POLYCHLORINATED BIPHENYLS, POLYCYCLIC AROMATIC HYDROCARBONS AND ALKYLPHENOLS IN SEDIMENTS FROM THE

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Toxicol. and Environ. Chem., 2003, Vol. 85, Nos. 4–6, pp. 51–60
POLYCHLORINATED BIPHENYLS,
POLYCYCLIC AROMATIC HYDROCARBONS
AND ALKYLPHENOLS IN SEDIMENTS FROM THE
ODRA RIVER AND ITS TRIBUTARIES, POLAND
K. KANNANa,*, J.L. KOBERc, J.S. KHIMc,
K. SZYMCZYKb,y, J. FALANDYSZb and J.P. GIESYc
a
Wadsworth Center, New York State Department of Health, Empire State Plaza, Albany, NY
12201-0509, USA; bDepartment of Environmental Chemistry and Ecotoxicology, University of
Gdańsk, PL80-952, Gdańsk, Poland; cDepartment of Zoology, 213 National Food Safety and
Toxicology Center, Institute for Environmental Toxicology, Michigan State University, East
Lansing, Michigan 48824, USA
(Received 6 November 2000; Revised 15 March 2001; In final form 16 March 2001)
Concentrations of polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), nonylphenol
(NP) and octylphenol (OP) were measured in sediments collected during June–August 1998 along the Odra
River and its tributaries (Warta, Obrzyca, Barycz, Kaczawa and Bóbr Rivers) in Poland. In addition,
raw and treated sewage sludge collected from Gdańsk, Poland, were analyzed for the target compounds.
Concentrations of PCBs in sediments varied widely, ranging from 2.7 to 412 ng/g, on a dry weight basis
(dry wt). PAHs were the predominant compounds in sediments with concentrations ranging from 150
to 19 000 ng/g, dry wt. The distribution of concentrations of PAHs was more homogenous than that of
PCBs. NP concentrations in sediments ranged from <1 to 762 ng/g, while that of OP from <1 to 9.8 ng/g,
dry wt. Measured concentrations of target analytes in sediments of the Odra River and its tributaries were
comparable to or greater than those reported for riverine sediments in other eastern European countries.
Concentrations of total PCBs, PAHs and NP in raw and treated sewage sludge collected from a sewage
treatment plant in Gdańsk, Poland, were in the ranges of 203–284, 11 720–13 880 and 6760–99 600 ng/g,
dry wt, respectively. Primary treatment of sewage did not appear to reduce PCB or PAH concentrations,
although NP and OP concentrations were much less in treated sludge than in raw sludge. This is one of
a few studies that document concentrations of PCBs, PAHs and NP in sediments of the Odra River and
its tributaries in Poland.
Keywords: PAHs; PCBs; Alkylphenols; Sediment; Sewage sludge
INTRODUCTION
The Baltic Sea is polluted by the discharge from various rivers, atmospheric deposition,
spills and dumping of dredged materials from the surrounding countries. The long
hydraulic residence time and cold waters of the Baltic Sea make it vulnerable as a
*Corresponding author. Tel.: þ1 518-474-0015. Fax: þ1 518-473-2895. E-mail: kkannan@wadsworth.org
y
Present address: University of Warmia and Mazury, Olsztyn, Poland
ISSN 0277-2248 print: ISSN 1087-2620 online/03/01-20001-06 ß 2003 Taylor & Francis Ltd
DOI: 10.1080/0277221042000
52
K. KANNAN et al.
sink for persistent and semi-volatile organic contaminants [1]. Organochlorine compounds such as polychlorinated biphenyls (PCBs) are among the most widespread contaminants in the Baltic Sea. The hydrophobic nature of these compounds favors them
to sorb onto suspended particulate matter, which are finally deposited in sediments.
While several studies have reported the occurrence of organochlorines in biota from
the Baltic Sea and its coastal areas [2–9], reports of organochlorines in sediments are
fragmentary [10,11]. In particular, on a regional scale, organochlorine concentrations
in sediments of rivers that drain into the southern part of the Baltic Sea are limited.
Monitoring of trace organic pollutants in sediments of rivers that discharge into the
Baltic Sea would provide information regarding local sources. In this study, PCBs,
polycyclic aromatic hydrocarbons (PAHs) and alkylphenols such as nonylphenol
(NP) and octylphenol (OP) were measured in sediments from the Odra River and its
tributaries in Poland, that drains into the southern Baltic Sea.
The Odra River is one of the largest rivers that empties into the Baltic Sea and drains
through urbanized, industrialized and agricultural areas of Poland, Czech Republic and
Germany. The Odra River is polluted by the discharges of wastewater from several
industries and municipal wastewater treatment plants [1]. A few studies have reported
the occurrence of trace organic contaminants in estuarine regions of the Odra River
[12–16]. In this study, sediment samples were collected from various locations along
the Odra and Warta Rivers and their tributaries in Poland to study the distribution
of PCBs, PAHs, NP and OP.
Few studies have reported the occurrence of PAHs, NP and OP in sediments from
Baltic countries [13–16] and, therefore, this is one of a few reports that document
the concentrations of PAHs, NP and OP in sediments. The target analytes were also
measured in raw and treated sewage sludge from a municipal sewage treatment plant
in Gdańsk, Poland. Since effluents from municipal wastewater treatment plants are a
major source of NP, OP and other organic contaminants to riverine systems, analysis
of sewage sludge provided information regarding the magnitude and sources of
contamination to rivers.
MATERIALS AND METHODS
Sample Collection and Analysis
Seventeen sediment samples were collected during June–August 1998 along the Odra
River and its tributaries (Warta, Obrzyca, Barycz, Kaczawa and Bóbr Rivers), and
the Odra River estuary (Roztoka Odrzańska) in Poland (Fig. 1). Several samples
(10) from each location were pooled to obtain a representative sample. Surface sediments (0–5 cm) were collected using a Van Veen grab sampler. After collection, pebbles
and twigs were removed, then samples were freeze dried and ground with a mortar and
pestle. Samples were stored in HDPE (high density polyethylene) bottles at 20 C until
extraction. Sewage sludge samples were collected from the Gdańsk–Wschód sewage
treatment plant (Oczyszczalnia Gdańsk-Wschód) in the city of Gdańsk (Fig. 1).
Sludge samples were collected before and after primary treatment. In the Gdańsk–
Wschód sewage treatment plant, open fermentation tanks were used for primary
sewage treatment. The period of sludge fermentation was between three and four
months.
POLYCHLORINATED SEDIMENTS OF ODRA RIVER
BALTIC SEA
RIVER ODRA
Gdansk
Gryfino
Gorzow
Szczecin
Odra R.
Szczecin
GERMANY
Estuary
Kostrzyn
53
POLAND
Poznan
Warsaw
Wroclaw
Poznan
Frankfurt
Krosno
Bytom Odrz.
Odrzanskie Bob R
Wroclaw
CZECH
REPUBLIC
Krakow
Zawiercie
Roztoka
FIGURE 1 Map of Poland and the Odra and Warta Rivers showing sampling locations of sediments.
PCBs, PAHs, NP and OP were analyzed following the methods described elsewhere
[17,18]. Sediment and sludge samples were Soxhlet extracted for 20 h using high purity
dichloromethane (DCM). Extracts were then treated with acid-activated copper granules to remove sulfur. Aliquots of extracts were concentrated to approximately 5 mL
by rotary evaporation (40 C), and then to 1 mL under a gentle stream of nitrogen.
Extracts were passed through 10 g of activated Florisil (60–100 mesh size) packed in
a glass column (10 mm i.d.) for clean up and fractionation. The first fraction (F1)
eluted with 100 mL of hexane contained PCBs. PAHs were eluted in the second fraction
(F2) using 100 mL of 20% DCM in hexane. NP and OP were eluted in the third fraction
(F3) with 100 mL of 50% DCM in methanol. Florisil separation was confirmed using
a spike recovery test (n ¼ 3) and standard reference material (SRM), 1974a sediment,
obtained from the National Institute of Standards and Technology (Gaithersburg,
Maryland, USA). Recoveries of the analytes were examined by spiking known
amount of PCBs (100 ng), PAHs (1000 ng) and NP (500 ng) to sodium sulfate, which
was extracted and processed through the whole analytical procedure. Recoveries of
these analytes were between 90 and 105%. Procedural blanks were run with every
five samples to check for interferences. Further details regarding the fractionation
procedure are presented elsewhere [17,18].
PAHs were quantified using a Hewlett Packard 5890 series II gas chromatograph
equipped with a 5972 series mass spectrometer detector. A fused silica capillary
column (30 m 0.25 mm i.d.) coated with DB-17 [(50% phenyl)-methyl polysiloxane;
J&W Scientific, Folsom, CA, USA] at 0.25 mm film thickness was used. The column
oven temperature was programmed from 80 C (1 min hold) to 100 C at a rate of
25 C/min, and then ramped at a rate of 5 C/min to 100 C with a final holding time
54
K. KANNAN et al.
of 6 min. The injector and detector temperatures were maintained at 250 and 300 C,
respectively. The PAH standard (AccuStandard, New Haven, CT, USA) consisted of
16 priority pollutant PAHs identified by the U.S. Environmental Protection Agency
(U.S. EPA Method 8310). The mass spectrometer was operated under selected ion
monitoring (SIM) mode using the molecular ions selective for individual PAHs.
Concentrations based on individually resolved peaks were summed to obtain the
total PAH concentrations. The detection limits of individual PAHs in sediment samples
were 10 ng/g, dry wt.
PCBs were quantified using a gas chromatograph (Perkin Elmer series 600) equipped
with 63Ni electron capture detector (GC-ECD). A fused silica capillary column coated
with DB-SMS [(5%-phenyl)-methylpolysiloxane, 30 m 0.25 mm i.d.] having a film
thickness of 0.25 mm was used. The column oven temperature was programmed
from 120 C (1 min hold) to 180 C at a rate of 10 C/min (1 min hold) and then to
260 C at a rate of 2 C/min with a final hold time of 12 min. Injector and detector
temperatures were kept at 250 and 300 C, respectively. Helium and nitrogen were
used as carrier and make up gases, respectively. A solution containing 98 individual
PCB congeners (AccuStandard, New Haven, CT, USA) with known composition
and content was used as a standard and concentrations of 98 individually resolved peaks
were summed to obtain total PCB concentrations [19]. Detection limits of individual
PCB congeners were 0.01 ng/g, dry wt.
Reverse phase high performance liquid chromatography (HPLC) with fluorescence
detection was used to quantify NP and OP. High-purity p-nonylphenol and p-tert-octylphenol standards (Schenectady International, Freeport, TX, USA) were used as
standards. Samples and standards were injected (10 mL) by a Perkin Elmer Series
200 autosampler (Perkin Elmer, Norwalk, CT, USA) onto an analytical column,
ProdigyTM ODS (3), 250 4.6 mm column (Phenomenex, Torrance, CA, USA),
which was connected to a guard column (ProdigyTM ODS (3), 30 4.6 mm), and
eluted with a flow of acetonitrile (ACN) and water at a gradient from 50% ACN in
water to 98% ACN in water delivered by Perkin Elmer Series 200 pump for 20 min.
Detection was accomplished using a Hewlett Packard 1046A fluorescence detector
(Hewlett-Packard, Wilmington, DE, USA) with an excitation wavelength of 229 nm
and an emission wavelength of 310 nm. NP and OP detection limits for the analytical
method were 1 ng/g, dry wt.
RESULTS AND DISCUSSION
Sediments
PCBs were found in all sediment and sewage sludge samples analyzed. Concentrations
of PCBs in sediments varied widely, and ranged from 2.7 to 412 ng/g, dry wt (Table I).
Sediment collected from the Obrzyca River contained the highest concentration of
PCBs, which was approximately 7-fold greater than the average PCB concentration
calculated for the Odra River basin (60.5 ng/g dry wt). Sediment from Police and
Gorzów Wielkopolski contained PCB concentrations greater than 100 ng/g, dry wt.
This suggests the presence of local sources in these locations. Several large chemical
industries (fertilizer manufacturers) are located in Police. The measured concentrations
of PCBs in sediments collected along the Odra River and its tributaries were greater
POLYCHLORINATED SEDIMENTS OF ODRA RIVER
55
TABLE I Concentrations of total PCBs, PAHs and alkylphenols (ng/g, dry wt) in sediment collected along
the Odra River and its tributaries, Poland
Location
Total PCBs
Total PAHs
OP
NP
Kaczawa River
Barycz River
Bytom Odrzański (Odra River)
Obrzyca River
Bóbr River
Police
Krosno Odrzańskie (Odra River)
Zawiercie (Warta River)
Poznań (Warta River)
Gorzów Wlpk. (Warta River)
Kostrzyn (Warta River)
Frankfurt (Odra River)
Mescherin
Gryfino (Odra River)
Podjuchy (Odra River)
Szczecin (Odra River)
Roztoka Odrzanska
15.3
41.4
12.0
412
7.2
131
18.1
65.8
9.7
125
2.7
18.5
4.0
25.4
44.7
11.2
85.1
5710
6150
10 400
1520
4280
19 000
6010
18 400
1480
4600
150
4230
1000
6560
1720
9690
9590
1.9
3.6
3.3
5.9
<1
2.5
<1
1.9
1.1
3.1
<1
3.5
<1
4.1
3.2
9.8
<1
47
161
762
91
48
224
48.7
498
185
71.7
11
65.8
18
682
35.2
757
<1
Max
Min
Mean
412
2.7
60.5
19 000
150
6500
9.75
<1
2.89
762
<1
232
than those reported for the Odra River Estuary, which ranged from 0.13 to 16 ng/g, dry
wt [12,13]. Roztoka Odrzańska is a part of the Odra River Estuary, which contained a
PCB concentration in sediment of 85.1 ng/g, dry wt (Table I). Sediments collected along
the western and eastern Odra River near Szczecin and Gryfina contained total PCB
concentrations in the range of 12–86 ng/g, dry wt [20]. The results suggest that the
Odra River and its tributaries are a source of PCBs in the southern Baltic Sea.
Sediment quality guidelines (SQG) have been proposed for PCBs in sediments using
theoretical and empirical approaches [21]. Based on the review of available SQGs, consensus threshold- (TEC) and moderate-effect concentrations (MEC) of 40 and 400 ng/g,
dry wt, respectively, have been proposed for total PCBs [21]. Sediment collected in the
Obrzyca River exceeded the MEC whereas 7 of the 17 sediments contained total PCB
concentrations greater than TEC but less than MEC. Concentrations of PCBs in 53%
of the sediments analyzed were less than the TEC.
PAHs were the predominant compounds in sediments of the Odra River and
its tributaries in Poland. Concentrations of PAHs were approximately two orders
of magnitude greater than those of PCBs (Table I). Concentrations of PAHs were
uniformly high in all the locations and were relatively less variable. PAH concentrations
greater than 10 000 ng/g, dry wt, were measured in sediments from Police, Zawiercie,
Bytom Odrzański. This suggests the presence of point sources of PAHs in these local
areas. Zawiercie and Bytom Odrzański are located in lower Silesia region in the
southwestern Poland; Several industrial activities in lower Silesia including coal burning
and processing could have contributed for the great PAH concentrations.
A recent study has reported the occurrence of PAHs in sediments of the Odra River
Estuary. A median PAH concentration of 395 ng/g, dry wt, was found in sediments
from the Odra River Lagoon [16]. Mean PAH concentration of 6500 ng/g, dry wt,
measured in the sediments of the Odra River and its tributaries was 16 times greater
than that reported for the Odra River Lagoon. A study on the spatial distribution of
K. KANNAN et al.
2.0
1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
ena
Ac
Na
ph
tha
le
pht ne
hyl
Ac
ene
ena
pht
hen
Flu e
or
Ph
ena ene
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An
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Flu
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ene
Be
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ant
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[k] orant
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Dib no[1
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Be
n
nth
nzo
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[gh
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i]p
er y
len
e
Mean concentration
(µg/g, dry wt)
56
FIGURE 2 Mean concentrations (mg/g) of individual PAHs in sediments collected from the Odra and
Warta Rivers. Bars indicate SD.
PAHs in the Baltic Sea suggested that sediments from the Odra Trough had the highest
PAH concentration of 1070 ng/g, dry wt, and suggested that the Odra River has been a
major source of PAHs in the southern Baltic Sea [22]. Concentrations of PAHs in sediments from the Morava and Drevnice Rivers in the Czech Republic were from 1160 to
40 000 ng/g, dry wt [23]. The mean concentrations of PAHs in sediments from the Odra
River were similar to those found in the Morava River in the Czech Republic.
Mean concentration of 16 PAH compounds analyzed in the study is shown in Fig. 2.
Three and four-ringed aromatic compounds such as chrysene, fluoranthene, phenanthrene and pyrene were the major PAHs accounting for, on average, 58% of the
total PAH concentrations in sediments. Some molecular ratios of specific PAH
compounds are used to distinguish between PAHs of various origin [24]. These criteria
are based on the characteristics of composition and distribution pattern as a function of
the emission source. Phenanthrene (Phe) is a thermodynamically more stable tricyclic
aromatic isomer than anthracene (Ant). Hence petroleum contains more phenanthrene
relative to anthracene (Phc/Ant >5). On the contrary, high-temperature processes such
as incomplete combustion of fossil fuel (e.g., coal) can result in low Phe/Ant ratios
(Phe/Ant <15) [25]. Similarly, fluoranthene (Flu) to pyrene (Py) ratios greater than
one are attributed to pyrolytic sources, whereas less than 1 are related to petrogenic
sources. However, exceptions exist in some cases [25] and, therefore, caution should
be exercised to use the above ratios. In this study, all sediments exhibited Flu/Py
ratios of greater than 1, which suggests pyrolytic inputs (Table II). Further, the ratios
of Phe/Ant were less than 15 in all locations except locations on the Barycz River
(Poznań and Kostrzyn), further suggesting that the major source of PAHs in sediments
is combustion of fossil fuel such as coal. The values of Flu/Py and Phe/Ant in sediments
from Barycz River as well as of the Warta River at the sites Poznań and Kostrzyn suggested that they receive inputs both from petrogenic acid pyrolytic sources of PAHs.
A variety of approaches to the development of biological effects-based SQG
have been proposed and compared (see [26] for review). A consensus threshold
concentration of total PAHs of 290 mg/g OC has been proposed [26]. Assuming
an organic carbon content of 1% in sediments, the organic carbon normalized PAH
POLYCHLORINATED SEDIMENTS OF ODRA RIVER
57
TABLE II Ratios of Phenanthrene to Anthracene (Phe/Ant) and Fluoranthene to
Pyrene (Flu/Py) in sediments collected along the Odra River and its tributaries in Poland
Location
Kaczawa River
Barycz River
Bytom Odrzański (Odra River)
Obrzyca River
Bóbr River
Police
Krosno Odrzańskie (Odra River)
Zawiercie (Warta River)
Poznań (Warta River)
Gorzów Wielkopolski (Warta River)
Kostrzyń (Warta River)
Frankfurt (Odra River)
Mescherin
Gryfino (Odra River)
Podjuchy (Odra River)
Szczecin (Odra River)
Roztoka Odrzańska (Odra River estuary)
Phe/Ant
Flu/Py
4.2
87.3
4.1
0.2
3.5
5.0
3.8
4.9
116
7.7
23.3
2.8
2.7
4.7
4.4
5.1
4.9
1.1
1.2
1.3
2.5
1.2
1.2
1.3
1.2
1.2
1.1
1.1
1.3
1.2
1.2
1.3
1.2
1.2
concentrations in Odra and Warta River sediments were estimated to be between 15
and 1900 mg/g OC. Twelve of the 17 sediments exceeded the consensus SQG for
PAHs of 290 mg/g OC.
Nonylphenol was detected in sediments from all the locations except that from
Roztoka Odrzańska. The highest NP concentration was 762 ng/g, dry wt, found for
the sediment from Bytom Odrzański. Very few studies have reported the occurrence
of alkylphenols in riverine sediments in Europe. The concentrations of NP in sediments
were comparable or greater than those found in sediments from the Morava River
(6–150 ng/g, dry wt) in the Czech Republic [27]. Sediments from rivers in the UK contained NP concentrations in the order of a few mg/g dry wt [28]. NP concentrations
in sediments from the Rhine, Glatt and Sitter Rivers in Switzerland ranged from 190
to 13 000 ng/g, dry wt [29]. Concentrations of OP were one to two orders of magnitude
less than those of NP. Greater concentrations of NP and OP suggest sources originating
from municipal wastewater treatment plants.
Sewage Sludge
PCBs, PAHs, NP and OP were found in raw and treated sewage sludge collected
from Gdańsk, Poland (Table III). Concentrations of PCBs in sludge ranged from
130 to 371 ng/g, dry wt. There was no significant reduction in PCB concentrations
after primary treatment (fermentation). Similarly, concentrations of PAHs in sewage
sludge ranged from 7980 to 18 400 ng/g, dry wt. In general, 4-ring aromatic hydrocarbons accounted for 58% of the total PAH concentrations in sludge (Fig. 3).
Fluoranthene, pyrene, chrysene and phenanthrene accounted for 62% of the total
PAH concentrations in sludge. Similar to that found for sediments, the ratios of
Phe/Ant and Flu/Py were <15 and >1, respectively, for all sewage sludge samples.
This suggests that the major source of PAHs in sewage sludge is combustion related.
Primary treatment of the sewage did not reduce PAH concentrations in sludge.
Concentrations of PCBs and PAHs were greater than those found in sediments from
several locations. These results suggest that the discharge of wastewater and sewage
58
K. KANNAN et al.
TABLE III Concentrations of PCBs, PAHs and alkylphenols (ng/g, dry wt) in raw and
treated sewage sludge from a treatment plant in Gdańsk, Poland
Location
Raw sewage sludge Tank #1
Raw sewage sludge Tank #2
Raw sewage sludge Tank #3
Raw sewage sludge Tank #4
Mean (raw)
Sewage sludge after clarification #1
Sewage sludge after clarification #2
Mean (treated)
Total PCBs
Total PAHs
OP
NP
186
253
130
242
203
371
198
284
12 100
7980
10 900
15 900
11 720
18 400
9360
13 880
4320
411
495
622
1460
365
361
363
17 800
154 000
111 000
116 000
99 600
6670
6840
6760
% of total PAH
concentrations
120
100
80
60
40
20
0
2
3
4
5
6
Number of rings
FIGURE 3 Profile of PAHs in sewage sludge collected from a treatment plant in Gdańsk, Poland. Values
are presented as (average) % of total PAH concentrations for individual PAH groups selected based on the
number of rings. Bars indicate SD.
sludge from treatment plants can contribute to a major source of PCBs and PAHs
in rivers. Concentrations of NP in sewage sludge ranged from 6670 to 154 000 ng/g,
dry wt. This is within the range of values reported for sewage sludge from various
countries (see [30] for review). NP concentrations in raw sludge were, on average, 68fold (range 4–370) greater than those of OP concentrations. In contrast to that observed
for PCBs and PAHs, NP and OP concentrations in treated sewage sludge were 7 and
25% of that found in raw sewage sludge. The reduction in NP and OP concentrations
in treated sewage sludge suggests degradation of these compounds during treatment.
Several studies have examined the degradation of NP in wastewater treatment processes
[31–33]. Although the rate of removal of NP can vary depending upon the type of
treatment applied, the results of this study suggest considerable reduction in NP
concentrations following treatment. However, the treated sludge still contained NP
concentrations of 6760 ng/g, dry wt.
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