Marine Pollution Bulletin 62 (2011) 1464–1475

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Marine Pollution Bulletin

journal homepage: www.elsevier.com/locate/marpolbul

The relationship between the concentrations and distribution of organic

pollutants and black carbon content in benthic sediments in the Gulf of Gdańsk,
Baltic Sea
M. Staniszewska a, D. Burska a,⇑, G. Sapota b, M. Bogdaniuk b, K. Borowiec a, I. Nosarzewska a, J. Bolałek a
a
Department of Marine Chemistry and Environmental Protection, Institute of Oceanography, University of Gdansk, Al. Marszałka Piłsudskiego 46, 81-378 Gdynia, Poland
b
Department of Environmental Protection, Maritime Institute in Gdansk Długi Targ 41/42, 80-830 Gdańsk, Poland

a r t i c l e i n f o a b s t r a c t

Keywords: The influence of the sediment’s physico–chemical properties and black carbon content, on the distribu-
Black carbon tion of polycyclic aromatic hydrocarbons and polychlorinated biphenyls in benthic sediments of the Gulf
Gulf of Gdansk of Gdansk (Baltic Sea) was determined. Sediments from port, marine dump site of dredged spoils, the Vis-
Polycyclic aromatic hydrocarbons tula river mouth, Gdansk Deep were selected.
Polychlorinated biphenyls P
The concentrations of PAHs (fluoranthene, pyrene, benzo(a)anthracene, benzo(k)fluoranthene, ben-
Sediments P
zo(a)pyrene, dibenzo(ah)anthracene, benzo(ghi)perylene) were 294–2200 ng/g d.w. and for PCBs (28,
52, 101, 118, 138, 153, 180) were 2.4–11.3 ng/g d.w.
The sediments content of loss on ignition was 1.13–16.15%, total organic carbon was 0.89–7.15%, black
carbon was 0.20–1.15%. The highest correlation coefficient values (r = 0.76–0.92, p < 0.05) for a relation-
ship between the concentrations of organic pollutants, and organic matter, organic and black carbon con-
tents were obtained in harbor sediments with low content of organic matter (<5%) and high share of black
carbon in total carbon (up to 40%).
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction the immune, reproductive and hormonal system (Falandysz,

Significant amounts of toxic hydrophobic organic contaminants
(HOCs) accumulate at sea in benthic sediments because these com-
pounds have poor solubility in water and tend to sorb to particles
of suspended matter (Oren et al., 2006). Theoretically, hydrophobic
contaminants become immobilized in bottom sediments where
they are relatively safe for the environment. However the sediment
is not only a trap for the contaminants. Sorption and desorption
processes can occur in the direction of bonding and release of toxic
compounds which will result in return fluxes. Consequently, this
may influence the compounds’ bioavailability to the marine organ-
isms in the water column. Benthic organisms are constantly ex-
posed to the contaminants stored in sediment. Moreover, toxic
compounds can be transferred up the food chain where they may
pose a threat to the organisms at higher trophic levels (Burton
and Landrum, 2003; Tremblay et al., 2005).
Among hydrophobic contaminants, polycyclic aromatic hydro-
carbons (PAHs) and polychlorinated biphenyls (PCBs) are consid-
ered the most widespread considered highly dangerous to the
marine environment. PAHs and PCBs are mainly detrimental to
⇑ Corresponding author. Tel.: +48 58 523 68 41; fax: +48 58 523 66 78.
E-mail address: ocedb@univ.gda.pl (D. Burska).
1999). PAHs can also trigger carcinogenesis (Xue and Warshawsky,
2005).
The source of PAHs emitted into the environment is burning of
solid fuels, mainly coal; vehicle exhaust fumes; accidental fires;
burning of waste; heavy industry; coke plants; electric power
plants and combined heat and power stations. PAHs are trans-
ported into the sea mainly via atmospheric deposition and waste-
water, and during tanker wrecks (Oren et al., 2006). PCBs, which
are non-flammable and chemically resistant compounds with very
stable dielectric properties, were produced in significant amounts
in mid-20th century. They were mainly used as the components
of insulting medium for transformers and condensers. That was
the exact point in time when PCBs were introduced into the envi-
ronment in large amounts (Falandysz, 1999).
Significant amounts of PAHs and PCBs accumulate in benthic
sediments (Mitra et al., 1999). PAHs are present in benthic sedi-
ments at concentrations ranging from couple to tens, or even hun-
dreds of mg/kg d.w., particularly in port and shipyard areas and in
the river mouths (Guz et al., 2000). PCBs occur in sediments at
much lower concentrations as compared to PAHs, i.e. at the levels
of couple to tens of lg/kg d.w. Determination and monitoring of
PAHs and PCBs in sediments is legally required during dredging
of waterways in the countries that are contracting parties to the

0025-326X/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.marpolbul.2011.04.013
 M. Staniszewska et al. / Marine Pollution Bulletin 62 (2011) 1464–1475
Helsinki Convention, and that includes Poland (Ministerstwo
Środowiska, 2002; HELCOM Guidelines, 2007).
The content and distribution of hydrophobic contaminants in
the marine bottom sediments depends on many factors, inter alia,
the distance from the potential emission source; the sediment’s
physico–chemical properties which determine its sorptive capabil-
ities; physico–chemical properties of water which influence among
others the solubility of compounds; and the properties of com-
pounds. The type of bonding between hydrophobic contaminants
and sediment is particularly significant in respect to toxicity, bio-
availability to organisms and the environmental pathways of
compounds.
Black carbon is one of the more important factors that influence
the retention of hydrophobic contaminants in benthic sediments
and the health risk resulting from the presence of these com-
pounds (Jonkers and Koelmans, 2002; Chin-Chang et al., 2006;
Koelmans et al., 2006). Due to occlusion in soot and carbon parti-
cles the hydrophobic compounds become very strongly bonded
to solid particles. Strong bonding between toxic compounds and
carbon in sediment limits the transport of HOCs into the water col-
umn, and therefore it decreases the risk of a secondary introduc-
tion of these contaminants into the ecosystem and making them
bioavailable to organisms (Jonkers and Koelmans, 2002; Ghosh
et al., 2003; Huang et al., 2003; Ahrens and Depree, 2004; King
et al., 2004; Koelmans et al., 2006). Inflow of new portions of car-
bon from the atmosphere results in sorption of hydrophobic organ-
ic compounds that are dissolved in water. This has a ‘‘cleansing
effect’’ on the water basin (Bucheli and Gustafsson, 2003; Ahrens
and Depree, 2004). It can be stated that black carbon plays a posi-
tive role in the marine environment as it allows ‘‘stable’’ immobi-
lization of hydrophobic organic contaminants in sediments
(Accardi-Dey and Gschwend, 2003; Koelmans et al., 2006).
In the presented study the influence of the sediment’s physico–
chemical properties, and specifically black carbon content, on the
distribution of PAHs and PCBs in benthic sediments of the Gulf of
Gdansk (Baltic Sea) was determined. Only very hydrophobic (Ko/
w > 5) PAHs (fluoranthene (FLU), pyrene (PYR), benzo(a)anthra-
cene (B(a)A), benzo(k)fluoranthene (B(k)F), benzo(a)pyrene
(B(a)P), dibenzo(ah)anthracene (D(ah)A) and benzo(ghi)perylene
(B(ghi)P)) and PCB congeners (PCB 28, PCB 52, PCB 101, PCB 118,
PCB 138, PCB 153 and PCB 180) were determined from sediments.
It is known that PAHs more than 4 rings are dominated over the
lighter PAHs in sediments (Sanchez-Gracia et al., 2010). Sediments
from the areas under the influence of anthropogenic pollution
sources (port, marine dump site of dredged spoils, the Vistula river
mouth), the transport and accumulation type sea bottom (from the
Vistula river mouth into the gulf, Gdansk Deep) were selected for
this work.
2. Materials and methods
2.1. Sampling sites
In spring 2007, benthic sediment cores were collected in the
Gulf of Gdansk area (Fig. 1) along the Vistula Spit, east from the
Vistula river mouth (stations W9, W6 and W1); in the Gdansk Deep
(G4); from the dredged spoils dump site (Klapowisko Gdansk, KL);
_ We˛glowe (Coal Pier)), P; sam-
and in the Port of Gdansk (Nabrzeze
pled in 2003) during cruises on k/h Oceanograf 2 and Polish Navy
vessel ORP Arctowski. Sediments were collected with a Niemistö
corer (int. diameter 7.6 cm; core length ca. 25 cm). Cores were
cut into the following segments: 0–2, 2–5, 5–10, 10–15, 15–
20 cm, with an exception of KL station where due to technical rea-
sons a 10-cm core was collected. Sediment samples were stored at
20 °C until analysis.
1465
2.2. Determination of PAHs and PCBs
In order to determine PAHs and PCBs, the frozen benthic sedi-
ment was lyophilized and next comminuted and homogenized.
PAHs, i.e. fluoranthene (FLU), pyrene (PYR), benzo(a)anthracene
(B(a)A), benzo(k)fluoranthene (B(k)F), benzo(a)pyrene (B(a)P),
dibenzo(ah)anthracene (D(ah)A) and benzo(ghi)perylene (B(ghi)P)
were extracted from sediment samples with dichloromethane in
an ultrasonic bath (1 h extraction at 30–35 °C). The obtained
dichloromethane extracts were purified in columns packed with
silica gel and copper powder. After evaporation to dryness dichlo-
romethane was replaced with acetonitrile (Song et al., 2002; Wol-
ska, 2002). The final determination was performed by using liquid
chromatography (Waters) equipped with a fluorescence detector
(kex = 270 nm, kem = 400 nm). Chromatographic separation was
conducted in the reverse-phase system with a column CC 250/4.6
NUCLEOSIL 100-5 C18 PAH (Macherey–Nagel) and acetoni-
trile:water mobile phase gradient.
The isolation of PCB congeners (PCB 28, PCB 52, PCB 101, PCB
118, PCB 138, PCB 153 and PCB 180) from sediment samples was
performed by extraction with 6 cm3 of dichloromethane in a sha-
ker (24 h extraction at 21 °C). The obtained dichloromethane
extracts were purified in columns packed with silica gel, and
the extract volume was brought down to 1 cm3 (Wolska and
Namieśnik, 2002; Smith et al., 2009). Next, polychlorinated biphe-
nyls were determined by means of Gas Chromatograph Hewlett
Packard 6890 equipped with 30 m  0.32 mm I.D. fused-silica cap-
illary column, coated with 0.5 lm nonpolar DB-5 phase (J&W), and
Mass Spectrometry Detector 5973 operated in the selected-ion
monitoring (SIM) mode.
2.3. Validation and quality parameters of PAHs and PCB analyses
All solvents (water, acetonitrile, dichloromethane and metha-
nol) were HPLC grade. Solutions of PAHs (10 lg/cm3) were
obtained from Supelco. PCBs standard solution of LGC Standards
(10 lg/cm3) was used. Multilevel external calibration of seven
PAHs in methanol (working solutions ranged: 10–200 ng/cm3)
and seven PCBs congeners in isooctane (working solutions ranged:
1–100 ng/cm3) was applied for quantification. The linearity were
calculated by least-squares linear regression analysis (correlation
coefficient r2 > 0.998). HPLC or GC system was calibrating before
each measurement series with minimum of three replications of
each concentration of working solution.
Concentration of each compounds was corrected by the rele-
vant mean recovery. Samples of different known PAHs or PCBs con-
tent were used. For calculation were used determinations of three
concentrations, three replicates each (Swartz and Krull, 2008). The
recovery was calculated on the bases of results of reference mate-
rial (SETOC – International Sediment Exchange for Tests on Organic
Contaminants – WEPAL programme). The mean recovery of deter-
mined PCBs varied from 93% to 114%. The mean recovery of deter-
mined PAHs depended on compounds and varied from 70% to 102%
for each from PAHs with exception fluoranthene (52%).
The obtained precision (by six repetition in samples of known
PAHs or PCBs content) was estimated by coefficient of variation
and varied from 2% to 15% for individual PAHs and from 0.2% to
16.9% for individual PCBs.
The accuracy of analytical method for determining PCBs in sed-
iment samples has been tested in International Sediment Exchange
for Tests on Organic Contaminants – WEPAL programme organised
by Wageningen University (the Netherlands) with a good result
(|Z| < 2).
The obtained background values for PAHs and PCBs were con-
trolled by analysis of the blank sample (in the same way as
1466 M. Staniszewska et al. / Marine Pollution Bulletin 62 (2011) 1464–1475
Fig. 1. Location of measuring stations.
sample). Limits of quantification for the specific PAHs ranged from
1 to 4 ng/g d.w. and for the specific PCBs was 0.1 ng/g d.w.
Each sample of sediments was analysed in two replicates. The
results were the averaged arithmetic means of these two
measurements.
2.4. Determination of physico–chemical parameters of benthic
sediments
Water content of sediment was determined by measuring the
loss of mass in wet sediment during a 24-h drying procedure at
105 °C after reaching constant mass weight.
A granulometric analysis was conducted via sieving of dry sed-
iment through a set of metal sieves with the following mesh size
diameters: 2.00, 1.00, 0.5, 0.25, 0.125 and 0.063 mm.
Loss on Ignition (LOI) was determined by igniting the dry sedi-
ment sample in a muffle furnace at 550 °C until reaching constant
mass weight for 4 h (Heiri et al., 2001).
Total Carbon (TC) was measured by burning the dry sediment
sample in a Perkin Elmer CHNS/O 2400 analyzer. Black carbon
(BC) was analysed with chemothermal oxidation method, as de-
scribed in Gustafsson et al. (1997) and Elmquist et al. (2004). Dry
sediment samples (ca. 10–20 mg) were heated at 375 °C for 18 h
under a constant air flow. The residual carbon content was deter-
mined as BC, after in situ acidification (with 1 M HCl) was mea-
sured in an elemental analyzer. TC and BC was analysed by
Elemental Microanalysis Ltd (Devon, United Kingdom).
The precision of the method ranges (replicates analysis of the
certified reference materials) was better than 5% and 7%
respectively.
3. Results
3.1. Physico–chemical characteristics of the analyzed sediments
In the deepest part of the Gulf of Gdansk, i.e. the Gdansk Deep
(G4; 104 m depth) the presence of silty-clay sediment with the
highest share (over 90%) of the smallest grain fraction
(<0.063 mm) was established. Also the sediments collected at sta-
tion W1 were characterized by a high content of the smallest grain
E
fraction ranging from 75% to 80%. Sediments from the remaining
stations were sandy (Table 1).
Surface sediments collected at the most eastern location rela-
tive to the Vistula river mouth (W1) and from the deepest station
in the Gdansk Deep (G4) had the highest organic matter content.
These sediments were also characterized by the highest percentage
of total carbon and water content (Table 1). The sediments col-
lected in the Port of Gdansk (P) and at the dredged spoils dump site
(Klapowisko Gdansk, KL) displayed 2–6 times lower LOI values
and, on average, 3.2 and 1.5 times lower values of TC and water
content, respectively, as compared to those from stations W1 and
G4 (Table 1).
Sediments collected from the Gulf of Gdansk (stations W9, W6,
W1 and G4) were characterized by a decreasing percent content of
organic matter, total carbon and water content with the increasing
sediment depth. Sediments collected in the port and at the dump
site did not show such trend (Table 1).
The highest content of black carbon was found in the sediments
collected at stations W1 and G4; the mean BC content for all sam-
ples was 0.82%. The sediment samples from stations W9, W6
(BC = 0.42%), and KL and P (BC = 0.39% for both) were characterized
by lower black carbon content. The highest share of black carbon in
total carbon was determined in sediment collected in the port, at
the dredged spoils dump site and from the deepest stations located
in the Gulf of Gdansk, i.e. G4 and W1 (Fig. 2). Percentage share of
black carbon in total carbon equaled, on average, 27%, 21%, 18%
and 14% for stations P, KL, W1 and G4, respectively.
3.2. Polycyclic aromatic hydrocarbons (PAHs) and Polychlorinated
biphenyls (PCBs)
The total concentrations of polychlorinated biphenyls and poly-
cyclic aromatic hydrocarbons had the lowest values in sediment
samples collected at the location closest to the Vistula river mouth,
while the highest concentrations of these compounds were ob-
served in the port sediments. In the case of PCBs, the measured
concentrations in the averaged sediment core sample varied from
ca. 2.4 ng/g d.w. (station W9) to 11.3 ng/g d.w. (station P). The total
PAH concentrations in the averaged sample from the entire sedi-
ment core ranged from 294 ng/g d.w. (station W9) to 2200 ng/g
d.w. (station P) (Table 2).
 M. Staniszewska et al. / Marine Pollution Bulletin 62 (2011) 1464–1475 1467

Table 1
Station depth and sediment parameters e.g. water content of sediment, total carbon, black carbon, loss on ignition, content of the <0.063 mm grain size fraction (%) and sediment
type.

Station Deep of Layer of Water content of TCa (%) (n = 2)d BCb (%) (n = 2) LOIc (%) (n = 1) Content of the Sediment type
station sediment sediment (%) <0.063 mm
(m) (cm) grain size fraction (%)
W9 0–2 n.d. 4.69 0.58 6.43 n.d. Medium sand
2–5 3.62 0.29 4.22
5–10 2.86 0.39 3.64
10–15 2.33 0.32 4.66
64 15–20 2.57 0.43 2.72
W6 0–2 68.38 4.76 0.65 9.16 56 Sandy-mud
2–5 64.99 4.48 0.49 9.09 47
5–10 60.01 2.74 0.34 4.32 50
10–15 59.10 3.89 0.39 4.17 49
68 15–20 58.71 2.84 0.34 4.69 38
W1 0–2 80.15 6.30 0.98 16.15 80 Sandy-mud
2–5 76.12 5.84 0.51 12.72 72
5–10 74.90 5.15 1.15 11.25 73
10–15 73.57 4.18 0.73 10.61 68
73 15–20 69.51 4.47 1.06 11.96 70
G4 0–2 81.36 7.15 1.02 13.40 94 Mud
2–5 79.20 6.18 0.8 15.66 92
5–10 77.63 5.37 0.67 9.23 94
10–15 78.34 4.38 0.6 7.09 90
104 15–20 76.39 3.89 0.69 6.73 91
KL 0–2 n.d. 1.56 0.35 1.70 n.d. Medium and coarse sande
2–5 0.89 0.20 1.13
45 5–10 1.12 0.19 4.86
P 0–2 48.41 1.15 0.20 1.20 14 Medium and coarse sand
2–5 38.10 3.36 0.50 4.50 15
5–10 56.45 1.57 0.46 2.20 16
10–15 47.37 1.80 0.61 2.40 12
8 15–20 59.52 1.62 0.61 2.10 11
a
TC, Total carbon (standard deviation was 0051% for TC P 4%, 0035% for 1% 6 TC < 4% and 0007% for TC < 1%.
b
BC, Black carbon (standard deviation was 0046% for BC P 1.0%; 0014% for 0.5% 6 BC < 1% and 0009% for BC < 0. 5%),
c
LOI, Loss on ignition.
D
Number of samples, n.d., No data.
e
Urbański (2007).

40

35

30

25
BC/TC (%)

20

15

10

0
02
25
5 10
10 15
15 20
02
25
5 10
10 15
15 20
02
25
5 10
10 15
15 20
02
25
5 10
10 15
15 20
02
25
5 10
02
25
5 10
10 15
15 20

W9 W6 W1 G4 KL P

stations/sediment layer (cm)

Fig. 2. Percentage share of black carbon (BC) in total carbon (TC) in the analyzed benthic sediment.

3.2.1. Vertical distribution of PAHs and PCBs in sediment cores
Klapowisko Gdansk, the dredged spoils dump site, was the only
station where the maximum PAHs concentration was observed in
the surficial sediment layer (0–2 cm). In the remaining cases, the
maximum total concentration values for PCB congeners and PAHs
were determined in the sediment layers, i.e. 2–5 and 5–10 cm. In
P
all cases, the lowest PAHs values were measured in the deepest
sediment layer, i.e. 15–20 cm, except G4 station were no indication
P
of decrease in concentration PAHs values in deepest layer of sed-
iment (Fig. 3).
1468 M. Staniszewska et al. / Marine Pollution Bulletin 62 (2011) 1464–1475

Table 2
Outcome of statistical analyses of concentrations PAHs and PCBs (ng/g d.w.) in sediment core.
P P
Station/ FLU PYR B(a)A B(k)F B(a)P D(ah)A B(ghi)P 7PAHs PCB28 PCB52 PCB101 PCB118 PCB138 PCB153 PCB180 7PCBs
parameters
W9
Min. 9 9 6 13 6 8 9 67 0.1 0.2 <0.1 <0.1 <0.1 <0.1 <0.1 0.6
Max. 96 89 68 80 81 40 46 462 1.6 2.3 0.5 0.5 0.3 1.0 0.3 5.9
Mean 59 53 41 41 47 23 29 294 0.6 1.2 0.3 0.4 0.2 0.6 0.3 2.4
V 65 65 70 72 69 54 60 61 106 70 – – – – – 88
W6
Min. 9 4 4 9 10 13 32 81 0.3 0.5 <0.1 0.2 <0.1 <0.1 <0.1 2.9
Max. 114 104 107 58 107 54 89 555 1.5 3 0.3 1.2 0.8 0.6 0.6 6.4
Mean 64 57 52 34 49 30 60 343 0.9 1.4 0.2 0.6 0.4 0.4 0.5 3.9
V 64 70 99 57 75 60 36 57 49 70 55 66 83 51 20 36
W1
Min. 59 66 64 58 58 18 12 392 0.6 0.5 0.1 1.0 0.2 0.1 <0.1 7
Max. 288 295 255 167 230 86 122 1442 5.4 6.0 3.3 2.4 1.8 0.9 1.8 15.4
Mean 120 139 133 85 108 46 79 709 2.6 3.4 1.4 1.5 0.7 0.6 1.2 10.9
V 80 65 61 55 64 61 61 60 81 58 91 39 96 57 73 37
G4
Min. 66 51 43 31 42 22 12 370 0.4 0.3 0.1 0.2 0.1 0.3 <0.1 2.5
Max. 162 112 98 86 63 64 130 547 0.7 1.5 0.3 1.1 0.9 1.5 2.0 6.7
Mean 111 86 61 61 52 38 68 477 0.6 0.7 0.2 0.5 0.4 0.8 1.0 3.8
V 32 30 36 38 18 42 66 15 20 62 35 69 75 60 82 44
KL
Min. 33 38 25 14 25 5 4 147 0.1 0.3 0.2 0.3 0.1 0.2 0.1 1.5
Max. 151 196 133 31 65 14 45 635 0.6 1 0.5 0.4 0.3 0.6 0.5 3.4
Mean 82 94 70 24 39 8 19 336 0.3 0.5 0.4 0.4 0.2 0.3 0.4 2.6
V 75 94 80 37 57 59 116 78 88 76 43 16 50 69 63 38
P
Min. 75 68 321 92 181 44 59 1181 <0.1 <0.1 0.3 <0.1 0.1 0.1 <0.1 4.2
Max. 924 697 989 256 636 120 306 3929 3.9 9.8 1.6 0.7 1.8 2.1 4.1 15.9
Mean 471 426 519 177 352 79 176 2200 2.8 5.9 0.7 0.3 1.2 1.1 1.9 11.3
V 70 63 53 36 51 35 57 50 43 50 70 94 58 71 105 43

Min./Max./Mean, Concentrations in whole sediment core.

V, Coefficient of variation from concentrations in whole sediment core (%).
Bold is used to underline the sum of measured compounds.

3.2.2. Distribution of individual congeners of PCB and PAHs
The largest share of the total content of PCBs was observed for
the congeners with low molecular weight, i.e. PCB 28 and PCB 52.
Exceptionally high contents of these two congeners were noted in
the sediment collected in the port (P) and at station W1. The lowest
concentration values were determined for the congeners with high
molecular weight, i.e. PCB 153 and PCB 180 (Table 2).
At all stations, the concentrations of congeners PCB 52 and PCB
28 in sediment showed the highest variability (Table 2). The con-
centration of PCB 52 ranged from the limit of quantification
(0.1 ng/g d.w.) to over 6.0 ng/g d.w., while the concentration of
PCB 28 from 0.1 ng/g d.w. to ca. 3.5 ng/g d.w. (Table 2).
Among the analyzed polycyclic aromatic hydrocarbons,
fluoranthene, pyrene, benzo(a)anthracene and benzo(a)pyrene
showed the highest concentrations in sediment; the respective
values equaled 156 ± 15, 146 ± 14, 151 ± 4 and 105 ± 7 ng/g d.w.
(Table 2). The mean content values of benzo(k)fluoranthene,
dibenzo(ah)anthracene and benzo(ghi)perylene were much lower
as compared to the aforementioned PAHs, and equaled 74 ± 13,
39 ± 14 and 76 ± 13 ng/g d.w., respectively.
4. Discussion
The obtained total concentrations of PCBs and PAHs did not dif-
fer from the results reported in literature for the Baltic Sea area.
The total PCB concentrations in benthic sediments in the Gulf of
Gdansk determined by other researchers varied from 0.1 ng/g
d.w. to tens of ng/g d.w., while the total PAH concentrations ranged
from hundreds to thousands of ng/g d.w. The results obtained in
the case of total PCB concentration in sediments collected in the
Gdansk Deep were an exception. In this area very high variability
was noted with concentration values ranging from couple to
140 ng/g d.w. (Table 3) (Kowalewska et al., 2003; Kowalewska
and Konat, 1997; Pazdro, 2004; Sapota, 2006).
According to the regulation of the Ministry of Environment in
reference to the types and concentrations of substances which can
contaminate the dredged spoils (Ministerstwo Środowiska, 2002),
the measured concentrations of PAHs and PCBs are safe for the mar-
ine environment and do not exceed the admissible values, i.e.
1.5 mg/kg d.w. for benzo(a)anthracene and benzo(k)fluoranthene;
1.0 mg/kg d.w. for benzo(a)pyrene, dibenzo(ah)anthracene and
benzo(ghi)perylene; and 0.3 mg/kg d.w. for total PCB concentration.
Moreover, based on the comparison of the obtained data with the
results reported for other areas of the world, it can be stated that
the Gulf of Gdansk in the Baltic Sea is not contaminated with the
compounds from PCB and PAH group (Table 3).
Combustion processes were the main source of polycyclic aro-
matic hydrocarbons found in the analyzed benthic sediments.
There are many specific indicators to identify possible sources
(pyrolytic or petrogenic) of PAHs in marine sediments. This obser-
vation (suggesting pyrolytic sources) was confirmed by the high
concentrations of fluoranthene, pyrene and benzo(a)pyrene (Oren
et al., 2006) and the FLU/PYR concentration ratio greater than 1
(Budziński et al., 1997; King et al., 2004). The FLU/(FLU + PYR) con-
centration ratio greater than 0.5 indicates grass, coal and wood
combustion (Yunker et al., 2002) (Table 4). In the Tri-city area,
i.e. in Gdansk, Sopot and Gdynia the potential PAHs sources emit-
ting to the atmosphere are mainly residential furnaces (during
winter), electric power plants and automobile transport. Research
conducted in the Tri-city demonstrates that it is the area character-
 M. Staniszewska et al. / Marine Pollution Bulletin 62 (2011) 1464–1475 1469

A 4500

4000

3500

PAHs (ng/g d.w.)

3000
2500

2000

1500

1000

500

0 15-20
0-2
2-5
5-10
10-15

10-15
15-20

10-15
15-20
0-2
2-5
5-10

0-2
2-5
5-10

0-2
2-5
5-10
10-15
15-20
0-2
2-5
5-10

10-15
0-2
2-5
5-10

15-20
W9 W6 W1 GG KL P
stations/sediment layer (cm)

B 18.0

16.0

14.0
PCBs (ng/g d.w.)

12.0

10.0

8.0

6.0

4.0

2.0

0.0
0-2
2-5
5-10
10-15
15-20

10-15
15-20
0-2
2-5
5-10

0-2

10-15
15-20
2-5
5-10

0-2
2-5
5-10
10-15
15-20
0-2

10-15
2-5
5-10
0-2
2-5
5-10

15-20
W9 W6 W1 GG KL P
stations/sediment layer (cm)

Fig. 3. Vertical profile of total concentration of PAHs (A) and PCBs (B) in sediment core.

ized by increased annual content of benzo(a)pyrene (>1 ng/m3)
(WSSE, 2007).
It was established that the main PAHs source in only two sedi-
ment layers at station W1 could have been crude oil spill (FLU/
PYR < 1, FLU/(FLU + PYR) < 0.4 (Budziński et al., 1997; Yunker
et al., 2002; King et al., 2004), while in two sediment layers from
the dredged spoils dump site the contamination consisted of petro-
leum/petrogenic or gasoline, diesel and crude oil combustion from
cars and diesel trucks (Table 4).
The calculated ratio of total polycyclic aromatic hydrocarbons
in specific sediment core segments to the PAHs concentration in
the deepest sediment layer (15–20 cm) was high. In the case of sta-
tions W9 and W6, the enrichment factor was the highest and ran-
ged from 3.5 to 7. Under the assumption that the mean
sedimentation rate in the study area is 1.93–2.32 mm/rok (Pem-
pkowiak and Knapińska-Skiba, 1988), it can be stated that the in-
creased inflow of PAHs into the environment has started at the
beginning of the 20th century which coincides with an increased
use of coal instead of wood for heating. Coal combustion results
in the generation of higher amounts of PAHs as compared to burn-
ing of wood, gas and liquid fuels (Hites et al., 1977). The presence
of subsurface maximum total concentration of PCBs in the ana-
lyzed sediment cores reflects the inflow of these compounds to
the environment that took place several decades ago during their
mass production and widespread use (Fig. 3).
The lower concentrations of PCBs and PAHs in the 0–2 cm
sediment layer as compared to those measured in deeper layers,
i.e. 2–5 and 5–10 cm are mainly related to the reduced inflow of
contaminants into the sediments at the present time. The observed
particularly low concentrations of PCB 28 and PCB 52 congeners in
the sediment surface layer (see Table 2) can also be explained, inter
alia, by better solubility of the lightest PCB congeners in water. In
the case of PAHs, the formation of soluble complexes with marine
humic substances is a significant factor in the process of PAHs
migration from surface sediments into the water phase (Farrington
et al.,1982). Sanders et al. (1992) suggested that small traces of
PCBs and PAHs may have been transferred from recent sediments
to deeper uncontaminated sediments by mixing, bioturbation, or
sampling extruding methods.
4.1. Dependence of HOCs concentration on the distance from potential
emission sources
The proximity of emission sources definitely has the strongest
influence on the content of hydrophobic organic contaminants in
P
benthic sediments. The highest concentrations of PAHs and
1470 M. Staniszewska et al. / Marine Pollution Bulletin 62 (2011) 1464–1475

Table 3
P P
Concentration range and/or mean concentration value for PAHs and PCBs, expressed in ng/g d.w., in sediments from different areas of the world.
P P
Area Sediment layer PAHs 7PCBs References
(cm)
Baltic Sea
Gulf of Bohnia – – 0.9–6.5 Van den Bavel et al.
(1996)
Baltic Proper – – (16) Gustavson and Jonsson
(1999)
– – 9–31 Jonsson (2000)
Swedish coast 0–2 120–9600 (16 PAHs) Sanchez-Garcia et al.
(2010)
Gulf of Gdańsk 0–5 247.3.0–1444.9 (12 PAHs) 2.98–5.29 Pazdro (2004)
0–10 – 2–35 Konat and Kowalewska
(2001)
0–20 294–1442 (7 PAHs) 2.4–10.9 Current work
0–31 – (2.8) Sapota, 2006
Gdańsk Deep 0–5 1933.6–2205.0 (12 PAHs) 58.3–78.13 Pazdro (2004)
0–10 – 20–145 Konat and Kowalewska
(2001)
0–20 477 2.5–6.7 Current work
(7 PAHs)
0–31 – (5.90) Sapota (2006)
Puck Bay (Jama Rzucewska) 0–31 – (1.5) Sapota (2006)
Open sea (near Hel) 0–5 235.0 (12 PAHs) 1.94 Pazdro (2004)
Arkona Basin, Belt Sea – 10–1870 (15 PAHs) – Witt (1995)
0–3 – 2.1–5.4 Dannenberger and Lerz
(1997)
Vistula River Estuary 0–5 1891.0 (12 PAHs) 25.0 Pazdro (2004)
0–31 – 2.4–3.29 Sapota (2006)
0–20 295 (7 PAHs) 2.4 Current work
Bornholm Deep 0–31 – (3.1) Sapota (2006)
Pomeranian Bay 0–5 4.7–273 (18 PAHs) Baumard et al., 1999
Oder River and Estuary 0–5 30.0–17,000 (18 PAHs) – Baumard et al. (1999)
Oder Estuary 0–10 Few – 9000 (12 PAHs) Few – 255 Kowalewska et al.
(11PCBs) (2003)
Szczecin Lagoon 0–10 3000 – 5000 (12 PAHs) 10–150 Kowalewska et al.
(11PCBs) (2003)
Szczecin Lagoon 0–31 – 2.31 Sapota (2006)
Gdańsk Harbour 0–320 Max.242 (0–20 cm) Max. 9620 (120–140 cm background 40 – Guz et al. (2000)
(150–320 cm) (6PAHs)
Kiel Harbour (Germany) 0–5 474–30,100 – Baumard et al. (1999)
(18 PAHs)
Warnemünde Harbour(Germany) 0–5 4.6–254 (18 PAHs) – Baumard et al. (1999)
Gdańsk Harbour 0–20 2200 (7 PAHs) 11,3 Current work
Others areas
Scheldt Estuary (North Sea) – 4000 (13 PAHs) 150(13 PCBs) Van Zoest and van Eck
(1993)
Eastern Mediterranean (of the shore) 0–1 14.6–158.5 (25 PAHs) – Gogou et al. (2000)
Mediterranean coast, near Marseille, – 86.5–48,090 (14 PAHs) – Benlahcen et al. (1997)
Cannes
Mediterranean, Coast of France 0.5–1 – 0.2–15,850 Picer (2000)
Mediterranean, Coast of Greece 0.5–1 – 0.6–775 Picer, 2000
Mediterranean, Coast of Italian 0.5–1 – 0.6–3200 Picer, 2000
Adriatic coastal 0.5–1 – 6–2203 Picer (2000)
Adriatic open sea – – n.d. – 332 Picer, 2000
Atlantic Ocean, Dominicana coast 0.46–41.9 Sbriz et al. (1998)
Kitimat Harbour, Canada (northern 0–15 310–41,000 (16 PAHs) – Simpson et al. (1996)
Pacific coast)
Broghton Marina, southeast coast of – 24–4710 (16 PAHs) – King et al. (2004)
England
Cotonou Harbour – benin, Nigeria – 25.1–1411 (16 PAHs) – Soclo et al., 2000
Yellow Sea, China 0–1 370–3800 (13 PAHs) – Wu et al., 2001
Kishon River (Israel) 0–20 59.5–298.9 (23 PAHs) 0.4–4.77 Oren et al. (2006)
Arctic Ocean – – 0.14 Iwata et al. (1994)
Fjords - North Spitsbergen 0–5 Below 1–36 (16 PAHs) 0.9–3.7 Sapota et al. (2009)

P
PCBs were determined in sediment samples collected from the
Port of Gdansk (Table 2). Harbor sediments are directly influenced
by anthropogenic activities, i.e. port operations and the proximity
of urban areas. Based on the published literature, a similar conclu-
sion can be formulated about significantly higher contents of
hydrophobic contaminants in benthic sediments in ports and estu-
aries (Table 3).
The sediments collected in the Port of Gdansk were sands char-
acterized by low sorptive surface and very low content of organic
matter and total carbon (Table 1). Therefore the aforementioned
parameters are not correlate with very high contents of organic
contaminants in the port sediments. Among the sediment’s phys-
ico–chemical parameters, only the high share of black carbon in to-
tal carbon (up to 40%) raised some questions (Fig. 2).
Vistula, which accumulates contaminants from the entire river
basin, is considered the main source of pollution entering the Gulf
of Gdansk. However the highest concentrations of hydrophobic
contaminants were not observed close to the river mouth. Total
 M. Staniszewska et al. / Marine Pollution Bulletin 62 (2011) 1464–1475 1471

Table 4
Pyrolytic or pyrogenic indicators of the origin of PAHs in the analyzed sediments.

Station Sediment layer (cm) FLU/PYR FLU/(FLU + PYR) Source

W9 0–2 1.2 0.54 Pyrolytic Grass, coal and wood combustion
2–5 1.2 0.54
5–10 1.0 0.51
10–15 1.1 0.52
15–20 1.0 0.50
W6 0–2 1.1 0.53 Pyrolytic grass, coal and wood combustion
2–5 1.1 0.52
5–10 1.2 0.55
10–15 1.1 0.52
15–20 2.3 0.69
W1 0–2 1.4 0.58 Pyrolytic grass, coal and wood combustion/petrogenic
2–5 0.5 0.34
5–10 1.0 0.50
10–15 1.1 0.51
15–20 0.5 0.33
G4 0–2 1.6 0.62 Pyrolytic grass, coal and wood combustion
2–5 1.0 0.51
5–10 1.5 0.60
10–15 1.1 0.53
15–20 1.3 0.56
KL 0–2 0.8 0.44 Pyrolytic grass, coal and wood combustion or traffic/petrogenic
2–5 1.2 0.55
5–10 0.9 0.46
P 0–2 1.1 0.52 Pyrolytic grass, coal and wood combustion or traffic
2–5 1.3 0.57
5–10 1.0 0.50
10–15 1.0 0.48
15–20 1.1 0.52

FLU/PYR: >1 pyrolytic source; <1 petrogenic source (selected by bold).

FLU/(FLU + PYR): >0.5 grass, coal and wood combustion; 0.4–0.5 gasoline, diesel and crude oil combustion car and diesel trucks (selected by italic); <0.4 petroleum/petrogenic
source.

concentrations of PCBs and PAHs in the collected sediments were
notably increasing (more than two-fold for PAHs and over four
times for PCBs) with the increasing distance from the Vistula river
mouth (Table 2). Therefore the transfer of material carried by Vis-
tula into the Gulf of Gdansk and the change of sea floor character
from transport to accumulation type play a significant role in this
situation.
The lowest total concentrations of PCBs and PAHs in sediment
were observed at the station located right in the Vistula river
mouth (W9; W6; Table 2). The sediments collected from this area
are sands characterized by low sorptive capability. Moreover, high
water dynamics in this area facilitate resuspension and transfer of
organic contaminants from sediment into the water column. Lower
salinity and higher water temperature, as compared to the more
seaward part of the Gulf of Gdansk, stimulate better solubility of
hydrophobic contaminants in water and, consequently, lower
accumulation of these compounds in sediment.
The increasing seaward distance from the Vistula river mouth
mainly results in the salinity increase and temperature decrease
which stimulates sorption of hydrophobic compounds onto sedi-
ment particles. Moreover, the share of small grain size fraction
(<0.063 mm) increases from ca. 50% to 90% and this results in the
increased sorptive capabilities of the sediment. The highest con-
centrations of PCBs and PAHs in the Gulf of Gdansk were observed
at stations characterized by intensive sedimentation (W1 and G4)
and located in the accumulation type area with large inflow of or-
ganic matter (Table 1).
The Vistula waters mostly carry lighter PCB congeners, i.e. PCB
28 and PCB 52 (Sapota, 2006). At stations located close to the Vis-
tula river mouth (W9 and W6) congeners with the lowest chlorine
content, i.e. PCB 28 and PCB 52 practically constitute the total PCBs
content. The concentrations of congeners with higher chlorine con-
tent such as, PCB 180 and PCB 153 are close to the limit of quanti-
fication (Table 2). Congeners with higher chlorine content are
mainly adsorbed onto river sediments. Moreover, polychlorinated
biphenyls with larger number of chlorine atoms may undergo
microbiological degradation in river sediments and transform into
the congeners substituted with low number of chlorine atoms
(Falandysz, 1999). Congeners with the highest number of chlorine
atoms, i.e. PCB 138, PCB 153 and PCB 180 were reaching the high-
est concentrations in sediments collected from the Port of Gdansk
(location proximal to possible contamination sources) and at sta-
tions situated most eastward from the Vistula river mouth (W1;
accumulation type site) (Table 2).
4.2. Dependence of HOCs concentration on physico–chemical
parameters
4.2.1. Granulometry of sediment
Many researchers, among others, Mayer (1993) and Keil et al.
(1994) reported high dependence of PAHs and PCBs concentrations
on the content of small grain size fraction in sediment. Therefore it
can be stated that hydrophobic organic contaminants are mainly
adsorbed onto the particles of small grain size sediments
(<0.063 mm) which have large surface area. In the case of sedi-
ments collected close to the Vistula river mouth and near the Gulf
of Gdansk, a statistically significant correlation between the con-
centration of PCBs and PAHs and the percentage share of the small-
est grain size fraction was found (Table 5). The sediments near the
Gulf of Gdansk mainly consist of mud with high content of the
<0.063 mm grain size fraction (Table 1).
In the case of sediments collected in the Port of Gdansk, a cor-
relation between the concentration of PCBs and PAHs and the per-
centage share of the smallest grain size fraction was not found.
Harbor sediments are mostly sands characterized by the low per-
centage share of the <0.063 mm grain size fraction and high
1472 M. Staniszewska et al. / Marine Pollution Bulletin 62 (2011) 1464–1475

Table 5
Pearson’s linear correlation coefficients (r) and equations describing the relationship between the total content of PCBs and PAHs, and sediment parameters, i.e. content of the
<0.063 mm grain size fraction, LOI, TC and BC.

Parameters Pearson’s linear correlation coefficients (r) (p < 0.05) for station:
W1,W6, W9, G4 P, KL
PCBs PAHs PCBs PAHs
Content of the < 0.063 mm grain size fraction (%) 0.72 0.52 No correlation No correlation
n = 10 n = 12
y = 0.2x 6.4 y = 3.9x + 158
LOI (%) 0.84 0.58 0.82 0.92
n = 15 n = 16 n=5 n=7
y = 0.6x 0.3 y = 33x 166 y = 8.4x 166 y = 1016x 516
TC (%) 0.64 0.66 0.76 0.89
n = 17 n = 17 n=7 n=8
y = 2.3x 3.6 y = 104x 16 y = 5.8x 1.5 y = 1495x 941
BC (%) 0.66 0.50 0.88 0.88
n = 17 n = 16 n=8 n=7
y = 6.9x + 0.3 y = 567x + 112 y = 28.5x 3.1 y = 9300x 1509

concentrations of PAHs and PCBs that are out of proportion to the

granulometric parameters (Tables 1 and 2). Other researchers also PAHs, PCBs, LOI, TC, BC
found out that the statistical dependence between the concentra- 0.00 0.50 1.00 1.50
tion of PCBs and PAHs and the percentage share of the sediment’s 0
smallest grain size fraction is not always present. Ahrens and
Depree (2004) measured the highest PAHs concentrations in the PAHs
0.25–0.50 mm sediment fraction which was collected in the Ports
PCBs
of Auckland, New Zealand and amounted to 48% of total sediment. 5
The <0.063 mm fraction, which amounted to >50% of total sedi- LOI
sediment [cm]

ment, contained only 17% of PAHs. Ahrens and Depree (2004) TC

pointed out that the 0.25–0.50 mm grain size fraction was enriched
BC
in black carbon (strong sorbent of hydrophobic contaminants) as 10
compared to the <0.063 mm fraction. In this particular case, black
carbon content could be mainly responsible for the sorption of
PAHs.
15
4.2.2. Organic matter
Mayer (1993) reported that in shallow water basins character-
ized by very high productivity and large flux of inflowing organic
matter the adsorption of hydrophobic organic contaminants is 20
not determined by the sediment’s granulometry, but rather by
the content of organic matter. Organic matter acts as specific sor- PAHs, PCBs, LOI, TC, BC
bent for hydrophobic organic contaminants in sediment (Witt, -0.01 0.09 0.19 0.29
1995; Konat and Kowalewska, 2001). Many researchers, e.g. Mayer 0
(1993), Keil et al. (1994), Witt (1995), Guz et al. (2000) and Konat
PAHs
and Kowalewska (2001) found strong correlation between the total
concentration of PAHs and PCBs and the organic matter content in PCBs
sediment. In this study particularly high correlation coefficient val-
sediment [cm]

ues were obtained for the relationship between the total PAHs and
PCBs concentration and organic matter content in samples of sed-
iment originating from harbor (P and KL) (Table 5). This finding
was also confirmed by a similar relationship between the normal-
ized concentration values of the analyzed compounds and organic
matter content in the downward direction along the sediment pro-
file (particularly to the 10-cm level) at stations KL and P (Fig. 4).
Port sediments were characterized by low content of organic mat-
ter that was most likely well saturated with PAHs and PCBs. Strong
dependence of the total PCB concentration on organic matter con-
tent was found in sediment samples from stations W1, W6, W9
and G4 (Table 4).
Particularly low correlation coefficient values for the relation-
ship between the total PAHs concentration and organic matter con-
tent in sediment samples from stations W1, W6, W9 and G4
(Table 4) could have resulted from the presence of different type
of organic matter carried by the Vistula river. This could stimulate
the formation, among others, of soluble complexes of PAHs and hu-
mic substances (Meyers and Quinn, 1973).
LOI
TC
5
BC
10
Fig. 4. Vertical profile of normalized concentrations of PAHs, PCBs , LOI, TC and BC
in sediment core on P and Kl station (were calculated Y=(X-Xmin)/(Xmax Xmin), were:
Y = normalized concentrations of PAHs, PCBs , LOI, TC or BC, X = detected concen-
tration of PAHs, PCBs , LOI, TC or BC, Xmin = minimum concentration detected of
PAHs, PCBs , LOI, TC or BC, Xmax = maxinimum concentration detected of PAHs, PCBs
, LOI, TC or BC).
The highest organic matter content, expressed as loss on igni-
tion, was determined in benthic sediments collected at the deepest
station (G4 and W1). The accumulation type sea floor is present at
 M. Staniszewska et al. / Marine Pollution Bulletin 62 (2011) 1464–1475
this location. Sediment carried by the Vistula waters together with
organic matter undergoes flocculation and slow sedimentation due
to the salinity gradient. During this process the enrichment of sed-
iment particles in water-insoluble and easily sorbed compounds
takes place (Means, 1995; Konat and Kowalewska, 2001). Also
the highest concentrations of PAHs and PCBs were noted in this
particular location in the Gulf of Gdansk (Table 2).
4.2.3. Total carbon
A statistically significant correlation was found for the relation-
ship between the total concentration of the analyzed compounds
and total carbon, the latter being the main component of organic
matter (Table 5). The relationship was stronger in the case of sed-
iments originating from harbors (port and dredged spoils dump
site) as compared to the samples collected at stations W9, W6,
W1 and G4. This finding was confirmed by the similar character
of the relationship between the normalized concentration values
of the analyzed compounds and TC in the downward direction
along the sediment profile (particularly to the 10-cm level) at sta-
tions KL and P (Fig. 4).
It should be noticed that the correlation strength of the relation-
ship between the total PCBs concentration and organic matter con-
tent was at the comparable level at all stations, while the
correlation between the total PCBs concentration and total carbon
content was stronger in sediment samples collected in the port and
at the dredged spoils dump site (Table 5). This could be explained
by different qualitative composition of sediments in the Gulf of
Gdansk and those originating from harbor. In the case of port sed-
iments, the share of TC in organic matter content was, on average,
79%, and was always >72%. In the case of sediments from the Gulf
of Gdansk, the share of TC in organic matter content was much
lower and on average equaled 59% (values < 72% except for three
samples). Many researchers (Mitra et al., 1999; Ahrens and Depree,
2004; Tremblay et al., 2005; Yu et al., 2006) reported that sorption/
desorption processes of HOCs in sediment are mainly dependent
on the quality, but not that much on quantity of organic matter.
4.2.4. Black carbon
Zhou et al. (2005) established that the measured PAHs and PCB
concentrations in sediment are much higher than those expected
on the basis of organic matter content expressed as total carbon.
Most likely, this phenomenon results from the presence of black
carbon (BC) which is an ‘‘extremely’’ strong sorbent (Mitra et al.,
1999; Jonkers and Koelmans, 2002; Koelmans et al., 2006; Yu
et al., 2006).
It is therefore possible that the better sorptive capabilities of the
port sediments with respect to hydrophobic organic contaminants
are caused by the higher black carbon content in total carbon (up
to ca. 40%) as compared to the sediments from the Gulf of Gdansk
(Fig. 2). Ghosh et al. (2000, 2003) proved that 62–90% of PAHs and
PCBs in sediment are bound to BC which constitutes only couple
percent of total sediment mass. Sanchez-Gracia et al. (2010) was
proved that BC control distribution PAHs in marine sediments near
the Swedish coast (observation on over 120 sediments samples).
PAHs form very strong bonds with black carbon which similarly
to PAHs is generated during incomplete combustion (Jonkers and
Koelmans, 2002; Bucheli et al., 2004). The highest concentrations
of pyrolytic PAHs were measured in sediments collected in the Port
of Gdansk. Black carbon is considered to have 10–1000 times more
sorption strength than organic matter, i.e. humic and fulvic acids
with respect to PAHs, PCBs, dioxins and polybrominated diphenyl
ethers (Bärring et al., 2002; Jonkers and Koelmans, 2002; Bucheli
and Gustafsson, 2003; Koelmans et al., 2006). This has been con-
firmed by higher values of correlation coefficient and larger slopes
of curves depicting the relationship between the PCBs and PAHs
concentrations and black carbon content for the port sediments
1473
as compared to the sediments collected at stations W1, W6, W9
and G4 (Table 5). It is also reflected in the similar concentration
variability of the analyzed compounds and BC in relation to depth
(Fig. 4). The main source of black carbon is incomplete combustion
of fossil fuels and biomass and it may be transported to the sea
(Carcaillet et al., 2002). Therefore its presence plays an essential
role in sediments that are close to the shore and anthropogenic
emission sources. The Port of Gdansk is situated in the proximity
of urban areas that emit large amounts of BC into the atmosphere,
particularly during winter season. The high percentage share of BC
in TC in the harbor sediment might also have been the result of
loading and unloading of coal and ores because sediment samples
were collected at Nabrzeze _ We˛glowe (Coal Pier).
Koelmans et al. (2006) postulated that BC begins to play a crit-
ical role in sorption of HOC in sediment when the BC/TC ratio is >5–
10%. A similar conclusion was formulated by Bucheli et al. (2004)
who observed that BC plays an essential role in sorption of PAHs
only in soils and sediments characterized by high BC content and
low organic carbon content. Benthic sediment collected at stations
W1, W6, W9 and G4 had higher contents of organic matter and or-
ganic carbon, and much lower BC content as compared to those
determined in the port sediments (Table 1). In such a case, adsorp-
tion sites in black carbon can be filled by organic matter (Koelmans
et al., 2006). The weakening of BC sorption strength is a result of
this competition. Consequently, the phenomenon was reflected in
lower values of correlation coefficient between the concentrations
of PCBs and PAHs and black carbon content in sediments collected
at stations W1, W6, W9 and G4.
The varying strength of correlations may be resulting from dif-
ferent origin of black carbon which determines its sorption
strength (Michiel et al., 2002). Several types of black carbon can
be distinguished, i.e. soot from automobile exhaust fumes, soot
originating from combustion of oils, soot resulting from wood
burning, pure carbon, charcoal, black carbon present in the atmo-
sphere as fine particles, activated carbon and, finally, graphite (Jon-
kers and Koelmans, 2002). Each of these forms differs with respect
to physico–chemical parameters, i.e. specific surface area, density,
and the size and number of pores which significantly influences
the sorptive properties (Jonkers and Koelmans, 2002; Koelmans
et al., 2006).
Most likely the port sediments are rich in black carbon originat-
ing from a different source than in the case of sediments from the
Gulf of Gdansk. The main source of PAHs and probably BC in all the
analyzed sediments is combustion of coal and wood. However it
should be noted that the port sediments had been collected from
the Coal Pier where coal loading/unloading was taking place. The
coal powder resulting from these operations could have undergone
deposition from the atmosphere into the water column and then
into the sediment. Pure carbon is characterized by very high sorp-
tive capabilities with respect to PCBs and PAHs (Jonkers and
Koelmans, 2001 and; Michiel et al., 2002). Moreover, considering
navigational and port operations, it can be assumed that port sed-
iments contain soot originating from automobile exhaust fumes
and burning of crude oil and oils. These forms of carbon have high-
er sorptive strength with regard to PCB congeners and PAHs in
comparison to, for example, soot resulting from wood burning
(Michiel et al., 2002). Bucheli et al. (2004) observed stronger corre-
lation between the PAHs concentration and black carbon content
for carbon originating from automobile exhaust fumes, particularly
from diesel combustion sources. Jonkers and Koelmans (2002)
noted stronger correlation between the PAHs concentration and
the content of black carbon resulting from automobile exhaust
fumes. These authors in particular point out the preferential sorp-
tion of PCBs onto diesel soot.
It should also be noted that sorption by the same type of black
carbon varies in dependency on carbon’s molecular weight and the
1474 M. Staniszewska et al. / Marine Pollution Bulletin 62 (2011) 1464–1475
structure of specific PCBs and PAHs (Michiel et al., 2002). PCBs
congeners with higher number of chlorine atoms and heavier PAHs
are characterized by higher values of the octanol/water partition
coefficient (Kow) and are more strongly adsorbed onto all types
of black carbon in sediment (Michiel et al., 2002). The port sedi-
ments had higher share of heavier congeners in the total concen-
tration of PAHs and PCBs (Table 2). This could significantly
increase the values of correlation coefficients between the PCBs
and PAHs concentration and black carbon content in the port sed-
iments as compared to those for the sediments collected at stations
W1, W6, W9 and G4.
5. Conclusion
The proximity of emission sources has the biggest influence on
the content of hydrophobic contaminants in benthic sediments in
P sediment contamination by polycyclic aromatic hydrocarbons in Gironde
the Gulf of Gdansk. The highest concentrations of PAHs and
P
PCBs were determined in sediments collected in the Port of
Gdansk, i.e. 2200 and 11.3 ng/g d.w., respectively. A significant role
is also played by the transport of material carried by the Vistula
River seaward into the Gulf of Gdansk. The total concentrations
of PCBs and PAHs in the collected sediments were noticeably
increasing with the increasing distance from the Vistula river
mouth as the sea floor character was changing from the transport
type into the accumulation type.
Particularly high correlation coefficient values were obtained
for the relationship between the total concentrations of PAHs
and PCBs and organic matter content, organic carbon content and
black carbon content in the samples of sediment collected in the
Port of Gdansk and at the marine dredged spoils dump site. It is
likely that the quality of organic matter, particularly the higher
content of BC (up to ca. 40%), was responsible for the stronger sorp-
tive capabilities of the port sediments as compared to those of the
sediments collected in the seaward locations in the Gulf of Gdansk
and close to the Vistula river mouth. The Port of Gdansk is situated
in the proximity of urban areas which emit large amounts of BC
into the atmosphere, particularly in winter.
The obtained lower values of correlation coefficient for the rela-
tionship between the total concentrations of PCBs and PAHs and
black carbon content in sediments collected in the seaward loca-
tions in the Gulf of Gdansk and close to the Vistula river mouth
can be explained by the weakened sorption strength of BC. Benthic
sediment collected in the Gulf of Gdansk and close to the Vistula
river mouth was characterized by much higher contents of organic
matter and organic carbon as compared to those in the port sedi-
ment. In this case, adsorption sites in carbon with high refractive
index could have been filled by organic matter.
The lack of correlation between the concentration of PCBs and
PAHs and percentage share of the smallest grain size fraction
(<0.063 mm) in the case of the port sediments may also prove that
the sorption of hydrophobic contaminants in these sediments de-
pends, to a large extent, on the presence of black carbon. Other
researchers indicated that the 0.25–0.50 mm grain size fraction
was richer in black carbon as compared to the <0.063 mm fraction
which would explain the lack of correlation in this particular case.
Acknowledgments
We would like to thank the crews of ORP Arctowski for their
support with field observations.
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