Baseline

Edited by Bruce J. Richardson

Contamination profiles of heavy metals, organochlorinepesticides, polycyclic aromatic hydrocarbons

and alkylphenols in sediment and oyster collectedfrom marsh/estuarine Savannah GA, USA

Kurunthachalam Senthil Kumar a,*, Kenneth S. Sajwan a, Joseph P. Richardson a,Kurunthachalam Kannan b

a Department of Natural Sciences and Mathematics, Savannah State University, 3219 College Street, P.O. Box 20600, Savannah, GA 31404, USAb Wadsworth Center, New York State Department of Health and Department of Environmental Health Sciences, School of Public Health,

State University of New York at Albany, Albany, NY, USA

Inorganic compounds from natural and anthropogenicsources continuously enter the aquatic ecosystem wherethey pose a serious threat because of their toxicity, longtime persistence, bioaccumulation, and biomagnificationin the food chain (Papagiannis et al., 2004). Increasedindustrialization and agricultural activities contribute totheir elevated levels in natural waters (Wahlberg et al.,2001). Aquatic animals accumulate large quantities of thesexenobiotics, and the accumulation depends up on theintake and elimination from their body (Karadede et al.,2004). Among different aquatic organisms; clams, oystersand mussels, accumulate large quantities of heavy metalsdue to their habitat and feeding nature. Inorganic com-pounds such as heavy metals are shown to have a multitudeof toxic effects such as acute syndrome and neurotoxiceffects (that ultimately cause disease in brain, kidney, skincancer, etc.).

Organochlorine compounds (OCs) such as polychlori-nated biphenyls (PCBs) and organochlorine pesticides(OCPs) such as hexachlorocyclohexane isomers (HCHs),

chlordane compounds (CHLs), DDT and its derivatives,as well as hexachlorobenzene (HCB) have been detectedin sediments and sediment-dwelling organisms from severalcountries (Tanabe et al., 1982; Haynes et al., 2000; Gurugeand Tanabe, 2001; Loganathan et al., 2001; Senthil Kumaret al., 1999, 2001; Fillmann et al., 2002; Menone et al.,2007; Sajwan et al., 2007). Despite a 1970s ban on use ofPCBs and DDTs in the USA, these compounds are ubiqui-tous and persistent in various environmental media andbiota. Organochlorines have been reported to cause a vari-ety of adverse effects including hormone dependent can-cers, compromised reproductive fitness, and abnormalreproductive system development in wildlife and humans(Giesy and Kannan, 1998), thus they remain a cause forsignificant concern. Therefore, monitoring of fish and shell-fish in an aquatic environment serves as an important indi-cator of the water quality in a given ecosystem (Faireyet al., 1997).

Polycyclic aromatic hydrocarbons (PAHs) are a groupof common environmental contaminants. PAHs originatefrom anthropogenic sources such as waste incineration,coal gasification, accidental oil spills, as well as naturalprocesses such as fossil fuel and wood combustion (Asikai-nen et al., 2002; Law et al., 2002; Koh et al., 2004;

The objective of BASELINE is to publish short communications on different aspects of pollution of the marineenvironment. Only those papers which clearly identify the quality of the data will be considered for publication.Contributors to Baseline should refer to ‘Baseline—The New Format and Content’ (Mar. Pollut. Bull. 42, 703–704).

* Corresponding author. Tel.: +1 912 303 1913; fax: +1 912 356 2315.E-mail address: kskumar@savstate.edu (K. Senthil Kumar).

www.elsevier.com/locate/marpolbul

Available online at www.sciencedirect.com

Marine Pollution Bulletin 56 (2008) 136–162

Takasuga et al., 2007). Because of their hydrophobicity,low water solubility, and vapor pressures, PAHs tend toaccumulate in sediment and various organic components(Savinov et al., 2000; Yamashita et al., 2000; Magi et al.,2002; Kannan et al., 2003a,b, 2005; Koh et al., 2004). Sed-iment concentrations of total PAHs vary depending on thelocations and range; from a few parts-per-billion to severalparts-per-million. Occurrence of PAHs in the environmentis of concern due to their carcinogenic properties, and theirability to exert toxic effects through the aryl hydrocarbonreceptor (AhR) mediated mechanism, similar to those ofdioxins (Villeneuve et al., 2002).

Alkylphenols (APs) such as butylphenol (BP), nonylphe-nol (NP), and octylphenol (OP) are degradation productsof alkylphenol ethoxylates (APEs) which are widely usedas surfactants (Nimrod and Benson, 1996). APEs havebeen used in a wide variety of industrial and householdproducts, and were being released into the environmentsince the 1940s (White et al., 1994). APs have been detectedin sediment, water, and aquatic organisms (Isobe et al.,2001; Kannan et al., 2003a,b). These compounds have beenreported to elicit estrogenic responses in aquatic organisms(Nimrod and Benson, 1996). Because of their commonusage in cleaning products and as industrial processingaids, APs enter aquatic environments via industrial andmunicipal wastewater effluents. Relative to reports on thepresence of APs in industrial and municipal wastewaterand sewage sludge, few studies have reported their occur-rence in sediment (Yamashita et al., 2000; Isobe et al.,2001; Kannan et al., 2003a,b). The high production vol-umes, moderate persistence in sediments, and documentedtoxicity, including estrogenic effects to aquatic organisms,have resulted in concern over the risk posed by this classof chemicals.

Estuaries and the coastal marine environments areknown to receive large amounts of chemicals and are con-sidered among the most sensitive areas for the accumula-tion of toxic compounds (Sericano et al., 1990). OCPs,PCBs, PAHs, and APs can be present in high concentra-tions (ppm) in the coastal marine environment (Yamashitaet al., 2000; Kannan et al., 2001, 2003a,b). This can affectthe productivity of marine organisms, and can ultimatelybe hazardous to human health. The Savannah River isranked 7th among 50 highly contaminated rivers in theUSA which receives 13,968,965 total pounds of direct toxicdischarges to water (Savitz et al., 2000). The SavannahRiver estuary is typical of many estuaries within the SouthAtlantic Bight. The port of Savannah located in this estu-ary handles kaolin, coal, ferrous minerals, and fuel oil, aswell as raw and processed chemicals. Many industries havedeveloped around the Savannah port; this includes a paperfactory, and fertilizer and chemical manufacturing compa-nies (Winger and Lasier, 1995). Additionally, the SavannahRiver estuary receives domestic waste water and other con-taminants from several industries and mosquito controloperations along its upstream waters. Considering the sig-nificant quantities of waste products from, both industrial

and domestic sources consistently being released into theSavannah River estuary every year, it is of particular con-cern to evaluate the presence of toxic organochlorine pollu-tants mainly from anthropogenic sources. Consideringthese critical facts, in this study we analyzed inorganiccompounds including toxic heavy metals (Al, As, Cd, Cr,Cu, Fe, Hg, Ni, and Pb) polychlorinated biphenyls (PCBs),hexachlorocyclohexane isomers (HCHs), chlordane com-pounds (CHLs), DDT and its derivatives, hexachloroben-zene (HCB), PAHs, and APs in archived sediment, andoyster tissue (Crassostrea virginica) collected in 2000 and2001.

The purpose of this research was to acquire baselinechemical data, necessary to provide an evaluation of theecological health of the salt marsh estuarine ecosystem.Particularly, this study was designed to evaluate the levelsof various chemical pollutants such as highly toxic heavymetals, OCPs, PCBs, PAHs and APs in marsh/estuarinesediment, and oyster tissue. In consultation with the FortPulaski’s National Monument staff and administrationregarding industrial activity, nine sampling sites (Fig. 1and Table 1) were chosen within or along Cockspur Islandand McQueen’s Island at Fort Pulaski’s National Monu-ment salt marsh ecosystem. Three of these sites were withinOyster Creek (sites 1, 2, and 3), two sites were along BullRiver (sites 4 and 9), one site was at the mouth of theSavannah River (site-5) at an inlet opening to the AtlanticOcean. Another site was near the northeastern entrance ofLazaretto Creek (site-6), while one site was along thenorth shore of Cockspur Island in the SavannahRiver (site-7), and the last site was at the western entranceof Lazaretto Creek on Tybee Island (site-8). All thesesites were selected based on the number of undisclosedindustries, factories, domestic influence, and non-pollutedareas.

At each site, water, sediment, and oysters (C. virginica)were collected during a five-day period in November of2000 and 2001. For the water sampling, approximately2 L of water was collected from 1 m below the surface. Inthe field, the following water quality parameters were mea-sured: Secchi disk depth, temperature, salinity, total dis-solved solids, conductivity, dissolved oxygen, anddissolved oxygen percent saturation (Table 2). Water sam-ples were transported back to the lab for additional analy-ses including: pH, turbidity, settleable solids, nitrate, andphosphate (Table 2). In the case of sediment sampling, fivesub-samples of sediment from depths of 1–5 m (Table 3)were collected from each sampling site using a bottom grabsampler (clam shell type). Clean stainless steel scoops wereused to remove the top 0–5 cm of sediment from the grabsample. Sediment from each sub-sample was immediatelyplaced in acetone-washed I-Chem bottles, sealed, labeled,transported to the lab with ice, and placed in a deep-freezeruntil chemical analysis. Sediment moisture content (sedi-ment dry method) and pH (sediment and water with 1:1suspension) were analyzed in the lab (Table 3). Individualsediments (five samples from each location) were analyzed.

Baseline / Marine Pollution Bulletin 56 (2008) 136–162 137

The oysters were collected by hand or rake at the samesites; from the mid and lower intertidal zone. Oysters wereimmediately opened, and the oyster’s edible tissue was

directly transferred into acetone-washed I-Chem bottles,sealed, labeled, transported to lab with ice, and placed intodeep-freezer until chemical analysis. Edible tissue of 25–36

1

8

7

6

54

3

2

9

W 8

0o58

’

N 32o0’

AtlanticOceanFort

Pulaski

Georgia N

EW

S

Oyster Creek

Lazaretto Creek

1

8

7

6

54

3

2

9

W 8

0o58

’

N 32o0’

AtlanticOceanFort

Pulaski

Georgia N

EW

S

N

EW

S

Oyster Creek

Lazaretto Creek

Fig. 1. The map showing sampling sites.

Table 1Sampling field data

Site No. Date Time Name Latitude Longitude

1 13th November 2000 13:30 Morgans Cut 31� 59.780 80� 54.580

2 13th November 2000 15:00 Morgans Cut 32� 00.140 80� 55.120

3 14th November 2000 14:30 Oyster Creek entrance 32� 00.890 80� 55.440

4 14th November 2000 16:00 Bull River 32� 00.890 80� 55.930

5 15th November 2000 14:00 Goat Point, Atlantic 32� 01.130 80� 52.930

6 15th November 2000 15:30 Screvens Point, SRa 32� 01.630 80� 57.840

7 04th November 2001 14:00 Coast Guard Station, SRa 32� 02.110 80� 54.640

8 04th November 2001 15:30 Lazaretto Creek 32� 00.560 80� 53.210

9 07th November 2001 16:30 Bull River at Lazaretto 31� 59.700 80� 55.550

a Savannah River.

Table 2Water quality parameters

SiteNo.

Watertemperature(�C)

Secchi(cm)

Turbidity(NTU)

Settleablesolids(mL/L)

Salinity(ppt)

TDS(mg/L)a

Conductivity(mS)

Dissolvedoxygen(mg/L)

Oxygenpercentsaturation

pH Nitrate(mg/L)

Phosphate(mg/L)

1 19.4 97 17 Trace 31.2 30,100 48.3 6.13 93 7.66 0.57 0.182 19.3 98 14 Trace 31.6 30,400 48.8 5.98 91 7.64 0.48 0.043 19.1 66 20 Trace 30.9 29,700 47.8 6.57 99 7.51 0.44 0.124 18.4 80 12 Trace 29.5 28,400 45.8 6.21 92 7.49 0.53 0.115 18.9 56 27 0.1 27.6 26,500 43.1 7.72 110 7.81 1.06 0.106 17.6 57 22 0.1 28.2 27,100 44.0 7.66 110 7.56 0.70 0.077 19.8 51 51 0.3 25.2 24,400 39.9 7.73 109 7.79 0.53 0.148 19.8 78 24 Trace 25.6 24,600 40.2 7.29 104 7.70 0.18 0.079 18.6 65 24 0.1 31.2 30,000 48.1 7.65 115 7.80 0.48 0.03

a TDS denote total dissolved solids.

138 Baseline / Marine Pollution Bulletin 56 (2008) 136–162

oysters, were collected at each site to form a single compos-ite oyster sample from each site.

Collected sediment samples for elemental analysis wereair dried in the greenhouse, and the air-dried samples wereanalyzed for pH and trace elements as follows: The pH ofsediment samples were measured by sediment:water (1:1)suspension using Fisher Accumet model-15 pH meter, asdescribed by the methods for soil analysis (McLean,1982). Extractable elements were analyzed by Mehlich-3(M-3) extraction method. Briefly, 2.5 g of air-dried sedi-ment sample was placed in a 50-mL screw-capped polypro-pylene centrifuge tube, and 25 mL of Mehlich-3 extractant(Mehlich, 1984) was added and shaken for 5 min. Thesesamples were centrifuged and the supernatant was filteredthrough Whatman 42 filter paper. The clear supernatantwas saved and analyzed for various metals using PerkinElmer RL 3300 (ICP-OES). Mercury and arsenic were ana-lyzed by instrumental neutron activation analysis (INAA).

In the case of oyster tissue analysis, the edible tissuesamples were subjected to moisture content determination,followed by freeze drying. Analysis of heavy metals in oys-ter tissues were described elsewhere (Kannan et al., 1998).One subset of oyster tissue composite was prepared foranalysis of lead, arsenic, and mercury by a hot acid diges-tion method. Mercury was analyzed by inductively coupledplasma-mass spectrometry (ICP-MS), and arsenic and leadwere analyzed by graphite furnace atomic absorption spec-trometry (GFAAS).

PCBs, PAHs, and APs were analyzed following methodsdescribed elsewhere (Khim et al., 1999a,b). Sediment andoyster tissue samples were briefly Soxhlet extracted for

20-h using dichloromethane (DCM; Burdick & Jackson,Muskegon, MI, USA). Extracts of sediment were then trea-ted with acid-activated copper granules to remove sulfur.For oyster extracts the fat content was analyzed (Table 3)using the gravimetric method. Aliquots of extracts wereconcentrated to approximately 5-mL by rotary evaporation(39 �C), and then to 1-mL under a gentle stream of nitro-gen. Extracts were passed through 10-g of activated Florisil(60–100 mesh size; Sigma, St. Louis, MO, USA) packed ina glass column (10 mm i.d.) for clean-up and fractionation.The first fraction (F1) eluted with 100-mL of hexane (Bur-dick & Jackson) contained OCPs and PCBs. PAHs wereeluted in the second fraction (F2) using 100-mL 20% dichlo-romethane (DCM) in hexane. NP, OP, and BP were elutedin the third fraction (F3) with 100-mL 50% DCM in meth-anol (Burdick & Jackson). Recoveries of target analytesthrough all the analytical steps were between 90% and105%. Sub-samples of F1 and F2 were treated with concen-trated H2SO4 to provide additional clean-up, whichimproved detection limits for PCBs.

OCPs and PCBs were quantified using a gas chromato-graph (Perkin Elmer series 600) equipped with 63Ni elec-tron capture detector (GC-ECD). A fused silica capillarycolumn coated with DB-5MS [(5%-phenyl)-meth-ylpolysiloxane, 30 m · 0.25 mm i.d.; J&W Scientific, Fol-som, CA, USA] having a film thickness of 0.25 lm wasused. The column oven temperature was programmed from120 �C (1 min hold) to 180 �C at a rate of 10 �C/min (1 minhold), and then to 260 �C at a rate of 2 �C/min with a finalholding time of 12 min. Injector and detector temperatureswere kept at 250 �C and 300 �C, respectively. Helium andnitrogen were used as carrier and make up gases, respec-tively. Known concentrations of OCPs were mixed andused as a reference standard. A solution containing 98 indi-vidual PCB congeners with known composition and con-tent was used as a standard, and concentrations of 98individually resolved peaks were summed up to obtaintotal PCB concentrations (Khim et al., 2000). Detectionlimits of PCBs for 2000 samples were set as 10 ng/g, andfor 2001 samples as 1.5 ng/g, while for OCPs, detectionlimits were set as 5 pg/g.

PAHs were quantified using a Hewlett Packard 5890 ser-ies II gas chromatograph equipped with a 5972 series massspectrometer detector (GC-MSD). A fused silica capillarycolumn (30 m · 0.25 mm i.d.) coated with DB-17 [(50%phenyl)-methylpolysiloxane; J&W Scientific, Folsom, CA,USA] at 0.25 lm film thickness was used. The column oventemperature was programmed from 80 �C (1 min hold) to100 �C at a rate of 25 �C/min, and then ramped up to a rateof 5 �C/min to 300 �C with a final holding time of 6 min.The injector and detector temperatures were maintainedat 250 �C and 300 �C, respectively. The PAH standard(AccuStandard, New Haven, CT, USA) consisted of 16 pri-ority pollutant PAHs identified by the US EnvironmentalProtection Agency (US EPA; Method 8310). The massspectrometer was operated under a selected ion monitoring(SIM) mode using the molecular ions selective for individ-

Table 3Sampling details and some physico-chemical properties of sediment andoyster

Sample Collection depth (m) Moisture (%) pH

Sediment

Site-1 2.8 (1–5) 73 (71–77) 7.8 (6.7–8.1)Site-2 3.2 (3–4) 59 (50–71) 7.9 (7.6–8.1)Site-3 3.0 (2–4) 60 (53–64) 7.8 (7.1–8.2)Site-4 3.6 (2–5) 47 (34–57) 8.0 (7.6–8.3)Site-5 2.8 (2–4) 48 (39–53) 8.1 (7.9–8.2)Site-6 3.8 (2–5) 60 (53–64) 5.0 (3.5–7.6)Site-7 2.6 (1–4) 61 (57–63) 7.6 (7.3–7.9)Site-8 3.0 (2–4) 66 (60–72) 7.6 (7.3–7.8)Site-9 1.4 (1–3) 58 (53–68) 7.9 (7.8–8.0)

Sample Moisture (%) Fat (%)

Oyster

Site-1 20.02 1.3Site-2 20.63 1.4Site-3 20.69 1.5Site-4 20.62 1.5Site-5 20.14 1.2Site-6 20.19 NASite-7 20.61 NASite-8 20.70 NASite-9 20.62 NA

Values in parentheses indicate range; NA = not analyzed.

Baseline / Marine Pollution Bulletin 56 (2008) 136–162 139

ual PAHs (Khim et al., 1999b). Calibration standards wereprepared at 0.25, 0.5, 1, 2, and 5 lg/mL. Concentrationsbased on individually resolved peaks were summed toobtain the total PAH concentrations. The detection limitsof total PAHs for sediment and oyster samples were0.1 ng/g ww.

Reverse phase high performance liquid chromatography(HPLC) with fluorescence detection was used to quantifyBP, NP, and OP (Khim et al., 1999c). High purity p-nonyl-phenol and p-tert-octylphenol standards (SchenectadyInternational, Freeport, TX, USA) were prepared in highpurity acetonitrile (ACN; Burdick & Jackson) at 0.32,0.63, 1.25, 2.5, 5, and 10 lg/mL for the calibration run.Standards were injected freshly along with every set of sam-ples and the R2 for calibration was maintained at P0.99.Samples and standards were injected (10-ll) by a PerkinElmer 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 ACN andwater at a gradient from 50% ACN in water to 98% ACNin water delivered by a Perkin Elmer Series 200 pump for20 min. Detection was accomplished using a Hewlett Pack-ard 1046A fluorescence detector (Hewlett-Packard, Wil-mington, DE, USA) with an excitation wavelength of229 nm and an emission wavelength of 310 nm. NP, OP,and BP detection limits for the analytical method were<0.2 and <0.5 ng/g ww for sediment and oysters, respec-tively. Blank analysis was performed with each batch con-taining five samples. However, none of the samplesdetected DDE, PCBs, PAHs, and APs at detection limitby 2.0, 0.2, 0.1, and 0.2/0.5 ng/g ww, respectively.

Water quality parameters (Table 2) were normal andtypical of the Georgia salt marsh ecosystems duringautumn. At this location near the Savannah River inletand Atlantic Ocean, salinity is expected to be relativelyhigh (mid to high 20s). Water clarity as indicated by Secchidisk depth was typical of Georgia estuarine river andmarsh creeks. Dissolved oxygen levels were high which istypical to autumn and winter conditions in these habitats.Nutrients, particularly nitrates, were slightly elevated; how-ever, during a previous study (Richardson, unpublisheddata) slightly elevated nitrate levels were noticed in watersamples from Savannah River estuary in comparison tosamples from Wilmington River/Wassaw Sound estuaryfurther south. Overall, water quality parameters measuredduring this study and taken during the limited time span ofsampling were typical and normal. Continued water qual-ity monitoring, with more frequent sampling should beconducted in order to reveal any temporal trends inquality.

Mean depth of sediment collection varied from 1.4 to3.8 m (average of five sub-sampling) at the 9 sites (Table3). Average sediment moisture content was 47–73% (aver-age of five sub-sampling), whereas pH was in between 5.0and 8.1. The lowest pH (3.5) was noticed at site-6, whereas

the highest (8.3) at site-4. Most sediment samples had pHvalues of 7–8. Site-6 was different from the other sites inhaving a relatively low pH value for four out of fivesediment sub-samples collected at the site. Most of thesediment samples were classified as pelite (silt-clay)(<0.063 mm in diameter of grains), sand (0.063–2 mm)and gravel (>2 mm). Fat percent in oyster tissue was 1.2–1.5, while site-6 oysters showed very low fat % of 0.005;sites 7–9 fat contents were not determined. Therefore, thefat weight basis of organic compounds should be ignoredfor further discussions. Moisture content in oyster tissuewas between 20% and 21% (Table 3).

Average concentrations of inorganic contaminants fromsediment (n = 5) have been illustrated in Table 4. Macronutrients such as calcium (Ca) was higher in sediment fol-lowed by magnesium (Mg) and phosphorus (P), whereassodium (Na), potassium (K), and sulfur (S) were not ana-lyzed in sediment (Table 4). Among the extractable metals,the following trace metals were of particular interest: alu-minum (Al), arsenic (As), cadmium (Cd), chromium (Cr),copper (Cu), iron (Fe), mercury (Hg), manganese (Mn),lead (Pb), and zinc (Zn). Contamination of heavy metalsin sediment were in the following order Fe > Al > Mn >As > Zn > Hg > Cr > Pb > Cd (Table 4). Whereas, Cuand Ni were not detected. Observed trace elements concen-trations in this study were less than in soil (Adriano, 2001),and the Florida Cedar and Ortega River sediments (Ouy-ang et al., 2001). With the exception of Hg, Fe, and Al;the contamination of other HM’s are not pronounced.

Mean mercury concentrations in sediment samplesfrom sites 1 to 6 ranged from 1200 to 1900 ng/g dw. Bycomparison, Adriano (2001) indicated a normal soilconcentration of mercury ranging from 20 to 250 ng/g.Kannan et al. (1998) reported total mercury concentra-tions in sediments from south Florida estuaries rangingfrom 1 to 219 ng/g dw. These comparisons show thatmercury concentrations in the Savannah estuary is com-paratively higher than the Florida coast. Mean arsenicconcentrations in sediment (sites 1–6) ranged from 11 to55 lg/g dw. By comparison, Adriano (2001) reportednon-contaminated USA soils having an average arsenicconcentration of 7.4 lg/g, and ocean sediments as havingaverage arsenic concentration of 34 lg/g (with a rangefrom <0.40 to 455 lg/g). Arsenic is often a componentof pesticides, and the highest sediment concentrationfound during this study was from site-6 which is the siteclosest to residential development areas.

Macronutrients in oyster tissue were observed in the fol-lowing order Ca P S > K > P > Mg (Table 4). Heavymetal contamination in oyster was observed in the follow-ing order Zn > Al > Fe > Si > B > Cu > Mn > Cr P Pb PCd P Ni > Mo P As > Hg (Table 4). Correlation relation-ships and the bioaccumulation factors (BAF; based on dryweight concentration in oyster/sediment) were calculated(data not shown). No significant correlation (R2 =0.2275) of Pb was observed (Fig. 2a). BAF for Pb was highat site-5 (5.3), whereas site-6 showed a low BAF (1.6)

140 Baseline / Marine Pollution Bulletin 56 (2008) 136–162

(Fig. 2b). However, BAF for P (range: 88–1867), and Zn(range: 188–632) were more elevated when compared toHg (range: 0.07–0.59) and As (range: 0.01–0.08) (data not

shown). These results suggested the bioaccumulation ofheavy metals in oysters varies depending upon their chem-ical properties.

1

y = 1.9715x + 0.671R2= 0.2275

0

1.25

2.5

3.75

5

0 0.5 1.0

0.0

1.8

3.5

5.3

7.0

Pbin

Oys

ter

(μg/

g dr

yw

t.)

Pb in Sediment(μg/g dry wt.)

BA

F of

Pb

St-1 St-2 St-3 St-4 St-5 St-6 St-7 St-8 St-9

y = 1.9715x + 0.671R2= 0.2275R2= 0.2275

0

1.25

2.5

3.75

5

0 0.5 1.0

0.0

1.8

3.5

5.3

7.0

Pbin

Oys

ter

(g/

g dr

yw

t.)

Pb in Sediment( g/g dry wt.)

St-1 St-2 St-3 St-4 St-5 St-6 St-7 St-8 St-9

a b

Fig. 2. Correlation of Pb (a) and their bio-accumulation factor (BAF) (b) in oyster.

Table 4Mean concentrations of extractable essential and non-essential elements in sediments and oyster (lg/g dw)

Site-1 Site-2 Site-3 Site-4 Site-5 Site-6 Site-7 Site-8 Site-9

Sediment

P 4.3 4.2 1.5 69 8.3 43 21 22 16Ca 5400 10,000 14,000 8900 7200 2900 2300 2200 3300Mg 2800 2400 2600 1500 1600 2400 840 690 950Zn 5.9 5.0 5.7 3.8 5.8 9.6 2.1 2.8 2.4Mn 54 43 37 43 78 93 36 20 25Fe 820 750 700 600 700 970 380 580 540Pb 0.59 0.62 0.95 0.41 0.45 0.95 0.64 0.47 0.48Al 560 380 410 360 190 820 120 130 17Cd 1.2 1.0 0.10 0.10 0.05 0.31 0.09 0.07 NDCr 0.78 0.72 0.67 0.66 1.4 1.0 0.42 0.74 0.68Hg 1.9 1.2 1.4 1.7 1.3 1.7 NA NA NAAs 48 28 11 29 21 55 NA NA NA

Oyster

P 3700 5600 2800 6800 5900 3800 6500 7900 6500Ca 30,000 27,000 20,000 53,000 28,000 39,000 87,000 23,000 44,000Mg 3600 6400 2800 6200 3900 4100 5100 6100 5600Zn 1300 2000 1400 2400 1300 1800 1100 1600 980Mn 32 52 17 54 23 29 25 38 38Fe 400 740 310 230 460 450 500 1400 930Cu 93 100 87 120 82 93 79 90 67Pb <1.5 <1.5 4.0 1.6 2.4 <1.5 <1.5 <1.5 <1.5Al 410 880 400 1300 740 640 610 810 1500Cd <1.5 <1.5 <1.5 <1.5 <1.5 <1.5 2.4 2.9 2.2Cr <1.5 <1.5 8.0 <1.5 <1.5 <1.5 1.6 2.1 1.8Ni <1.5 <1.5 <1.5 <1.5 <1.5 <1.5 1.8 2.5 2.3K NA NA NA NA NA NA 10,000 12,000 10,000B NA NA NA NA NA NA 230 250 250Mo NA NA NA NA NA NA 0.61 <0.5 0.64S NA NA NA NA NA NA 16,000 17,000 17,000Si NA NA NA NA NA NA 240 260 380Hga 170 130 160 710 93 910 250 120 140Asa 480 200 830 600 720 910 3000 1900 350

Cu and Ni were not detected in sediment; values rounded.a ng/g dry weight.

Baseline / Marine Pollution Bulletin 56 (2008) 136–162 141

The World Health Organization (WHO) has establisheda provisional tolerable weekly intake (PTWI) for Cd at7 lg/kg of body weight. This PTWI weekly value corre-sponds to a daily tolerable intake level of 70 lg of Cd forthe average 70-kg man, and 60 lg of Cd per day for theaverage 60-kg woman. Clearly, the daily Cd intake forthe general population from oysters analyzed in this study(<1.5–2.9 lg/g dw), is well below the guidelines establishedby WHO. The United States Food and Drug Administra-tion (USFDA, 1993) set an estimated safe and allowabledaily consumption level for Cr at 200 lg/person/day, andfor Ni at 1200 lg/person/day. Concentrations of Cr in oys-ter tissues were <1.5–8.0 lg/g on dry weight basis. Con-sumption of oyster from any of study sites do not poseany significant health problems to humans. Concentrationsof Ni in oysters were <1.5–2.5 lg dw. Even a 500 g/dayintake of oyster from site-8 with Ni 2.5 lg may not produceany significant detrimental effects. The tolerable dailyintake of Pb was 25 lg/kg body wt which is well belowthe concentrations observed in oyster tissues in Savannahcoastal waters. United States Environmental ProtectionAgency (USEPA) has established an interim reference dose(RfD) for methylmercury (MeHg) of 1 · 10�4 lg/kgbody wt/day. The EPA recommends, however, that theconservative assumption be made that all mercury is pres-ent as MeHg. Therefore, in order to be the most protectiveof human health; the EPA indicates that the typical USconsumer, eating less than 10 g of fish and shellfish perday which have average mercury concentrations between100 and 150 ng/g, may actually have adverse health impact.Concentrations of Hg in 1 g of oysters were between 93 and908 ng/g. Therefore oyster’s collected from sites 1, 3, 4, 6,and 7 crossed the 150 ng/g limit, and are considered to poseadverse health effects. Arsenic was detected in all oystertissue samples greater than Hg, with a range from 200 to3042 ng/g dw (Table 4). Based on World Health Organiza-tion (WHO), the lethal dose of arsenic trioxide is 10–180 lg, and for arsenide is 70–210 lg. These As levels aremuch higher than those observed concentrations found inoyster tissue analyzed in this study.

Among OCPs, a,b,c,d-HCHs, chlordane compoundssuch as cis/trans-chlordane, cis/trans-nonachlor, oxychlor-dane, heptachlor and heptachlor epoxide, DDT and itsmetabolites such as o,p 0/p,p 0-DDT, o,p 0/p,p 0-DDD ando,p 0-DDE and HCB were under the detection limits(<13 pg/g) in sediment and oyster tissue. While p,p 0-DDE(a final metabolic product of DDT in biological samples)were in the range of <13–210 pg/g dw (Table 5) in sedi-ment. Oyster showed greater DDE concentrations rangingfrom 180 to 650 pg/g dw (Table 5). Correlations for PCBscould not be performed, while DDE showed no significantcorrelation (R2 = 0.5496; Fig. 3a). However, BAF weregreater in site-9 (33) and lower in site-1 (4.7) oysters(Fig. 3b). Overall, OCPs contributed less contaminationthan inorganic pollutants.

DDT undergoes a degradation process from DDD thanto DDE. The DDE accounts for 70–90% of total DDT bur-

den in biological samples (Senthil Kumar et al., 2001). Inspite of continued usage, DDT was not detected in anyof the brackish water environment in India (Sankar et al.,2006). Sediment DDE concentrations in Argentina was inthe range of 11–23 ng/g. Low levels of DDEs in sedimentin this study may be due to a ban passed in 1970; whichresulted in less agricultural activity and more natural influ-ences like weathering and metabolic activity of aquaticbiota and bacteria. Sediments with a higher ratio of claycan retain larger amounts of pesticide residues thansandy-clay or sandy-silt sediments. Also sediment contain-ing the higher levels of organic carbon would have less bio-availability of chemicals. These factors explain all thereasons for finding low levels of OCPs in sediments in thisstudy. Altogether, from a public health point, residue levelsof DDE in oyster samples analyzed in this study are muchlower than the Food and Agriculture Organization’s(FAO) recommended levels of 300 ng/g DDT. AverageDDE concentrations in 2001 sediments (9.2) and oysters(180) were less than those samples collected in 2000s sedi-ments (22) and oysters (320), this trends shows a temporalvariation. However, the concentration is very low, and thenumber of samples analyzed is not sufficient enough for atemporal variation interpretation.

Predominant PCBs (72 congeners) were less than detec-tion limit in sediment (<19 to <37) and oysters (<13) col-lected in 2000. On the other hand, 2001 samplescontained 5.0–11 (sediment) and 10–15 (oyster) ng/g dwafter an improvement of the detection limit. An earlierstudy reported low concentrations of total PCBs in fin fishfrom Savannah coastal waters (Loganathan et al., 2001).Our recent study (Sajwan et al., 2007) reported compara-tively lower PCBs and DDE concentrations in fin fish.

Table 5Concentrations of DDE and total PCBs in sediment and oyster

Sample DDE PCBs

pg/g ww pg/g dw ng/g ww ng/g dw

Sediment

Site-1 21 (2.1–28) 78 (7.8–100) <10 <37Site-2 15 (2.7–29) 37 (6.6–71) <10 <24Site-3 17 (2.3–25) 42 (5.8–63) <10 <25Site-4 27 (4.3–48) 51 (8.1–91) <10 <19Site-5 35 (2.5–48) 67 (4.8–92) <10 <19Site-6 19 (2.5–23) 47 (6.3–58) <10 <25Site-7 7.3 (<5–24) 19 (<13–62) 3.6 (<1.5–6.1) 9.2 (<3.8–15)Site-8 18 (<5–72) 53 (<13–210) 1.7 (<1.5–3.2) 5.0 (<4.4–9.4)Site-9 2.3 (<5–11) 5.5 (<13–26) 4.5 (2.4–8.4) 11 (5.7–20)

Oyster

Site-1 290 370 <10 <13Site-2 250 310 <10 <13Site-3 200 250 <10 <13Site-4 350 440 <10 <13Site-5 520 650 <10 <13Site-6 320 400 <10 <13Site-7 140 180 11 14Site-8 260 320 12 15Site-9 140 180 8.1 10

ww and dw, respectively, wet weight and dry weight; values rounded.

142 Baseline / Marine Pollution Bulletin 56 (2008) 136–162

Regional variation in sampling, animal species, and thetime trend should be considered. Sediment quality guide-lines (SQG) have been proposed for PCBs in sedimentsusing theoretical and empirical approaches. Based on thereviews available for SQGs consensus threshold and mod-erate-effect concentration (MEC) of 40 and 400 ng/g dw,respectively, has been proposed for total PCBs. Conse-quently, total PCBs concentrations in this study were lessthan the SQG values.

Global comparison of total PCBs and DDE in sedimentsuggests that the concentrations were lower in this presentstudy when compared to Estuaries in India, China, Viet-nam, Sri Lanka and Korea (Chen et al., 1986; Honget al., 1995; Nhan et al., 1999; Senthil Kumar et al.,1999, 2001; Guruge and Tanabe, 2001; Yuan et al., 2001;Guzzella et al., 2005), and to rivers in Poland, and Detroit,MI, USA (Kannan et al., 2001, 2003a). The measured con-centrations of total PCBs in oysters from estuarine Savan-nah were very less than the (USFDA) tolerance limit of2 lg/g ww for total PCBs in fish and shellfish (Kannanet al., 1997).

Among the chemicals studied, PAHs were greater thanOCPs however; they were still lower than the heavy metals(Table 6). Concentrations of total PAHs in sedimentsranged from 1.2 to 160 ng/g dw. Overall contaminationpatterns of total PAHs from different sites were indecreasing order: site-8 > site-9 > site-5 > site-6 = site-4 >site-1 > site-2 P site-7 > site-3. Fluoranthene was preva-lent in sites 1, 2, 3, 5, 6, and 7; while pyrene was slightlyhigher in site-8; benzo[k]fluoranthene was slightly higherin site-4; and benzo[a]pyrene was slightly higher in site-9.Slight variations in PAH concentrations between sites sug-gests different sources of contamination. Changes in thePAH pattern may reflect changes in the source of PAHssuch as coal, oil, gas, and petroleum combustion, and theresulting effect of combustion conditions. However, PAHsoriginate mainly from petrogenic and pyrolytic sources.

Four- and five-ring PAHs were the most abundant com-pounds in sediment, whereas two- and three-ring PAHswere less abundant. In terms of composition patterns ofPAHs in sediment, it was dominated by five-ring PAHs.Pereira et al. (1996) showed that four-ring PAHs domi-nated PAH distributions in sediments from the San Fran-cisco Bay. Pyrolysis/combustion of fossil materials yieldsthese PAH assemblages, which are subsequently intro-duced into the marine environment by coastal and riverrunoff (Hoffman et al., 1984), and by direct dry or wetdeposition from the atmosphere (Dickhut and Gustafson,1995). Industrial and/or domestic wastes are often anotherimportant local source. Greater benzofluoranthenes con-centrations suggests a major source from high temperaturepyrolytic processes (Simoneit, 1987). In this study, sedi-ment from site-4 contained slightly higher benzofluoranth-ene and therefore thermal industries from the Bull Rivermay have been an influential factor. On average, fluoranth-ene, pyrene, benzo[a]pyrene, and benzo[k]fluoranthenetogether accounted for 75% of the total PAHs in sediment.

The possible sources of PAHs in sediments may beassessed by the ratios of individual PAH compounds (Ben-laheen et al., 1997). A ratio of phenanthrene/anthracene<10 and fluoranthene/pyrene >1 tends to indicate thatthe PAH contamination is from combustion processes(Benlaheen et al., 1997). In contrast fluoranthene/pyreneratios >1 are attributed to pyrolytic origin whilst values<1 are related to petrogenic sources. Except sites 4 and 5,the ratios of phenanthrene/anthracene was <10 and there-fore these results indicate combustion source of PAHs froma majority of sites. On the other hand, fluoranthene/pyreneratios were <1 in sites 7 and 8. Petrogenic sources in sites 7and 8 may have had a possible influence on contaminationwhile other sites are considered to be a pyrolytic source.Overall, it is apparent that multiple sources would haveaccounted for the PAH contamination in the Savannahestuary.

y = 4.8337x + 128.1R2 = 0.5496

0

200

400

600

800

0 50 100

0

10

20

30

40

DD

E in

Oys

ter

(pg/

g dr

y w

t.)

DDE in Sediment(pg/g dry wt.)

BA

F of

DD

E

St-1 St-2 St-3 St-4 St-5 St-6 St- St-8 St-9

y = 4.8337x + 128.1R2 = 0.5496R2 = 0.5496

0

200

400

600

800

0 50 100

0

10

20

30

40

DD

E in

Oys

ter

(pg/

g dr

y w

t.)

DDE in Sediment(pg/g dry wt.)

BA

F of

DD

E

St-1 St-2 St-3 St-4 St-5 St-6 St-7 St-8 St-9

a b

Fig. 3. Correlation of DDE (a) and their bio-accumulation factor (BAF) (b) in oyster.

Baseline / Marine Pollution Bulletin 56 (2008) 136–162 143

Temporal variation of total PAHs were not pronouncedbetween 2000 (32 ng/g dw) and 2001 (34 ng/g dw) sedimentsamples. The measured concentrations of PAHs in sedi-ment were relatively low compared to sediment from theDetroit River, Michigan River, Casco Bay, ChesapeakeBay, Penobscot Bay, and San Diego Bay in the USA;and several aquatic bodies in Japan, Poland, United King-dom, the White Sea, Barents Sea, Hong Kong, PuertoRico, Caribbean Island, Adriatic Sea, Korea, China, andCanada (Johnson et al., 1985; Forster and Wright, 1988;Kennicutt et al., 1994; Kleowski et al., 1994; Andersonet al., 1996; Bernard et al., 1996; Simpson et al., 1996; Yun-ker et al., 1996; Khim et al., 1999a,b,c; Savinov et al., 2000;Yamashita et al., 2000; Kannan et al., 2001, 2003a, 2005;Tam et al., 2001; Law et al., 2002; Magi et al., 2002;Maskaoui et al., 2002). Earlier studies of PAHs in sedimentcores collected from USA, Europe, and Japan revealed agradual decrease in overall concentrations in the 1970sand the 1980s. However, other recent studies have sug-gested that the emissions of PAHs have actually increasedin certain urban areas of the United States. Therefore, con-tinuous PAH monitoring studies are warranted in sedimentsamples from estuarine environment of Savannah GA,USA.

Contaminated sediments can directly affect bottom-dwelling organisms and represent a continuing source fortoxic substances in aquatic environments that may affectwildlife and humans via the food chain. This was foundto be true in the present study because greater number ofPAHs were detected in oyster tissues (Table 7), than in sed-iments (Table 6). Concentrations of PAHs in oysters ran-ged from 4.0 to 260 ng/g dw. Overall the contaminationpattern for total PAHs in various sites were observed inthe following decreasing order site-2 > site-1 > site-5 > site-6 P site-3 > site-8 P site-4 > site-7 P site-9. Withcontrast to the sediment concentration, PAH bioaccumula-tion varied in oyster tissues. Fluoranthene was predomi-nant in sites 7 and 8 oysters; pyrene was abundant insites 2, 6, and 9 oysters; and indeno(1,2,3-cd)pyrene wasabundant in sites 1, 3, 4, and 5 oysters (Table 7). This sug-gests a greater bioaccumulation potential for the highermolecular weight PAHs compounds. In particular,indeno(1,2,3-cd)pyrene was prevalent in all the oyster sam-ples. Consumption of contaminated oysters may lead tohuman exposure of indeno(1,2,3-cd)pyrene. No positivecorrelation was observed between sediment and oysters(Fig. 4a). Furthermore, PAH-BAF in oysters (Fig. 4b)was also lower when compared to DDE (Fig. 3b).

Seven of the 16 priority PAHs tested to induce signifi-cant dioxin-like responses. Benzo[a]anthracene anddibenzo[a,h]anthacene induce significant responses in theMVLN bioassay (Villeneuve et al., 2002). Some representa-tive studies have shown PAHs to be capable of inducingdioxin-like responses in vitro in fish (Villeneuve et al.,1998; Bols et al., 1999; Fent and Batscher, 2000; Behrenset al., 2001) and mammalian cell lines. PAHs have alsobeen shown to induce ethoxyresourufin-O-deethylaseT

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ree

dig

its

has

bee

nro

un

ded

.

144 Baseline / Marine Pollution Bulletin 56 (2008) 136–162

(EROD) activity in vivo (Brunstrom et al., 1991; Basuet al., 2001). Three PAHs-benzo[a]pyrene, chrysene, andbenzo[a]anthracene have been reported to elicit estrogenicresponses in vitro (Clemons et al., 1998). For all sedimentsamples, chrysene was detected in all sites; benzo[a]anthra-cene was detected at 6 sites (sites 1, 2, 4, 5, 6, and 8), ben-zo[a]pyrene was detected at 5 sites (sites 1, 4, 6, 7, 8, and 9)and dibenzo(a,h)anthracene was detected at site-6. In oys-ter tissue benzo[a]anthracene was detected at 5 sites (sites1, 5, 6, 7, and 8); chrysene was detected at 3 sites (sites 5,6, and 9), benzo[a]pyrene was detected at 3 sites (sites 1,2, and 5); and dibenzo(a,h)anthracene was detected at 3sites (sites 1, 3, and 5). Consequently the presence of alltoxic PAH compounds found in sediments and oystersfrom sites 1, 5, and 6 are of major concern.

Alkylphenols, in particular, NP, was detected in somesediments and oysters (Table 8). Mean concentrations ofBP, OP, and NP in sediments were in the ranges of <0.3–28, <0.3–29 and <0.3–78 ng/g dw, respectively. Althoughthe concentrations were relatively low compared to thosein industrialized areas, the presence of NP in sedimentssuggests exposure to alkylphenolic surfactants from sewagedisposal. APs were not measured in oyster collected in sites7, 8, and 9 in 2001. However, samples collected in 2000contained APs ranging from <0.5 to 1.2, <0.5 to 7.9, and<0.5 to 16 ng/g ww BP, OP, and NP, respectively (Table8). Greater NP concentrations in sediment samples sug-gested recent inputs. NPs are used as detergents, emulsifi-ers, wetting agents, and dispersing agent’s in household,and industrial products, and in agricultural applications.

Table 7Concentrations of PAHs in oyster tissue

PAHs Site-1 Site-2 Site-3 Site-4 Site-5 Site-6 Site-7 Site-8 Site-9

Naphthalene 0.30 <0.1 <0.1 0.40 <0.1 <0.1 <0.1 <0.1 0.73Acenaphthalene <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1Acenaphthene 0.53 0.55 <0.1 0.32 0.38 <0.1 0.12 0.28 <0.1Fluorene <0.1 1.0 0.69 0.64 0.96 <0.1 <0.1 <0.1 0.20Phenanthrene <0.1 6.5 1.9 1.6 3.3 1.7 0.84 2.7 0.43Anthracene <0.1 <0.1 <0.1 <0.1 0.28 <0.1 <0.1 <0.1 <0.1Fluoranthene 2.2 15 1.3 0.30 3.7 5.3 2.1 9.8 0.71Pyrene 10 106 7.2 0.07 5.5 33 0.59 6.2 0.78Benzo[a]anthracene 0.24 <0.1 <0.1 <0.1 0.28 0.30 0.60 2.4 <0.1Chrysene <0.1 <0.1 <0.1 <0.1 0.58 0.83 <0.1 <0.1 0.30Benzo[b]fluoanthene <0.1 <0.1 <0.1 1.4 4.4 <0.1 <0.1 <0.1 <0.1Benzo[k]fluoranthene 11 <0.1 <0.1 <0.1 3.7 <0.1 <0.1 <0.1 <0.1Benzo[a]pyrene 40 7.2 <0.1 <0.1 48 <0.1 <0.1 <0.1 <0.1Indeno(1,2,3-cd)pyrene 109 73 43 14 64 20 <0.1 <0.1 <0.1Dibenz(a,h)anthracene 6.4 <0.1 0.77 <0.1 3.8 <0.1 <0.1 <0.1 <0.1Benzo(g,h,i)perylene <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

Total PAHs (ng/g ww) 180 210 55 18 140 60 4.2 21 3.2Total PAHs (ng/g dw) 220 260 70 23 170 76 5.3 27 4.0

NC = not calculated; values with three digits were rounded.

y = -0.057x + 98.127

R2 = 9E-05

0

75

150

225

300

0 20 40 60

PAH

sin

Oys

ter

(ng/

gdr

y w

t.)

PAHs in Sediment(ng/g dry wt.)

0

5

10

15

20

BA

F of

PA

Hs

St-1 St- St-3 St-4 St- St-6 St-7 St-8 St-9

y = -0.057x + 98.127

R2 = 9E-05R2 = 9E-05

0

75

150

225

300

0 20 40 60

PAH

sin

Oys

ter

(ng/

gdr

y w

t.)

PAHs in Sediment(ng/g dry wt.)

0

5

10

15

20

BA

F of

PA

Hs

St-1 St-2 St-3 St-4 St-5 St-6 St-7 St-8 St-9

a b

Fig. 4. Correlation of PAHs (a) and their bio-accumulation factor (BAF) (b) in oyster.

Baseline / Marine Pollution Bulletin 56 (2008) 136–162 145

Some 4-NP polyethoxylates (NPEOs) and to a lesser extentNPs, have been used in a variety of cleaning products, pes-ticide formulations, plastics, cosmetics, and birth controlproducts. The NPs exhibit lower water solubilities andhigher lipophilicities than their ethoxylate precursors.Thus, they have a greater tendency to bioaccumulate andpartition to organic-rich sediment. No positive correlation(OP: R2 = 0.0627 and NP: R2 = 0.0371) that was observedbetween sediment and oysters (Fig. 5a and c). FurthermoreOP and NP-BAF in oysters also were lower when com-pared to DDE and PAHs, and even several orders of mag-nitude lower than those of in inorganic compounds (Fig. 5band d).

Two estrogenic PAHs were characterized as potent, andsimilar to those reported for other environmental xenoes-trogens of concern, including NP and OP (Villeneuveet al., 1998). Particularly, NPs have been reported to dis-rupt endocrine function and sexual development in aquaticorganisms at low concentrations. Carboxylated metabolitesof NP and OP are known to exert estrogenic effects inaquatic organisms and in mammals and birds, while thehigher ethoxylates of NPEOs lack estrogenic activity.Although the APs accumulated at low levels; the presenceof NP and OP in sediment and oysters analyzed in thisstudy is of particular concern, due to the interactive effectof these compounds with DDE, PCBs, PAHs, Hg andother toxic elements.

In this study, NP concentrations in sediments rangedfrom less than the MDL to 15 ng/g dw. NP concentrationsin sediments were less than those reported for 30 riversinfluenced by municipal and industrial waste waters (Nay-lor et al., 1992). Relatively lesser concentrations of NP insediment could be due to the small organic carbon contentof sediments (<1%). Concentrations of BP and OP in sed-iment in this study, were lower than the Detroit River,USA, Odra River, Poland, and Tokyo River, Japan (Isobeet al., 2001; Kannan et al., 2001, 2003a). Similarly concen-trations of NP in this study were lower when compared tosediments from the Detroit River, Virginia mid-Atlantic,Kalamazoo River, USA, Odra River, Poland, and theTokyo Bay, and Tokyo River in Japan (Hale et al., 2000;Yamashita et al., 2000; Kannan et al., 2001, 2003a,b; Isobeet al., 2001).

On the whole, among the analyzed toxic heavy metals,mercury (Hg) and macronutrient phosphorus (P) was highlevels in sediments and oysters, and therefore consumptionof oysters may lead to the intakes of highly toxic mercury,and high accumulations of P levels. Contamination oforganochlorine compounds such as DDTs and PCBs werenegligible due to their trace levels. PAHs were the secondpredominant contaminants and their accumulation in sed-iment and oyster tissues varied. Nonylphenols were thepredominant contaminants among the APs. However, theirlevels were similar to PCBs. Higher concentrations of themacronutrients, Al, As, Cd, Cr, Pb, Zn, DDE, PCBs,PAHs, and APs were found in oyster tissue versus sedi-ments. This suggests that they were efficiently bioaccumu-T

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146 Baseline / Marine Pollution Bulletin 56 (2008) 136–162

lated. Especially greater bioaccumulation of Zn and P is ofmajor concern. Geographical and temporal variations wereless pronounced (except DDE) and therefore not signifi-cant. International comparisons of DDE, PCBs, PAHs,and APs suggest much less contamination in the presentstudy. Continued monitoring is needed in the SavannahRiver due to rapid development of industries in this riverbasin and the routine dumping of all domestic sewagewastes and industrial effluents.

Acknowledgements

Part of this study was financially supported by the USNational Park Service, Department of Interior (Grant/Or-der No. P5420050005). Part of this research was performedunder the auspices of Contract No. DE-FG09-96SR18558,United States Department of Energy and EnvironmentalProtection Agency. We wish to thank the managementand staff of the Bull River Marina for allowing us to usespace at their marina for overnight boat docking and forallowing us to load and unload equipment and personnelduring the field sampling period. We thank Captain JayRosenzweig, Savannah State University, for his co-opera-tion and skill during boat sampling trips. We thank Savan-nah State University Marine Sciences Program studentsJames Smith, Chrissy Sellers, and Dori-Lynn Coburn fortheir valuable and skillful assistance in the field and the lab.

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0

0.5

1.0

1.5

2.0

0

0.3

0.6

0.9

1.2

y = 0.5631x + 1.1172R2= 0.0627

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P in

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0 5 10 15 20

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in O

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r (n

g/g

dry

wt.)

N

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Oys

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(ng/

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F of

OP

St-1 St-2 St-3 St-4 St-5 St-6

St-1 St-2 St- St-4 St-5 St-6St-1 St-2 St-3 St-4 St-5 St-6

ab

c d

Fig. 5. Correlation of OP and NP (a,c) and their bio-accumulation factor (BAF) (b,d) in oyster.

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doi:10.1016/j.marpolbul.2007.08.011

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