Bench-scale testing of selected remediation alternatives for contaminated sediments

The Assessment and Remediation of Contaminated Sediments (ARCS) Program within the U.S. Environmental Protection Agency's Great Lakes National Program Office (GLNPO) contained a component for demonstrating and evaluating sediment remediation technologies. Toward this end, bench-scale tests of solvent extraction, thermal desorption, and wet air oxidation technologies were conducted. Contaminated sediments were tested from the Grand Calumet River, Indiana; Buffalo River, New York; Saginaw River, Michigan; and Ashtabula River, Ohio. The primary contaminants of concern in these sediments were polychlorinated biphenyls (PCBs) and polynuclear aromatic hydrocarbons (PAHs). The solvent extraction tests were conducted with sediments from the Grand Calumet, Buffalo, and Saginaw rivers. The thermal desorption studies were conducted with sediments from the Grand Calumet, Buffalo, and Ashtabula rivers. The wet air oxidation testing was performed with the Grand Calumet River sediment. Raw sediment contaminant concentrations ranged from 0.32-21.9 mg/kg dry mass for PCBs and 2.70-266 mg/kg dry mass for PAHs. PCB removal or destruction efficiencies ranged from approximately 6-99%. PAH removal or destruction efficiencies ranged from 65-99%. Mass balance closures ranged from 40-99% for solids; 59-139% for water; 29-3500% for oil; 16-129% for PCBs; and 69-3170% for PAHs.     

SITE Demonstration of the Basic Extractive Sludge Treatment Process

The Superfund Innovative Technology Evaluation (SITE) Program, in cooperation with EPA Region 5, the Great Lakes National Program Office (GLNPO), and the U.S. Army Corps of Engineers (COE) planned and executed a pilot-scale evaluation of the Basic Extractive Sludge Treatment (B.E.S.T.®) process on sediment samples obtained from the Grand Calumet River in Gary, Indiana. Two separate sampling locations were selected based upon previous data. One location had sediments with total polychlorinated biphenyl (PCB) concentrations averaging 10 mg/kg, and total polynuclear aromatic hydrocarbon (PAH) concentrations averaging 520 mg/kg. The other location had sediments with average total PCB and PAH concentrations of 427 mg/kg and 72,000 mg/kg, respectively. The sediment samples were segregated by location, then screened, homogenized, and stored prior to treatment. A total of ten batches of sediments were treated (five for each sample location).

Results showed that of the samples which had low original contaminants concentrations, 96 percent of the PAHs and >99 percent of the PCBs were removed following seven sequential extractions. Treated samples which had high original contaminant concentrations were found to have removal efficiencies of >99 percentfor both PAHs and PCBs. Costs for applying this technology were estimated at $94.19/ton (assuming the system is on-line 80 percent of the time) excluding fixed costs associated with system mobilization/ demobilization and setup, and profit.     

Bioaccumulation of toxicants in the zebra mussel, Dreissena polymorpha, at the Times Beach Confined Disposal Facility, Buffalo, New York

This study consisted of a site characterization followed by biomonitoring the zebra mussel, Dreissena polymorpha, at the Times Beach Confined Disposal Facility (CDF), located in Buffalo, New York. Concentrations of selected contaminants, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and metals -arsenic (As), chromium (Cr), barium (Ba), mercury (Hg), cadmium (Cd), lead (Pb), selenium (Se) and silver (Ag)-were at or below detection limits in the water column. Sediment contaminant concentrations, recorded as dry weight, were as high as 549 mg/kg for total PAHs, 9 mg/kg for PCB Aroclor 1248 and 54, 99, 6, 355, 637 and 16 mg/kg for the metals As, Ba, Cd, Cr, Pb and Hg, respectively. To predict contaminant bioavailability, elutriate and whole sediment toxicity tests were performed utilizing the cladoceran, Daphnia magna. Whole sediment tests indicated significant impact. Control survival was 84%, while sediment treatment had survival ranging from 1 to 7%. Mean control reproduction was 86.8 neonates, whereas treatment reproduction ranged from 1.4 to 9.0. Zebra mussels placed both in the water column (Upper) and at the sediment level (Lower) survived the 34-day exposure. Contaminants that significantly accumulated in zebra mussel tissue (wet wt mg/kg) were total PAHs (6.58), fluoranthene (1.23), pyrene (1.08), chrysene (0.98), benzo(a)anthracene (0.60), PCB Aroclor 1248 (1.64), As (0.97), Cr (2.87) and Ba (7.00). Accumulation of these contaminants in zebra mussel tissue represent a potentially realistic hazard to organisms (i.e. fish and birds) that feed on them.     

Slurry-phase ozonation for remediation of sediments contaminated by polycyclic aromatic hydrocarbons

Polycyclic aromatic hydrocarbons (PAHs) are a group of toxic, persistent, bioaccumulating organic compounds containing two or more fused aromatic rings. They are listed by the U.S. Environmental Protection Agency as priority pollutants because of their carcinogenicity and toxicity. Employing ozonation as a remediation technique, this work investigated the treatability of a sediment sample from a freshwater boat slip subjected to coal tar contamination over a long period. The contaminated sediment sample contained high levels of PAHs in the forms of naphthalene, phenanthrene, pyrene, and benzo[a]pyrene, among other byproducts present in the humic and solid phases of the sediment. The objectives of this work were to examine (1) the degradation of PAHs in the contaminated sediment as treated by ozonation in the slurry form, (2) the effects of ozonation upon the soil matrix and the biodegradability of the resultant PAH intermediates, and (3) the feasibility of a combined technique using O3 as a pretreatment followed by biological degradation. The sediment was made into 3% w/w soil slurries and ozonated in a 1.7-L semi-batch, well-stirred reactor equipped with pH control and a cold trap for the gaseous effluent. Samples were collected after different ozonation durations and tested for biochemical oxygen demand (BOD), chemical oxygen demand (COD), UV absorbance, and toxicity, along with quantitative and qualitative determinations of the parent and daughter intermediates using gas chromatography/flame ionization detection (GC/FID), GC/mass spectrometry (MS), and ion chromatography (IC) techniques. The GC/MS technique identified 16 compounds associated with the humic and solid phases of the sediment. Intermediates identified at different ozonation times suggested that the degradation of PAHs was initiated by an O3 attack resulting in ring cleavage, followed by the intermediates' oxidation reactions with O3 and the concomitant OH radical toward their mineralization. Results suggested that ozonation for 2 hr removed 50-100% of various PAHs in the solid and liquid phases (as well as the aqueous and gaseous media resulting from the treatment process) of the sediment sample and that organic and inorganic constituents of the sediment were also altered by ozonation. Measurements and comparisons of BOD, COD, UV absorbance, and toxicity of the samples further suggested that ozonation improved the bioavailability and biodegradability of the contaminants, despite the increased toxicity of the treatment effluent. An integrated chemical-biological system appeared to be feasible for treating recalcitrant compounds.     

Source apportionment of polychlorinated biphenyls in the New York/New Jersey Harbor

The New York/New Jersey Harbor (also known as the Hudson River Estuary) is heavily contaminated with polychlorinated biphenyls (PCBs) arising in part from inputs from the Upper Hudson River, which is a Superfund site containing historical PCB contamination, and also due to inputs from the New York City metropolitan area. The Contamination Assessment and Reduction Project (CARP) measured PCBs and other contaminants in ambient water samples collected throughout the Harbor region during 1998-2001. In order to investigate the sources of PCBs to the NY/NJ Harbor, this data base of PCB concentrations was analyzed using Positive Matrix Factorization (PMF). This analysis resolved seven factors that are thought to be associated with sources such as the Upper Hudson River, storm water runoff, combined sewer overflows (CSOs), and wastewater effluents. The PMF model also produced a factor that appears to be related to sites contaminated with Aroclor 1260. To the extent that the NY/NJ Harbor is typical of urbanized estuaries throughout the United States, these results suggest that storm water runoff is probably a significant source of PCBs to surface waters in urban areas.     

Chlorinated and polycyclic aromatic hydrocarbons in riverine and estuarine sediments from Pearl River Delta, China

Spatial distribution of chlorinated hydrocarbons [chlorinated pesticides (CPs) and polychlorinated biphenyls (PCBs)] and polycyclic aromatic hydrocarbons (PAHs) was measured in riverine and estuarine sediment samples from Pearl River Delta, China, collected in 1997. Concentrations of CPs of the riverine sediment samples range from 12 to 158 ng/g, dry weight, while those of PCBs range from 11 to 486 ng/g. The CPs concentrations of the estuarine sediment samples are in the range 6-1658 ng/g, while concentrations of PCBs are in the range 10-339 ng/g. Total PAH concentration ranges from 1168 to 21,329 ng/g in the riverine sediment samples, whereas the PAH concentration ranges from 323 to 14,812 ng/g in the sediment samples of the Estuary. Sediment samples of the Zhujiang River and Macao harbor around the Estuary show the highest concentrations of CPs, PCBs, and PAHs. Possible factors affecting the distribution patterns are also discussed based on the usage history of the chemicals, hydrologic condition, and land erosion due to urbanization processes. The composition of PAHs is investigated and used to assess petrogenic, combustion and naturally derived PAHs of the sediment samples of the Pearl River Delta. In addition, the concentrations of a number of organic compounds of the Pearl River Delta samples indicate that sediments of the Zhujiang river and Macao harbor are most likely to pose biological impairment.     

Levels, persistence and bioavailability of organic contaminants present in marine harbor sediments impacted by raw sewage

As part of a program to investigate the levels, fate and bioaccumulation of organic contaminants in a polluted marine harbor, organochlorine compounds including the polychlorinated biphenyls (PCBs), dichloro diphenyltrichloroethane and metabolites (DDTs), chlordanes, dibenzo-p-dioxins (Ds) and dibenzofurans (Fs), polycyclic aromatic hydrocarbons (PAHs) and sulphur hetero cycles were analysed in sediments spiked with St. John's Harbor sludge. Winter flounder (Pseudopleuronectes americanus) were exposed to these sediments containing six levels of harbor sludge during four winter months. Following exposure, sediments were reanalysed to investigate the persistence of the contaminants. The primary contaminants detected were PAHs (approximately 5000 ng/g), predominantly alkylated phenanthrenes, fluoranthene and pyrene; PCBs with a predominance of Aroclor 1260 signature (approximately 64 ng/g), DDTs (approximately 5 ng/g), hepta and octachloro dioxins and furans (approximately 0.5 ng/g) with very low levels of less chlorinated congeners. The PAHs degraded with an estimated half life of 2 to 3 months, while no significant degradation could be attributed to the other compounds. Bioaccumulation to muscle showed the potential uptake of contaminants in biota inhabiting the harbor. A dose-response relationship was observed between spiked sediments and the concentrations of PCB congener 153 and unresolved congeners 138/163/164 in muscle. Of the dioxins and furans, only 2, 3, 7, 8-tetrachlorofuran was detectable in muscle and at a similar concentration in all exposures indicating a similar bioavailability independent of the fraction of sludge in sediments. Of the PAHs, only naphthalene and methyl naphthalenes were detected in muscle, but did not display a dose-response. One bile metabolite of pyrene was quantified and demonstrates metabolism. Biota-sediment accumulation factors were of 0.2 to 7 indicating that equilibrium was approached, with the exception of the hepta and octachloro dioxins and furans which were not significantly bioaccumulated.     

Combined steam distillation and electrochemical peroxidation (ECP) treatment of river sediment contaminated by PCBs

A combined treatment process utilizing steam distillation followed by electrochemical peroxidation (ECP) has been utilized to remove >90% of the polychlorinated biphenyls (PCBs) in St. Lawrence River sediment and destroy 95% of the PCBs recovered in the condensate. 2 l of condensate were collected by boiling 500 grams of sediment containing 4.3 mg PCBs. Most of the PCBs (82.3%) were recovered as a small volume (<1 ml) of yellow oil floating on the condensate and coating glassware surfaces. The aqueous phase PCBs (182 μg/l) were destroyed (95%) by three sequential ECP treatments at 16.8°C and pH 5, utilizing 1 ml of H₂O₂ (3%) and periodically reversed current (0.75–1.0 A @ 10 volts). Oxidation is primarily mediated by hydroxyl radicals produced by the reaction of hydrogen peroxide with electrochemically generated ferrous iron (Fenton's reagent). This work suggests steam extraction, in combination with advanced oxidation technologies, provides an effective treatment strategy for contaminated solids.     

Polychlorinated biphenyl, polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran residues in sediments and fish of the River Nile in the Cairo region

The levels of organohalogenated contaminants, i.e. PCBs, PCDDs and PCDFs were determined in sediment and fish samples collected from different locations in the River Nile, Egypt. Thirty-six sediment and eighteen fish samples were carried out during a period of 12 months from February 2003 to February 2004. Determination of PCBs and dioxins was carried out using a high resolution GC mass spectrometer. The results indicated that the PCB and PCDD/F mean concentrations in sediment samples ranged from 1461 to 2244 and from 240 to 775pgg(-1) dry wt basis, respectively. The mean concentration of PCBs and PCDD/Fs in fish samples were found to be in the range from 695 to 853pgg(-1) fresh wt for PCB congeners and from 27.7 to 121pgg(-1) lipid for total PCDD/Fs. Moreover, the concentrations of both PCBs and PCDD/Fs were found to be different at different locations along the River Nile. It could be concluded that the contamination of the River Nile is within the permissible limits set by the FDA and the Egyptian Standards for fish and shellfish.     

Impacts of urbanization on surface sediment quality: evidence from polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) contaminations in the Grand Canal of China

Introduction

Organic pollutants, especially synthetic organic compounds, can indicate paces of anthropogenic activities. Effects of urbanization on polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) distributions in surface sediment were conducted in urban sections of the Grand Canal, China, consisting of a four-level urbanization gradient.

Materials and methods

The four-level urbanization gradients include three countryside towns, two small-size cities, three medium-size cities, and a large-size city. Diagnostic ratio analysis and factor analysis?Cmultiple linear regression model were used for source apportionment of PAHs. Sediment quality guidelines (SQGs) of USA and Canada were employed to assess ecological risks of PAHs and PCBs in surface sediments of the Canal.

Results and discussion

Ranges of PAH and PCB concentrations in surface sediments were 0.66?C22?mg/kg and 0.5?C93???g/kg, respectively. Coal-related sources were primary PAH sources and followed by vehicular emission. Total concentration, composition, and source apportionment of PAHs exhibited urbanization gradient effects. Total PCB concentrations increased with the urbanization gradient, while total PAHs concentration in surface sediments presented an inverted U Kuznets curve with the urbanization gradient. Elevated concentrations of both PAHs and PCBs ranged at effect range low levels or interim SQG, assessed by USA and Canadian SQGs.

Conclusions

PAHs and PCBs in surface sediments of the Grand Canal showed urbanization gradient effects and low ecological risks.     

Occurrence of PAHs, PCBs and organochlorine pesticides in the Tonghui River of Beijing, China

Tonghui River, a typical river in Beijing, People's Republic of China, was studied for its water and sediment quality, by determining the levels of 16 polycyclic aromatic hydrocarbons (PAHs), 12 polychlorinated biphenyls (PCBs) and 18 organochlorine pesticides in water and sediment samples. Total PAHs, PCBs and organochlorine pesticides concentrations in water varied from 192.5 to 2651 ng/l, 31.58-344.9 ng/l and 134.9-3788 ng/l, respectively. The total PAHs, PCBs and organochlorine pesticides concentrations in surficial sediments were 127-928 ng/g, 0.78-8.47 ng/g and 1.79-13.98 ng/g dry weight, respectively. The results showed that the concentration of these selected organic pollutants in sediment was higher than those in surface water. It may be due to the fact that organic hydrophobic pollutants tend to stay in the sediments. The PAHs were dominated by 2-, 3-ring components in water samples and by 3- and 4-ring compounds in sediment. For organochlorines, alpha-HCH, delta-HCH, Heptachlor, Endosulfan II, DDT are the major organochlorine pesticides in water while Heptachlor, Dieldrin and DDE composed of 95% of total organochlorine pesticides in sediment. For HCHs (HCHs=alpha-HCH+beta-HCH+gamma-HCH+delta-HCH), the predominance of alpha-HCH of total HCHs were clearly observed in water and sediment. PCB18, PCB31 and PCB52 were predominant in water, on average these compounds collectively accounted for 67% of total PCBs. But in sediment, the predominant compounds were PCB28, PCB31 and PCB153, which accounted for 71% of total PCBs in sediment. The levels of micro pollutants in our study areas were compared with other studies.     

Residues of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides in organically-farmed vegetables

The residues of polyaromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in soils from organic farms and their uptake by four varieties of organic-produced potatoes and three varieties of organic carrots from England were investigated. Samples of the soils, crop peels and cores were all Soxhlet-extracted in triplicate, cleaned up by open-column chromatography and analysed by a multi-residue analytical method using gas chromatography with mass selective detection. The concentrations of PAHs, PCBs and OCPs in soils from organic farms ranged from 590+/-43 to 2301+/-146 microg/kg, 3.56+/-0.73 to 9.61+/-1.98 microg/kg and 52.2+/-4.9 to 478+/-111 microg/kg, respectively. Uptake by different crop varieties were 8.42+/-0.93 to 40.1+/-4.9 microg/kg sigmaPAHs, 0.83+/-0.19 to 2.68+/-0.94 microg/kg sigmaPCBs and 8.09+/-0.83 to 133+/-27 microg/kg sigmaOCPs. Residue uptake from soils depended on plant variety; Desiree potato and Nairobi carrot varieties were more susceptible to PAH contamination. Likewise, uptake of PCBs and OCPs depended on potato variety. There were significant positive correlations between the PCB and OCP concentrations (P<0.05) in soils and carrots but no significant correlation was found between the concentrations of any contaminants in soils and potatoes. Peeling carrots and potatoes was found to remove 52-100% of the contaminant residues depending on crop variety and the properties of the contaminants. Soil-crop bioconcentration factors (BCFs) decreased with increasing logK(ow) for PAHs up to about 4.5 and for PCBs up to about 6.5, above which no changes were discernible for either class of contaminants. No relationship was observed between soil-crop BCFs and logK(ow) for OCPs, most likely because their concentrations were low and variable.     

Tidal salt marsh sediment in California, USA. Part 1: occurrence and sources of organic contaminants

Surface sediment samples (0-5 cm) from five tidal marshes along the coast of California, USA were analyzed for organic pollutants to investigate their relationship to land use, current distribution within marshes, and possible sources. Among the study areas, Stege Marsh, located in San Francisco Bay, was the most contaminated. Compared to San Francisco Bay, Stege Marsh had much higher levels of organic contaminants such as PCBs (polychlorinated biphenyls), DDTs, and chlordanes. At reference marshes (Tom's Point and Walker Creek in Tomales Bay), organic contaminants in sediments were very low. While PAHs (polycyclic aromatic hydrocarbons) were found at all of the study areas (22-13,600 ng g(-1)), measurable concentrations of PCBs were found only in the sediments from Stege Marsh (80-9,940 ng g(-1)). Combustion related (pyrogenic) high molecular weight PAHs were dominant in sediments from Stege and Carpinteria Marshes, while in sediments from Tom's Point and Walker Creek petroleum related (petrogenic) low molecular weight PAHs and alkyl-substituted PAHs were much more abundant than pyrogenic PAHs. PCB congener patterns in all of the Stege Marsh samples were the same and revealed that Aroclor 1248 was a predominant source. In all marshes, the sum of DDE and DDD accounted for more than 90% of total DDTs, indicating that DDT has degraded significantly. The ratios of p,p'-DDE to p,p'-DDD in sediments from Stege Marsh provide evidence of possible previous use of technical DDD. Chlordane ratios indicated that chlordanes have degraded slightly. Bis(2-ethylhexyl)phthalate (280-32,000 ng g(-1)) was the most abundant phthalate. The data indicates that Stege Marsh may be a source of contaminants that continue to be discharged into San Francisco Bay.     

A GIS-based multimedia watershed model: development and application

A multimedia model was developed using publicly available geographical information system (GIS) data, chemical release information and local monitoring networks to assess the fate of trichloroethene (TCE) within the Passaic River Watershed. Seven environmental media, air, water, sediment, surface soil, terrestrial vegetation, root zone soil and vadose zone soil, were modeled in this study along with their sub-compartments. The Passaic River Watershed is described using the NJDEP geographical information system (GIS) resources, the United States Geological Survey (USGS) and the United States Soil Conservation Services (US SCS) soil data. The introduction of spatial resolution to a multimedia, unsteady state model is performed in this work, and represents an important step in expanding the use of equilibrium models to provide far reaching information on the fate of toxic contaminants within a given environmental unit. The spatial representation of cross-boundary fluxes was successfully demonstrated with the use of sub-watershed as an environmental unit and the direct assessment of TCE for each of the 11 sub-watersheds that make up the Passaic River Basin in northern New Jersey. Important data gaps identified during the development of this model include the lack of comprehensive monitoring data on organic contaminants, and non-uniformity among available physical environmental data from different government agencies.     

Assessing PAH and PCB emissions from the relocation of harbour sediments using equilibrium passive samplers

Large-scale dredging of contaminated sediments is taking place in the harbor of Oslo, Norway. The dredged sediment masses are transferred into a confined aquatic disposal facility (CAD) in a natural 70-m deep basin within the Oslofjord. Currently there is no established method to determine how much dissolved contaminants are released during relocation and deposition of these sediments. For this reason we tested the use of equilibrium passive samplers consisting of 55 microm thin polyoxymethylene (POM-55) for studying the release of freely dissolved and thus bioavailable PAHs and PCBs at the disposal site, and found this to be a suitable method. In order to use POM-55 for monitoring PCBs, it was necessary to measure their POM-55/water partition coefficients, which was also presented as part of this study. Elevated turbidity (average 4.1 mg l(-1)) was observed at one side of the basin where no natural sill exists. Analysis of POM-55 at this location before and after deposition revealed that there was an increase in freely dissolved concentrations (C(W,free)) during deposition by a factor 37.5 for PAHs and a factor of 2.9 for PCBs. In addition, during deposition phenanthrene-to-anthracene aqueous concentration ratios at this location (values of 3-4) were more similar to those of the deposited sediments (approximately 2) than to those of the CAD water prior to deposition (approximately 14). This was not observed for the other locations where a natural sill exists at approximately 30 m water depth. The POM-55 equilibrium passive samplers are here shown to be useful tools for measuring and understanding the dynamics involved in the release of dissolved contaminants during sediment relocation.     

Diffusion of PAH and PCB from contaminated sediments with and without mineral capping; measurement and modelling

A novel laboratory microcosm test was developed to measure the diffusion of native PAHs and PCBs from sediments in the presence and absence of a capping layer. Diffusive flux of 15 PAHs and 7 PCBs from uncapped sediment from Oslo harbour was 3.8+/-0.9 microg m(-2)d(-1) and 0.010+/-0.003 microg m(-2)d(-1), respectively. The flux from sediments capped with 1cm mineral cap (crushed limestone or crushed gneiss (0-2mm)), observed during the first 410 d, was 3.5-7.3% of the flux from uncapped sediments. By measuring freely dissolved pore water concentrations of 10 PAHs the flux in the microcosm was modelled with steady state and transient diffusion models. The measured flux from uncapped sediment was 27-290% of modelled steady state flux. Good agreement was also found between the measured flux of pyrene from capped sediment and the flux modelled with the transient model when fitting only with the distribution coefficients for pyrene between the cap material and water (Kd_pyr). Fitted Kd_pyr, (210 and 23 l kg(-1) for limestone and gneiss, respectively) was in the same order of magnitude as K(d) calculated from organic carbon content in the cap materials (68 and 14 l kg(-1) respectively). Calculation of the efficiency of a hypothetical cap with 10 cm diffusion path shows that the increased diffusion path length alone can yield a flux reduction >99% through a strong increase in the stagnant diffusive boundary layer from <1 to 100mm.     

Polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) distributions in the Bay of Marmara sea: Izmit Bay

In 1999, the concentrations of 16 polycyclic aromatic hydrocarbons (PAHs), the total PAH and polychlorinated biphenyls (PCBs) were measured in sea water, sediment and mussels collected along the coast of Izmit Bay, the most important bay of the Marmara Sea. The total-PAH concentrations, measured by Spectrofluorometry were in the range of 1.16-13.68 microg/l in sea water, in the range of 30.0 1670.0 microg/g dry weight in sediments and in the range from 5.67 to 14.81 microg/g wet weight in edible part of mussel. HPLC revealed Phenanthrene (three rings), chrysene (four rings) and benz[a]antracene (five rings) to be the dominant PAHs in sea water, while 16 different PAHs compounds were observed and measured in mussel samples. The most pollution occured at Dogu Kanali and Dil Deresi where were the main rivers containing wastes fall into the the Izmit Bay. Although the maximum mono-ortho PCB concentrations in sea water were measured in the Dil Deresi River (26.33 ng/l) and the Solventa? (22.19 ng/l) stations, maximum PCB concentrations in mussels were measured in the SEKA (28.11 microg/kg) and the Dil Deresi River (25.68 microg/kg). The dominant congeners of PCBs were from tetra to hexachlorobiphenyls. The toxicity equivalent values were very low in sea water and mussels.     

The potential contribution of urban runoff to surface sediments of the Passaic River: sources and chemical characteristics

Urban runoff has been reported as the second most frequent cause of surface water pollution in the United States. Due to the incidence of runoff in urban areas, it was of interest to estimate the impact runoff may have to recent sediment quality within the lower reaches of the Passaic River. Study objectives included i) review of recent urban runoff studies to determine the occurrence and pattern of distribution of chemicals in runoff; ii)comparison of the "fingerprints" from urban runoff studies to the contaminant distributions in surface sediments from the River; and iii) estimation of mass loadings to the surface sediments using surrogate data. The analyses showed that metals and PAH distributions in the sediments were similar to those observed in runoff from diverse locations, suggesting that urban runoff composition within the Passaic watershed is similar to other urban areas. Mass loading calculations demonstrated that urban runoff is a significant source of the metals observed in the sediments, and that PAH and DDT sediment loadings could, in some cases, be accounted for by urban runoff. Observed sediment loads for PCBs, however, were significantly higher than were estimated from urban runoff.     

Assessment of decadal changes in sediment contamination in a large connecting channel (Detroit River,North America)

Concentrations of selected heavy metals (Cd, Cu, Hg, Pb, Zn) and organic contaminants (PCBs, PAHs) were investigated in samples from the Detroit River (Great Lakes, North America) in 1999 and 2008/09 collected using a stratified random sampling design. Getis–Ord geospatial analysis was used to further establish locations of areas demonstrating significantly high and low contaminant concentrations in the river. Based on the stratified random sampling design, a majority of the examined metals and organic contaminants demonstrated little or no trends with respect to regional sediment concentrations and river-wide mass balances over the investigated time interval. The Getis–Ord analysis revealed local scales of contaminated and clean areas which did not conform to the original strata used in the geostatistical sampling design. It is suggested that geospatial analyses such as Getis–Ord be used in the design of future sediment quality surveys to refine locations of strata that can simultaneously address sediment recovery over system-wide, regional and local spatial scales.     

Persistent organic pollutants in soil density fractions: distribution and sorption strength

The sorption strength of persistent organic pollutants in soils may vary among different soil organic matter (SOM) pools. We hypothesized that polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) were unevenly distributed and had different soil organic carbon (SOC)-water partition coefficients (K(OC)) among soil density fractions. We determined the concentrations and K(OC) values of 20 PAHs and 12 PCBs in bulk samples and three density fractions (light, <2.0, medium, 2.0-2.4, and heavy, >2.4 g cm(-3)) of 11 urban topsoils (0-5 cm) from Bayreuth, Germany. The K(OC) values were determined using sequential extraction with methanol-water mixtures (35% and 65% methanol) at 60 degrees C. The sum of 20 PAH concentrations in bulk soil ranged 0.4-186 mg kg(-1), and that of 12 PCB concentrations 1.2-158 microg kg(-1). The concentrations of all PAHs and PCBs decreased in the order light>medium>heavy fraction. When normalized to the SOC concentrations, PAH concentrations were significantly higher in the heavy than in the other density fractions. The K(OC) values of the PAHs in density fractions were 3-20 times higher than those of the PCBs with similar octanol-water partition coefficients (K(OW)). The K(OC) values of individual PAHs and PCBs varied up to a factor of 1000 among the studied soils and density fractions. The K(OC) values of 5- and 6-ring PAHs tended to be highest in the heavy fraction, coinciding with their enrichment in this fraction. For the other PAHs and all PCBs, the K(OC) values did not differ among the density fractions. Thus, there is no relationship between sorption strength and distribution among density fractions, indicating that density fractionation is not a suitable tool to distinguish among differently reactive PAH and PCB pools in soils.