.98
0.12
5.6 ± 5.6 (0.12–14)
1.2 ± 1.7
(0.073–6.8)
0.3 4 ± 0.41
(0.049–1.5)
TBT
taken or adopted from the references cited, respectively; MBT (monobutyltin); DBT (dibutyltin), TBT (tributyltin); ND (not detected); NA (Not
analyzed); ∗∗ For the sites localization see Figs. 1–3; Quantification limit of the method for COMPRENDO samples is, in mg butyltin cation/kg dry
weight, 0.044 for MBT, 0.10 for DBT and 0.37 for TBT; 0.007 for MBT, 0.016 for DBT and 0.073 for TBT in sediments 7, 8, 14, 50 and 51.
∗ Data
Szczecin Lagoon
Karnocice site, 1994
Stepnica harbour, 1994
Inland waters
Gdańsk region
Wieżyca River, Starogard Gd. below
Polfa,1994
Gdańsk, Olszynka site, drainage
canal, 1993
Gdańsk, RN Gdańsk site, drainage
canal, 1993
Gdańsk, Czarna Łacha River, RN site,
1993
Szczecin region
Świna River, Płachnin, 1994
Świnoujście, Mieliński Canal, 1994
Bydgoszcz region, Brda River
–outlet to the Vistula River, 2002 (50)
- sewage treatment plant site, 2002
(51–52)
1
0.42
2.1
1
0.59
1.5
1
0.11
0.32
1
0.017
<0.0008
7 3.2 ± 0.3 (0.20–9.9) 2.0 ± 1.8 (0.12–5.3)
15 1.7 ± 1.5 (0.26–4.8)
0.97 ± 1.09
(0.08–4.3)
11
0.45 ± 0.30
0.18 ± 0.10
(0.15–0.90)
(0.04–0.29)
DBT
Ostrów Island area, 2002 (2)
Channel, Siennicki site, 2002 (4)
Motława River site, 2002 (5)
Channel, Sobieszewo site, 1993
Marina—Yacht Club “Neptun”, 1998
Marina—Yacht Club of Gdańsk
Shipyard, 1998
Marina—AKM-AZS, 1998
MBT
n
Site and year
Table 7: Butyltins (BTs) content of surface sediments (mg butyltin cation/kg dry matters) from the southern part of the Baltic Sea
and inland Poland. (Continued)
2155
2
3
4
5
6
7
8
11
14
31
40
43
50
51–52
80
81
82
83
R1
R2
Sampling site no.
20
26
19
12
9.3
9.5
2.3
5.7
5.6
1.7
1.3
1.9
17
27
3.2
4.8
7.3
7.7
9.8
8.0
Ni
180
67
120
30
34
13
1.7
7.3
5.8
1.9
1.0
1.4
59
77
14
14
26
23
5.7
5.6
Cu
550
240
590
260
270
61
13
41
366
14
17
17
520
110
29
77
130
140
38
37
Zn
8.4
7.0
7.3
4.7
3.0
4.3
0.92
3.6
3.0
0.85
0.78
1.7
3.2
2.8
1.3
2.2
3.2
3.7
6.6
6.6
As
2.4
0.75
1.8
1.4
2.1
0.37
0.08
0.32
0.26
0.11
0.05
0.06
1.1
1.1
0.12
0.35
0.69
0.66
0.22
0.22
Cd
Co
Tl
190
9.0
0.51
130
8.1
0.46
150
11
0.36
48
5.9
0.40
61
3.2
0.31
21
3.9
0.24
7.0
1.2
0.15
19
2.3
0.25
14
2.8
0.24
5.0
0.96
0.16
4.1
0.92
0.12
5.1
1.0
0.15
99
10
0.20
54
6.1
0.19
21
3.4
0.18
19
2.9
0.21
29
3.6
0.25
36
3.7
0.28
18
5.0
0.32
18
5.0
0.32
(Continued on next page)
Pb
Table 8: Concentrations of metallic elements in surface sediments (µg/g dry matter) at selected sites in coastal region of the
Gulf of Gdańsk, inland Poland and the Wadden Sea at the German North Sea coast (for the sites localization see Figs. 1–3).
2156
2
3
4
5
6
7
8
11
14
31
40
43
50
51–52
80
81
82
83
R1
R2
Sampling site no.
63
64
81
38
37
29
11
19
15
6.9
2.3
4.0
55
130
11
30
26
29
44
31
Cr
21000
37000
37000
18000
12000
26000
4600
15000
13000
4400
2200
2400
13000
12000
5200
8800
12000
12000
11000
9300
Fe
250
400
725
290
190
240
160
110
180
110
68
53
500
240
100
115
150
160
240
230
Mn
24000
20000
25000
26000
19000
19000
13000
18000
17000
12000
7500
9100
13000
14000
14000
18000
18000
22000
27000
20000
Al
11000
16000
10000
14000
9200
11000
7300
11000
9600
7600
4800
6700
4700
6500
8800
10000
11000
12000
13000
9200
K
3900
1200
4100
3500
2400
2700
900
3000
2700
740
170
260
2500
1100
1200
1900
1700
3100
4000
3000
Mg
5000
9200
5900
5100
5900
4200
4400
5500
4100
3500
2100
2200
2200
2900
3800
4400
4400
5200
9300
7100
Na
19000
12000
15000
26000
11000
18000
3000
8700
6700
4600
1100
4000
38000
39000
12000
13000
16000
15000
25000
15000
Ca
370
400
360
310
240
250
180
230
220
170
130
170
230
190
180
220
270
280
270
200
Ba
Ti
1800
1700
1600
1800
1100
1300
1500
1400
1300
1200
250
130
1500
570
1000
1300
1600
1700
1800
1400
Table 8: Concentrations of metallic elements in surface sediments (µg/g dry matter) at selected sites in coastal region of the
Gulf of Gdańsk, inland Poland and the Wadden Sea at the German North Sea coast (for the sites localization see Figs. 1–3).
(Continued)
Surface Sediment Contamination at the the Baltic Sea Coastal Region
2157
and Zn, while concentrations of Al, Fe, Ti, Th, Ni, Co, K, Ca, Mg, U and Mn
are more uniformly distributed, indicating a more terrigenous origin.[47,50] It
was also shown that surface sediments (unsieved fraction < 2 mm) collected
from 24 sites in the Gulf of Gdańsk in 1988–1989 were characterised by an
anthropogenic enrichment with Ag, Cd, Pb and Zn, while concentrations of Al,
Ca, Co, Cr, Cs, Cu, Mn, Ni, Fe, K, Li, Mg, Na, Sr and Rb were in the range of
the geochemical background.[49] In another attempt, a sediment core collected
at the mouth of the Vistula River and two cores taken at the inner part of the
Puck Bay in 1991 showed in their finest fraction of < 2 µm anthropogenically
enriched loads of Ag, Cd, Pb and Zn and possibly also Cu and Ni, but not for
Al, Ca, Co, Cr, Fe, K, Mg, Mn and Na.[50]
In our study particularly high concentrations of Cu (120–180 µg/g d.m.),
Pb (130–190 µg/g d.m.), Cd (1.4–2.4 µg/g d.m.) and Zn (260–590 µg/g d.m.)
were found in sediments from the Gdańsk city waterways of the Dead Vistula
River Channel, the Motlawa River and around the Island of Ostrów (Table 8).
At some of these sites also highly elevated concentrations of Ni, Co, Cr, Fe, Mn
and Mg were noted (Table 8).
Sediments were assigned to contamination classes according to the chemical classification system of LAWA (1998) with its transformation according
to the five-stage ecological status classes system of the EU Water Framework
Directive (EU-WFD) developed by Duft et al.[51,52] Sediments are assigned to
a ecological status class, based on the measured concentrations for Cd, Cr, Cu,
Ni, Pb, and Zn. Ecological status classes I and II represent a high and good
ecological status and thus the aim that should be achieved for all European
water bodies in the next years. Status classes III, IV and V indicate increasing
levels of distortion resulting from human activity and require remediation
action. In status class III, the first community-level effects are apparent,
while in status class IV relevant biological communities deviate substantially
from those normally associated with the water body type under undisturbed
conditions. In class V large portions of the relevant biological communities are
absent.[51,52] Among the examined sediments those taken at sites 2, 4 and 50
were assigned to class V (EU-WFD) due to highly elevated Cd, Cr, Cu, Ni, Pb
and Zn concentrations, sediments from sites 3, 5–7, 11, 51–52 and 82–83 were
assigned to class IV, while remaining sediments (R1, R2, 8, 14,31, 40, 43, 80
and 81) showed low (status class III) or no risk (status classes I and II) got the
benthic community (Table 8).
CONCLUSIONS
Thirty-five bulk surface sediment samples were collected in the coastal area
of the Gulf of Gdańsk in the neighbourhood to the cities of Gdańsk, Gdynia
and Puck, and at the selected inland locations in Brdyujście in Poland
2158
Falandysz et al.
as well as at two reference sites in the German Wadden Sea (Norderney
Island). These sediments were comprehensively analysed for androgenic and
antiandrogenic compounds such as butyltins, phenyltins, p pDDE, Fenarimol,
Vinclozolin, Linuron and Diuron, the metabolites DCPU and DCPMU as
well as for p pDDT, p pDDD, PCBs, 16 PAHs and 19 metallic elements. The
analytical findings revealed high contamination levels, indicating a possible
direct sediment toxicity and resulting ecological problems for the benthic
biological communities at the most polluted locations.
There was a wide span of measured concentrations for most analytes
and the different sites investigated. Among chemicals examined butyltins,
PAHs and heavy metals were found to play a most significant role as possible
anthropogenic stressors for the bottom communities in the areas investigated.
The potential impact of PCBs or DDTs, although present in almost all samples,
was lower, while pesticides such as Diuron, Linuron, Fenarimol, Vinclozolin
and phenyltins were only found occasionally. Spatial distribution of chemicals
pointed on the high impact from ship repair facilities, shipyards, industrial
and municipal sewage outfall and dumping areas as sources of the compounds
examined. When compared with earlier investigations in the same are, there
was only little evidence for a decline especially in sediment-associated butyltin
concentrations at high risk sites (ship repair and shipyard industry, port and
navy activities). Consequently, sediments in these areas continue to pose a
detrimental stress for the aquatic communities. Polychlorinated biphenyls
diffusion seems to continue also at a few of the industrial sites investigated.
The two reference surface sediments collected at Norderney Island in the
German Wadden Sea exhibited a comparable contamination level for most
of the analysed compounds when compared with the lowest contaminated
sediment samples from the southwestern part of the Gulf of Gdańsk.
ACKNOWLEDGMENT
This study has been funded under 5 FP of the European Union (COMPRENDO
project, contract EVK1-CT-2002–00129).
REFERENCES
1. Falandysz, J.; Trzosińska, A.; Szefer, P.; Warzocha, J.; Draganik, B. The Baltic Sea:
especially southern and eastern regions. In Seas at The Millenium: An Environmental
Evaluation. Vol. I Regional Chapters: Europe, The Americas and West Africa; Sheppard,
C.R., Ed.; Elsevier Science Ltd.: 2000; 99–120.
2. Monitor 16. Persistent Organic Pollutants. A Swedish View of an International
Problem; Swedish Environmental Protection Agency: 1998. ISBN 98–620–1189–8.
3. Newmann, J.W.; Becker, J.S.; Blondina, G.; Tjeerdema, R.S. Quantitation of Aroclor
using congener-specific results. Environ. Toxicol. Chem. 1998, 17, 2159–2166.
Surface Sediment Contamination at the the Baltic Sea Coastal Region
2159
4. CIPAS. Commissione Internazionale per la Protezione delle Acque Italo-Svizzere.
Monitoraggio della presenza del DDT e di altri contaminanti nell’ecosistema Lago
maggiore, Rapporto annuale Campagna 2003, CNR., I.N.E. Verbania Pallaza, 2003; 69
pp.
5. CIPAS. Commissione Internazionale per la Protezione delle Acque Italo-Svizzere.
Monitoraggio della presenza del DDT e di altri contaminanti nell’ecosistema Lago
maggiore, Rapporto annuale Campagna 2003, CNR., I.N.E. Verbania Pallaza, 2004; 78
pp.
6. DIN 38414 S21. Bestimmung von 6 polyzyklischen aromatischen Kohlenwasserstoffen (PAK) mittels Hochleistungs-Flüssigkeitschromatographie (HPLC). In: Fachgruppe Wasserchemie der GDCh und Normenausschuss Wasserwesen (NAW) im DIN
Deutsches Institut für Normung e.V. (ed.): Deutsche Verfahren zur Wasser-, Abwasserund Schlammuntersuchung. Band 1. VCH, Weinheim; Beuth, Berlin, Germany. Loseblattsammlung, 1996.
7. DIN 38406 E29. Bestimmung von 61 Elementen durch Massenspektrometrie mit
induktiv gekoppeltem Plasma (ICP-MS). In: Fachgruppe Wasserchemie der GDCh und
Normenausschuss Wasserwesen (NAW) im DIN Deutsches Institut für Normung e.V.
(ed.): Deutsche Verfahren zur Wasser-, Abwasser- und Schlammuntersuchung. Band
1. VCH, Weinheim; Beuth, Berlin, Germany. Loseblattsammlung, 1996.
8. Konstantinou, I.K.; Albanis, T.A. Worldwide occurrence and effects of antifouling
paint booster biocides in the aquatic environment: A review. Environ. Intern. 2004, 30,
235–248.
9. Ahlborg, U.; Lipworth, L.; Titus-Ernstaff, L.; Hsieh, C.; Hanberg, A.; Baron,
J.D.; Trichopoulos, D.; Adami, H. Organochlorine compounds in relation to breast
cancer, endometrial cancer and endometriosis: An assessment of the biological and
epidemiological evidence. Crit. Rev. Toxicol. 1995, 25, 463–531.
10. Falandysz, B.; Strandberg, L. Strandberg and C. Rappe, C. Tris(4chlorophenyl)methane and tris(4-chlorophenyl)methanol in environmental matrices
from the Baltic south coast. Environ. Sci. Technol. 1999, 33, 517–521.
11. UNECE. Risk profile and summary report for Dicofol., 2003.
12. Falandysz, J. Polychlorinated biphenyl concentrations in cod-liver oil: Evidence of
a steady-state condition of these compounds in the Baltic area oils and levels noted in
Atlantic oils. Arch. Environ. Contam. Toxicol. 1994, 27, 266–271.
13. Strandberg, B.; Strandberg, L.; van Bavel, B.; Bergqvist, P-A.; Broman, D.;
Falandysz, J.; Näf, C.; Papakosta, O.; Rolff, C.; Rappe, C. Concentrations and spatial
variations of cyclodienes and other organochlorinaes in herring and perch trom the
Baltic Sea. Sci. Total Environ. 1998, 215, 68–93.
14. Falandysz, J.; Brudnowska, B.; Iwata, H.; Tanabe, S. Organochlorine pesticides
and polychlorinated biphenyls in the Vistula River water (in Polish). Roczn. Państw.
Zakł. Hig. 1999, 50, 123–130.
15. Falandysz, J.; Brudnowska, B.; Iwata, H.; Tanabe, S. Organochlorine pesticides
and polychlorinated biphenyls in ambitne air in Gdańsk. Roczn. Państw. Zakł. Hig.
1999, 50, 39–47. (in Polish).
16. Falandysz, J.; Brudnowska, B.; Kawano, M.; Wakimoto, T. Polychlorinated
biphenyls and organochlorine pesticides in soils from the southern part of Poland. Arch.
Environ. Contam. Toxicol. 2000, 40, 173–178.
17. Falandysz, J. Organochlorine pesticides and polychlorinated biphenyls in surface
layer of sandy sediment in Puck Bay. Bromat. Chem. Toksykol. 1992, 25, 387–390. (in
Polish)
2160
Falandysz et al.
18. Falandysz, J.; Strandberg, B. Persistent organochlorine compounds in sludge and
sediments from the Gdańsk region, Baltic Sea. Pol. J. Environ. Stud. 2004, 13, 133–
138.
19. Kawano, M.; Falandysz, J.; Brudnowska, B.; Wakimoto, T. Organochlorine
residues in freshwater sediments in Poland. Organohalogen Compd. 1998, 39, 331–
335.
20. IFREMER.. Reseau National d’Observation de la qualite du Milieu Marin (RNO),
1998. www.fremer.fr
21. Koci, K.The trend of POP pollution in the Albanian Adriatic Coast. Case study of
PCBs UNEP/IFCS (1992–1996) 1998, 101–106.
22. Albanis, T.A.; Danis, T.G.; Kouriga, M.K. Transportation of pesticides in estuaries
of the Axios, Loudias and Aliakmon rivers (Thermaikos Gulf), Greece. Sci. Total
Environ. 1994, 156, 11–19.
23. Albanis, T.A.; Danis, T.G.; Hela, G.D. Transportation of pesticides in estuaries of
Louros and Arachthos rivers (Amvrakikos Gulf, N.W. Greece). Sci. Total Environ 1995,
171, 85–93.
24. Kannan, K.; Kober, J.L.; Khim, J.S.; Szymczyk, K.; Falandysz, J.; Giesy, J.P. Polychlorinated biphenyls, polycyclic aromatic hydrocarbons and alkylphenols in sediments
from the Odra River and its tributaries, Poland. Toxicol. Environ. Chem. 2003, 85,
51–60.
25. Witt, G. Polycyclic aromatic hydrocarbons in water and sediment of the Baltic Sea.
Mar. Pollut. Bull. 1995, 31, 237–248.
26. Norta, M.; Leskovsek, H.; Fagneli, J. Composition, distribution and sources of
polycyclic aromatic hydrocarbons in sediments of the Gulf of Trieste. Mar. Pollut. Bull.
2001, 42, 36–44.
27. Olajire, A.A.; Altenburger, R.; Küster, E.; Brack, W. Chemical and ecotoxicological
assessment of polycyclic aromatic hydrocarbon—contaminated sediments of the Niger
Delta, Southern Nigeria. Sci. Total. Environ. 2005, 340, 123–136.
28. Bernner, B.A.; Gondon, G.E.; Wise, S.A. Mobile sources of atmospheric polycyclic
aromatic hydrocarbons: a roadway tunnel study. Environ. Sci. Technol. 1989, 23, 1269–
1274.
29. Geschwend, P.M.; Hites, R.A. Fluxes of PAH to marine and lacustrine sediments
in the northeastern USA. Geochim. Cosmochim. Acta 1981, 45, 2359–2367.
30. Colombo, J.C.; Pelletier, E.; Brochu, C.; Khalil, M.; Catoggio, J.A. Deteremination
of hydrocarbons sources using n-alkanes and polycyclic aromatics distribution indexes.
Case study: Rio de la Plata, Argentina. Environ. Sci. Technol. 1989, 23, 888–894.
31. Budziński, H.; Jones, J.; Bellocq, J.; Pierrad, C.; Garrigues, P. Evaluation of
sedyment contamination by polycyclic aromatic hydrocarbons in the Gironde estuary.
Mar. Chem. 1997, 58, 85–97.
32. Dahle, S.; Savinov, V.M.; Matishov, G.G.; Evenset, A.; Naes, K. Polycyclic aromatic
hydrocarbons (PAHs) in bottom sediment of the Kara Sea Shelf, Gulf of Ob and Yenisei
Bay. Sci. Total Environ. 2003, 306, 57–71.
33. Sicere, M.A.; Marty, J.C.; Saliot, A.; Aparicio, X.; Grimalt, J.; Albaiges, J. Aliphatic
and aromatic hydrocarbons in different sized aerosols over the Mediterranean Sea:
Occurrence and origin. Atmosph. Environ. 1987, 21, 2247–2259.
34. Institute for Environmental Chemistry Bremen. Analyses and Assessment of
Sediment Samples from Bremen and Bremerhavens by Biological Effect Tests. Final
Surface Sediment Contamination at the the Baltic Sea Coastal Region
2161
report 001.89.01 for the Senator for Construction and the Environment Bremen (in
German), 1984.
35. Hoch, M. Organotin compounds in the environment—An overview. Appl. Geochem.
2001, 16, 719–743.
36. Albalat, A.; Potrykus, J.; Pempkowiak, J.; Porte, C. Assessment of organotin
pollution along the Polish coast (Baltic Sea) by using mussels and fish as sentinel
organisms. Chemosphere 2002, 47, 165–171.
37. Belfroid, A.C.; Purperhart, M.; Ariese, F. Organotin levels in seafood. Mar. Pollut.
Bull. 2001, 40, 226–232.
38. Guruge, K.S.; Tanabe, S. Contamination by persistent organochlorines and
butyltin compounds in the West Coast of Sri Lanka. Mar. Pollut. Bull. 2001, 42,
179–186.
39. De Mora, S.J.; Fowler, S.W.; Cassi, R.; Tolosa, I. Assessment of organotin contamination in marine sediments and biota from the Gulf and adjacent region. Mar. Pollut.
Bull. 2003, 46, 410–409.
40. Ueno, D.; Inoue, S.; Takahashi, S.; Ikeda, K.; Tanaka, H.; Subramanian, A.N.;
Fillmann, G.; Lam, P.K.; Zheng, J.; Muchtar, M.; Prudente, M.; Chung, K.; Tanabe, S.
Global pollution monitoring of butyltin compounds using skipjack tuna as a bioindicator. Environm. Pollut. 2004, 127, 1–12.
41. Dowson, P.H.; Bubh, J.M.; Williams, T.P.; Lester, J.N. Persistence and degradation
pathways of tributyltin in freshwater and estuarine sediments. Water Sci. Technol.
1993, 28, 133–137.
42. Landmeyer, J.E.; Tanner, T.L.; Watt, B.E. Biotransformation of tributyltin to tin
in freshwater river-bed sediments contaminated by an organotin release. Environ. Sci.
Technol. 2004, 38, 4106–4112.
E. Butyltins in marine and
43. Szpunar, J.; Falandysz, J.; Schmitt, V.; Obrebska,
freshwater sediments of Poland. Bull. Environ. Contam. Toxicol. 1997, 58, 859–864.
44. Kannan, K.; Falandysz, J. Butyltin residues in sediment, fish, fish-eating birds,
harbour porpoise and human tissues from the Polish coast of the Baltic Sea. Mar. Pollut.
Bull. 1997, 34, 203–207.
45. Falandysz, J.; Brzostowski, A.; Szpunar, J.; Rodriguez-Pereiro, I. Butyltins in
sediments and three-spined stickleback (Gasterosteus aculleatus) from the marinas of
the Gulf of Gdańsk, Baltic Sea. J. Environ. Sci. Health. 2002, A37, 353–363.
46. Senthilkumar, K.; Duda, C.A.; Villeneuve, D.L.; Kannan, K.; Falandysz, J.; Giesy,
J.P. Butyltin compounds in sediment and fish from the Polish coast of the Baltic Sea.
Environ. Sci. Poll. Res. 1999, 6, 200–206.
47. Skwarzec, B.; Bojanowski, R.; Bolałek, J. Rozmieszczenie pierwiastków
chemicznych w wybranych basenach południowego Baltyku. Stud. Mat. Oceanolog.
KBM PAN 1985, 48, 69–72.
48. Szefer, P.; Skwarzec, B. Distribution and possible sources of some elements in the
sediments of the southern Balic. Mar. Chem. 1988, 23, 109–129.
49. Szefer, P.; Szefer, K.; Glasby, G.P.; Pempkowiak, J.; Kaliszan, R. Heavy-metal
pollution in surfacial sediments from the Baltic Sea off Poland. J. Environ. Sci. Health
1996, A31, 2723–2754.
50. Szefer, P.; Kusak, A.; Szefer, K.; Glasby, G.P.; Jankowska, H.; Wołowicz, M.; Ali,
A.A. Heavy-metal pollution in surficial sediments from the southern Baltic Sea off
Poland. Appl. Geochem. 1998, 13, 293–304.
2162
Falandysz et al.
51. Länderarbeitsgemeinschaft Wasser (LAWA).Beurteilung der Wasserbeschaffenheit
von Fließgewässern in der Bundesrepublik Deutschland–Chemische Gewässer-güteklassifikation; Kulturbuchverlag: Berlin, Germany, 1998.
52. Duft, M.; Tillmann, M.; Oehlmann, J. In Ecotoxicological sediment survey of large
German rivers; et al., Ed.; Federal Environmental Agency: Berlin, Germany, 2003. (in
German)