Distribution and source differentiation of PAHs and PCBs among size and density fractions in contaminated harbor sediment particles and their implications in toxicological assessment

Sediment samples collected from Kaohsiung Harbor (Taiwan) were analyzed for 15 priority polycyclic aromatic hydrocarbons (PAHs) and 118 individual polychlorinated biphenyl (PCB) congeners in various particle size fractions and two density fractions. The PAHs in the low density fraction were a much more sensitive and effective indicator of the PAH source than those in the sediment as a whole. Hierarchical cluster analysis of PAH analytes in the low density sediments revealed significant differences in compositional patterns between locations and among size fractions. In the sediment samples from both study sites, the low density fraction particles had up to 155 and 150 times higher concentrations of PAHs and PCBs, respectively, than those in the corresponding high density fractions. In addition, the total toxic benzo[a]pyrene and 2,3,7,8-tetrachlorodibenzodioxin (TCDD, dioxin) equivalents in the sediment low density fractions were much higher (up to 170 and 273 times, respectively) than the corresponding high density fractions.     

Depositional history of organic contaminants in Narragansett Bay, Rhode Island, USA

Sediment cores were taken at three locations in Narragansett Bay, Rhode Island, USA in 1997 and analyzed for a variety of organic contaminants including polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), chlordanes, linear alkyl benzenes (LABs), benzotriazoles (BZTs) and dichlorodiphenyltrichloroethanes (DDTs) and metabolites. The distributions of these chemicals at Apponaug Cove and in the Seekonk River indicate that there was a disturbance in the depositional environment relative to cores collected at these locations in 1986 demonstrating the potential for buried contaminants to be remobilized in the environment even after a period of burial. Sharp breaks in the concentration of several organic markers with known dates of introduction were successfully used to determine the sedimentation rate at Quonset Point. Both the Quonset Point and Seekonk River cores had subsurface maximums for DDTs, PCBs, PAHs and BZTs, which are consistent with expected inputs to the environment. The Apponaug Cove core showed an increase of most contaminants at the surface indicating a recent event in which more contaminated sediments were deposited at that location.     

Sediment disturbance off the Tagus Estuary, Western Portugal: chronic contamination, sewage outfall operation and runoff events

Sediment disturbance patterns in the coastal area off the Tagus Estuary (Portugal) have been assessed using a set of combined techniques. The potential sources of disturbance in the area include chronic contamination of the fine sediments originating from the estuary, a local input from a long-sea sewage outfall and occasional high runoff episodes following torrential rain. The Sediment Quality Triad approach, combining environmental chemistry (namely organic contaminants), macrofaunal benthic communities and laboratory sediment toxicity assays, was performed on sediment samples from 20 sites. The samples were collected before the outfall commenced operation and four years after commissioning, in order to evaluate the relative magnitudes of the three potential sources of disturbance. The sediment contamination created by the estuary was identified as the most important cause of reduced sediment quality, as disturbance in all three components of the Sediment Quality Triad were only found in a site located near the estuary.     

Levels and spatial distribution of polycyclic aromatic hydrocarbons (PAHs) in sediments from Lenga Estuary, central Chile

The Lenga Estuary is a small brackish wetland located southwest of San Vicente Bay, Region VIII, Chile. Surface sediment from nine sites in the estuary were analysed for PAHs and compared to Sediment Quality Guidelines (SQG). Sediment samples were freeze dried and soxhlet extracted for 16 h using DCM. Identification and quantification was carried out by HPLC. Organic carbon was also determined. Results showed total PAH concentrations ranged from 290 to 6118 (2025 ± 1975) ng g⁻¹ d.w. (2025 ± 1975). Results for organic carbon percentages ranged from 1% to 7%. Statistical analysis showed a significant positive correlation (Pearson test) between organic carbon percentage PAHs. Comparison of contaminant levels and international Sediment Quality Guidelines (SQG) (ERL and ER) suggested that sediment of the Lenga estuary did not show any ecotoxicologial risk for benthic organisms where high levels of PAHs were detected. Monitoring of this and other contaminants is recommended in Chile.     

Distribution and origins of polycyclic aromatic hydrocarbons (PAHs) in riverine, estuarine, and marine sediments in Thailand

To assess the status of polycyclic aromatic hydrocarbon (PAH) contamination in coastal and riverine environments in Thailand, we collected 42 surface sediment samples from canals, a river, an estuary, and coastal areas in Thailand in 2003 and analyzed them for PAHs with 3-7 benzene rings by gas chromatography-mass spectrometry (GC-MS). The total concentration of PAHs ranged from 6 to 8399 ng/g dry weight. The average total PAH concentrations were 2290+/-2556 ng/g dry weight (n=8) in canals, 263+/-174 (n=11) in the river, 179+/-222 (n=9) in the estuary, and 50+/-56 (n=14) in coastal areas. Comparison of the concentration range with a worldwide survey of sedimentary PAH concentrations ranked PAH contamination in Thai sediments as low to moderate. The ratio of the sum of methylphenanthrenes to phenanthrene (MP/P ratio) allows discrimination of PAH sources between petrogenic (>2) and pyrogenic (<0.5) origins. Sediments from urban canals in Bangkok showed the highest PAH concentrations and petrogenic signatures (MP/P=1.84+/-0.98 [n=6] in canal sediments) with abundant alkylated PAHs, indicating major sources of petrogenic PAHs in the city. To identify the sources of the petrogenic inputs in Thailand, we analyzed triterpanes, biomarkers of petroleum pollution, in the sediment samples and in potential source materials. Hopane profiles were remarkably uniform throughout the nation, suggesting a diffuse single source (e.g. automobiles). Molecular profiles of hopanes and PAHs in sediments from the urban canals were similar to those in street dust, indicating that street dust is one of the major sources of petrogenic PAHs in the urban area. On the other hand, low levels of PAHs (approximately 50 ng/g) with a pyrogenic signature (MP/P ratio approximately 0.5) were widely recorded in remote areas of the coast and the Chao Phraya River. These pyrogenic PAHs may be atmospherically transported throughout the nation. Middle and lower reaches of the Chao Phraya River, the river mouth, and the upper Gulf of Thailand showed intermediate concentrations and profiles of PAHs, indicating mixtures of petrogenic and pyrogenic origins. Perylene was abundant in sediments, representing up to approximately 60% of total identified PAHs. High inputs of soil due to frequent heavy rains could contribute to the high perylene abundance in the sediments. Sedimentary PAH concentrations decreased offshore with a half distance of approximately 10 km in the upper Gulf off the mouth of the Chao Phraya River. This is probably due to active deposition of laterally transported riverborne particles.     

Nutrient,heavy metal and organic pollutant composition of suspended and bed sediments in the Rhone River

The environmental quality of the Rhone River (Switzerland-France) has been assessed with a geochemical survey of the pollutants bound to suspended sediments. Ten samples were collected between Lake Geneva and the Mediterranean Sea in Nobember 1989 by continuous flow centrifugation and analysed for grain size distribution, carbonate, organic C, N, forms of particulate P, trace metals, and organic compounds (chlorobenzenes, organochlorine pesticides, PCBs, and PAHs). Four bed sediment samples were also studied for comparative purposes. The suspended solids provide lower variance by parameter than the bed sediments and are clearly most suitable for synoptic monitoring.The Upper Rhone River carries a glacial derived sediment with a low nutrient content, the stretch from Geneva to Lyon provides a sediment dominated by carbonate, and in the Lower Rhone the organic matter and phosphorus are relatively increased, mainly due to wastewater effluents and to an industrial P source. High concentrations of metals and organic micropollutants downstream of Lyon indicate a multiple contamination in the Lower Rhone, whereas more specific inputs are located downstream of Geneva and Arles.The comparison with data from other polluted major systems, the Rhine, the Niagara and the Detroit rivers, shows on overall similarity confirming that the Rhone quality is degraded downstream of Lyon. The levels of particular concern are for Hg, DDT metabolites which reveal a recent release in the basin, PCBs with a likely high chlorine content, and PAHs.The statistical evaluation of the compositional variables indicates a limited number of well defined associations, suggesting that the contamination of the suspended sediments results from the combination of numerous and intermittent point and diffuse sources in the Rhone River basin.     

Distribution and sources of polynuclear aromatic hydrocarbons in Mangrove surficial sediments of Deep Bay, China

Twelve sediment samples collected from three transects of mangrove swamp of Deep Bay, Shenzhen, China, were determined for polynuclear aromatic hydrocarbons (PAHs). The total PAHs concentrations ranged from 237 to 726 ng g(-1) dry weight, and showed strong correlation with total organic carbon (TOC), clay content and Pb concentrations. The highest PAHs concentrations were found in the samples from mangrove sediments. Overall, PAHs in Deep Bay sediment were lower than those in other developed areas. The biological effect due to PAHs alone in Deep Bay is expected to be low, based on the comparisons of individual and total PAHs concentrations determined in the sediment with those in USEPA sediment quality guidelines. Four and five-ring compounds dominated the PAHs composition pattern profiles. Principal component analysis (PCA) was applied to further investigate the source of PAHs. The PAH sources of Deep Bay mangrove swamp were suggested to be primarily combustion of fossil fuel, especially leaded-gasoline exhaust.     

Assessment of polycyclic aromatic hydrocarbon input to urban wetlands in relation to adjacent land use

The relationship between polycyclic aromatic hydrocarbons (PAHs) in wetland surface sediments and adjacent land use was assessed in the Elizabeth River, VA, an urbanized sub-estuary of the Chesapeake Bay. Significant differences (p<0.05) in surface sediment PAH concentration between sites indicated adjacent land use had a substantial influence on PAH concentration in wetland sediments. Wetlands adjacent to parking lots and petroleum industrial sites exhibited the highest PAH concentrations of all wetlands examined. Overall, commercial land uses had the highest PAH concentrations and automotive sources dominated (52-69%) PAH input to wetland surface sediments irrespective of adjacent land use.     

Polycyclic aromatic hydrocarbons loads into the Mediterranean Sea: estimate of Sarno River inputs

The polycyclic aromatic hydrocarbons (PAHs) pollution in the Sarno River and its environmental impact on the Gulf of Naples (Tyrrhenian Sea, Central Mediterranean Sea) were estimated. The 16 PAHs identified by the USEPA as priority pollutants and perylene were determined in the water dissolved phase (DP), suspended particulate matter (SPM) and sediments. Total PAHs concentrations ranged from 23.1 to 2670.4 ng L(-1) in water (sum of DP and SPM) and from 5.3 to 678.6 ng g(-1) in sediment samples. Source analysis revealed that PAHs mainly came from combustion process. Contaminant discharges of PAHs into the sea were calculated in about 8530 gd(-1) showing that this river should account as one of the main contribution sources of PAHs to the Tyrrhenian Sea.     

Marine meiobenthic and nematode community structure in Victoria Harbour,Hong Kong upon recovery from sewage pollution

Sediment quality, meiofaunal and nematode communities were monitored across six time points at two inside-harbour and three outside-harbour sites over a three-year period in Victoria Harbour, Hong Kong, after the implementation of a sewage treatment project. Twenty-one meiofaunal groups comprising mainly free-living nematodes and harpacticoid copepods and 188 species of free-living nematodes were identified. The outside-harbour area had a more diverse and significantly different nematode community structure as compared to that in the inside-harbour area. Such spatial difference was highly correlated with the total Kjeldahl nitrogen content of the sediments. Over the study period, there was no significant improvement in sediment quality within the harbour. However, in the last sampling time, an increase in meiofaunal abundance and a closer similarity in nematode composition between one of the inside- and outside-harbour sites suggested signs of recovery of the meiofauna as a response to abatement of sewage pollution.     

Marine meiobenthic and nematode community structure in Victoria Harbour, Hong Kong upon recovery from sewage pollution

Sediment quality, meiofaunal and nematode communities were monitored across six time points at two inside-harbour and three outside-harbour sites over a three-year period in Victoria Harbour, Hong Kong, after the implementation of a sewage treatment project. Twenty-one meiofaunal groups comprising mainly free-living nematodes and harpacticoid copepods and 188 species of free-living nematodes were identified. The outside-harbour area had a more diverse and significantly different nematode community structure as compared to that in the inside-harbour area. Such spatial difference was highly correlated with the total Kjeldahl nitrogen content of the sediments. Over the study period, there was no significant improvement in sediment quality within the harbour. However, in the last sampling time, an increase in meiofaunal abundance and a closer similarity in nematode composition between one of the inside- and outside-harbour sites suggested signs of recovery of the meiofauna as a response to abatement of sewage pollution.     

TEMPORAL AND SPATIAL DISTRIBUTIONS OF PAHS AND PCBS IN LAKE CALUMET AREA, CHICAGO

1 INTRODUCTION Lake Calumet is located 15 miles southeast of downtown Chicago. The geographical boundaries include 130th Street to the south, Stony Island Avenue to the east, an industrial area to the north, and interstate highway I-94 to the west. The major continuous water inflow to the lake is Pullman Creek, a drainage ditch, which carries the runoff from the nearby expressway, industries, and landfills into the lake at the northwest corner. The outlet of the Lake is the Calumet R…     

Comet assay for the detection of genotoxicity in blood cells of flounder (Paralichthys olivaceus) exposed to sediments and polycyclic aromatic hydrocarbons

To investigate the genotoxic effect of marine sediments on aquatic organism, sediment samples were collected from 13 sites along the coast of Gwangyang Bay (Korea). Concentrations of polycyclic aromatic hydrocarbons (PAHs) in sediments were determined and the relationship between exposure of flounder blood cells to sediment extracts and DNA single-strand breakage in the blood cells was examined using the comet assay. Levels of DNA damage were proportionally increased by exposure concentration and the highest sediment-associated DNA damage was observed at the station showing the highest PAHs contamination. DNA damage in blood cells exposed to five types of PAHs (benzo[a]pyrene, fluoranthene, anthracene, pyrene and phenanthrene) and in flounder (Paralichthys olivaceus) exposed to benzo[a]pyrene (BaP) for 0, 2 and 4 days were assessed by measuring comet tail length. The tail lengths of five PAHs-exposed groups at 50 and 100 ppb were significantly different from the non-exposed group, and the genotoxic effect of BaP correlated with both concentration and duration of exposure. Throughout the study, significant differences in DNA breakage were recorded between cells exposed to sediment extracts or PAHs and non-exposed control. This study demonstrated the comet assay as a successful tool in monitoring contamination of marine sediments and assessing genotoxicity of PAHs in marine organisms, either in vitro or in vivo.     

Dynamic behaviour of polycyclic aromatic hydrocarbons in Brighton marina, UK

The distribution of polycyclic aromatic hydrocarbons (PAHs) between various phases is fundamental in the control of their movement and impact in the marine environment. In this study samples of water and sediments were regularly collected from Brighton marina, UK, to quantify the intensity, spatial and temporal variations of PAH contamination. The results show clearly that PAH behaviour in marine systems is highly complex, and controlled by the interplay of PAH sources, compound physicochemical properties, water and sediment movement, and field conditions. Levels of total PAHs (16 compounds) in the dissolved phase were found to vary between <2 and 11,400 ng/l, with higher values observed in the winter months. Total PAH concentration in sediment samples varied between 24 and 4710 ng/g dry weight. PAHs in water were dominated by low molecular mass compounds (2-ring), while PAHs in sediments were mainly derived from 2-4 ring compounds. In addition, dissolved concentrations were increased during sediment dredging and after a period of severe rainfall. PAHs in Brighton marina are likely to be from both pyrolytic and petrogenic sources; as a result, field-derived distribution coefficients for individual PAHs between sediment and water tend to follow the equilibrium partition models, although slight exceedance is apparent. The extended partition model incorporating soot carbon has achieved limited success in better predicting PAH behaviour.     

Using a fluvial archive to place extreme flood sediment (dis)connectivity dynamics in context of a longer-term record

The aim of this study was to establish the source and provenance of sediments deposited in a large floodplain sink during extreme floods in the Lockyer Creek catchment, Australia, in 2011 and 2013. We place the sediment source patterns in context of the longer-term record to determine whether coarse-grained sediment sources (i.e., very fine sand to very coarse sand) and the spatio-temporal pattern of (dis)connectivity have changed over time. We do this by matching the geochemical properties and age structure of a sediment profile located in a downstream floodplain sink to the elemental composition of source sediments. One hundred and fifty-seven sediment samples from 20 sites across the catchment are analysed using X-ray fluorescence (XRF) spectrometry to compare the elemental ratio composition of the downstream floodplain sink to its source materials. We use Optically Stimulated Luminescence (OSL) dating to determine the age structure of the sediments in the floodplain sink. The northern tributaries and parts of the Lockyer River trunk stream are the primary sources of coarse sediment. These areas are connected (coupled) to the lower trunk stream and floodplain sediment sink. Southern tributaries are largely disconnected (decoupled) and supply little sediment to the floodplain sediment sink. This pattern of sediment source contribution has remained similar over the last 6.8 ka at least. Sediment sources as observed in the 2011 flood have predominated over the mid-late Holocene whilst those in the 2013 flood are rare.     

The Consequences of the Oder Flood in 1997 on the Distribution of Polycyclic Aromatic Hydrocarbons in the Oder River

Changes in the levels and spatial distribution of PAHs as a consequence of the Oder flood in the summer of 1997 were investigated in post‐flood sediments from the Oder River and the Oder Lagoon. The aim of this study was to identify sources of the PAH pollution and in particular investigate polluted sites (“hot spots”) in the most highly suspected locations of the drainage area. Molecular indices based on isomeric PAH ratios and the ratio of the parent PAHs to methylated PAHs were used to distinguish between the pollution sources. Elevated levels of PAHs were discovered in the post‐flood sediments of the Oder River in comparison to the average regional values. Elevated concentrations of PAHs were also found in fluffy layer samples taken from the Oder Lagoon and the Pomeranian Bight in late August. The highest concentrations of PAHs were observed near power plants or roads with heavy traffic. Most of the contamination originates from high temperature pyrogenic sources with some slight overlays of petrogenic sources. These increased concentrations of pyrogenic origin may be attributable to flooding of municipal and industrial waste disposal areas in the Oder River drainage.     

Changes in sediment and organic carbon accumulation in a highly-disturbed ecosystem: The Sacramento-San Joaquin River Delta (California, USA)

We used the Sacramento-San Joaquin River Delta CA (Delta, hereafter) as a model system for understanding how human activities influence the delivery of sediment and total organic carbon (TOC) over the past 50–60 years. Sediment cores were collected from sites within the Delta representing the Sacramento River (SAC), the San Joaquin River (SJR), and Franks Tract (FT), a flooded agricultural tract. A variety of anthropogenic tracers including ¹³⁷Cs, total DDE (∑DDE) and brominated diphenyl ether (BDE) congeners were used to quantify sediment accumulation rates. This information was combined with total organic carbon (TOC) profiles to quantify rates of TOC accumulation. Across the three sites, sediment and TOC accumulation rates were four to eight-fold higher prior to 1972. Changes in sediment and TOC accumulation were coincident with completion of several large reservoirs and increased agriculture and urbanization in the Delta watershed. Radiocarbon content of TOC indicated that much of the carbon delivered to the Delta is “pre-aged” reflecting processing in the Delta watershed or during transport to the sites rather than an input of predominantly contemporary carbon (e.g., 900–1400 years BP in surface sediments and 2200 yrs BP and 3610 yrs BP at the base of the SJR and FT cores, respectively). Together, these data suggest that human activities have altered the amount and age of TOC accumulating in the Delta since the 1940s.     

The nematode/copepod ratio and its use in pollution ecology

The nematode/copepod ratio is critically examined with a view to adding some precision to its proposed use in pollution ecology. At two unpolluted intertidal sites, differing markedly in sediment grade, the metabolic requirements of copepods are shown to be equivalent to the requirements of that fraction of the nematode population which feeds in the same way. The partitioning of this total energy requirement among individuals depends on the distribution of individual metabolic body sizes and the relative rates of metabolism. The distribution of body sizes is constrained by the sediment granulometry, which affects nematodes and copepods differently. These considerations enable precise predictions of the nematode/copepod ratios expected in unpolluted situations, against which observed ratios can be compared.     

Seasonal variation in the toxicity of sediment-associated contaminants in Corpus Christi Bay, TX

Seasonal variation in pore water and sediment-water interface (SWI) toxicity at two sites of suspected contamination was investigated using sea urchin embryological development (Arbacia punctulata) and copepod hatching success (Schizopera knabeni). Site S1, located inside a marina, was fine-grained and S2, located near a neighboring stormwater outfall, was sandy. Both sites were cored in summer and winter, along with reference sites of equivalent grain sizes. Whereas the muddy contaminated site displayed a slight decrease in sea urchin toxicity from summer to winter, pore water from the sandy contaminated site exhibited an increase in sea urchin toxicity. The sandy sites displayed slight toxicity increase to copepod hatching success in winter, which occurred in the SWI of S2 and in the pore water from the reference site, R2, where it coincided with sedimentation. Cu was the most prevalent metal in the sediment samples. Although Cu concentration increased in the whole sediments and pore waters from summer to winter, its concentration in overlying SWI exposure decreased from summer to winter. Organic compounds exhibited opposite behavior, with smaller variety identified in the winter pore water samples, but more chemicals detected in the SWI samples in winter.