Richard J. Wenning

Polycyclic aromatic hydrocarbon and petroleum hydrocarbon contamination in sediment from the Newark Bay Estuary, New Jersey

The presence of numerous industrial and municipal sources such as former creosote wood preserving facilities, petroleum storage and refinery facilities, paint and chemical manufacturers, combined sewer overflows, and sewage treatment facilities along the shores of Newark Bay, New Jersey and its major tributaries suggests the potential for widespread contamination by polycyclic aromatic hydrocarbons (PAHs) and petroleum hydrocarbons. In this study, the concentrations and distributions of 19 PAHs and total extractable petroleum hydrocarbon (TEPH) were determined in 213 sediment samples obtained from 58 sediment cores collected between November 1991 and March 1993 from the Arthur Kill, Elizabeth River, Hackensack River, Kill Van Kull, Newark Bay, Upper New York Bay, and Rahway River. Chronological profiles of PAH and TEPH deposition from pre-1930 to the present were determined in each sediment core using 137Cs and 210Pb radioisotope measurements. The concentrations of total PAHs (tPAH) and individual PAHs were compared to National Oceanic and Atmospheric Administration (NOAA) benchmark sediment effects-range median (ER-M) values. The objectives of this study were to: (a) determine the spatial and temporal distributions of PAHs in sediments; (b) identify their possible sources; and (c) assess the potential for sediment toxicity within the estuary. The results indicate elevated concentrations of PAHs and TEPH in surface and buried sediments throughout the estuary, particularly in the Elizabeth River, the Arthur Kill, and in the Passaic River above the Dundee Dam and below the Jackson Street Bridge. Sediments collected from ship berths at Port Newark and Port Elizabeth in Newark Bay were also found to contain elevated levels of PAHs and TEPH. The concentrations of PAHs and TEPH in sediment generally increase with depth throughout the estuary. Comparisons to NOAA ER-M values indicate that the concentrations of many PAHs in surface and buried sediments at several locations in the estuary pose a significant hazard to aquatic organisms. Radiodating of sediment cores reveals that the highest concentrations of PAHs, and the greatest potential hazards to aquatic biota, occur in sediments deposited during the 1950s. Although the major inputs of PAHs are probably combustion sources and urban runoff entering the estuary through combined sewer overflows and storm drains, the unusually high concentrations of PAHs and TEPH found in some sediments may be best explained by point source inputs or catastrophic oil spills.

Chemometric comparisons of polychlorinated dibenzo-p-dioxin and dibenzofuran residues in surficial sediments from Newark Bay, New Jersey and other industrialized waterways

The distributions of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) measured in surficial sediments from the lower Passaic River and Newark Bay, New Jersey were compared to those observed in sediments from other waterways located within industrial or heavily populated areas using chemometric techniques. Comparisons were conducted using published data to determine whether the distributions of 2,3,7,8-substituted isomers in surficial sediments from industrialized waterways have similar or different fingerprint patterns. Chemometric evaluations consisted of principal components analysis and the complete linkage: farthest neighbor cluster method. The concentrations of individual isomers were normalized to the combined sum of the 2,3,7,8-substituted PCDD and PCDF isomer concentrations in order to evaluate relative distribution patterns. Several of the isomeric fingerprint patterns found in sediments from the lower Passaic River and Newark Bay were similar to those found in sediments from New Bedford Harbor, MA, USA, Black Rock Harbor, CT, USA, Providence River, RI, USA, Eagle Harbor, WA, USA, the Inner Stockholm archipelago, Sweden, Hamburg Harbor, Germany, and St. Laurensharbor, The Netherlands. Pattern differences were observed in sediments from Frierfjorden, Norway, Niagara River, NY, USA, and Chemieharbor, The Netherlands. The variations among the 2,3,7,8-substituted isomer patterns observed in different sediments were largely explained by the distributions of the higher chlorinated isomers. Other differences may be attributed to environmental conditions unique to each waterway such as tidal flux, shipping traffic, urbanization, sedimentation rates, and the presence of different industrial sources. Similarities in PCDD and PCDF patterns among the waterways were related to the presence of similar municipal and industrial sources, including effluents from pentachlorophenol and polychlorinated biphenyl manufacturing facilities, pulp and paper mills, automobile and shipping traffic, and municipal solid waste and industrial incinerators. The distributions of PCDDs and PCDFs in surficial sediments from some areas of the Newark Bay estuary were representative of those found in many industrialized regions. It wsa evident from this analysis that the application of chemometric analysis can be useful in characterizing the distribution of complex multi-constituent chemical residues and identifying sources of these compounds in freshwater, estuarine, and marine sediments.

Oxidant-mediated biochemical effects of paraquat in the ribbed mussel, Geukensia demissa

The role of reduction/oxidation cycling in the toxic effects of the bipyridyl herbicide paraquat was examined in the hepatopancreas of the ribbed mussel, Geukensia demissa. In vitro studies indicated a dose-dependent increase in the rate of superoxide anion (O2−) generation, as measured by the reduction of cytochrome c, in the microsomal fraction of the hepatopancreas. The highest concentration of paraquat employed (4 mM) elicited an 81% increase in O2− production above controls, which was inhibited by the addition of superoxide dismutase (SOD). For in vivo studies, a single application of paraquat (0.5, 1.0, or 2.0 mM) was added to aerated salt-water aquaria containing mussels. Biochemical analyses of antioxidant enzymes, reduced glutathione (GSH), and lipid peroxidation were performed in hepatopancreatic tissue of mussels after exposures of 6, 12, 24, and 36 h. Catalase activities were significantly elevated (p < 0.05) in all treatment groups above controls at 6 h, in the 0.5 and 1.0 mM treatment groups at 12 h, and in the 0.5 mM group at 36 h. Total SOD activities were nearly doubled from controls in each treatment group at 12 h. However, SOD activities in exposed mussels were generally similar to or below controls at other times. GSH concentrations were generally higher in exposed mussels than in controls at all exposure periods. Lipid peroxidation in most treatment groups was significantly higher than in controls at 6, 12, and 24 h. The results support the hypotheses that these bivalves can activate redox cycling compounds and demonstrate in vivo responses typical of oxidative stress as observed in other organisms.

Uncertainties and data needs in risk assessment of three commercial polybrominated diphenyl ethers: probabilistic exposure analysis and comparison with European Commission results

Some environmental monitoring programs have reported increasing levels of certain polybrominated diphenyl ether (PBDE) isomers in aquatic biota and in human breast milk. The commercial PBDE products are known as penta-, octa-, and deca-brominated diphenyl ethers (PeBDE, OBDE and DBDE, respectively). Aside from the current European Commissions risk assessment initiative and efforts underway in Sweden, Canada and elsewhere to evaluate environmental levels, little is understood about sources of exposure and risks to humans. In this study, a multi-pathway human health risk assessment was performed to predict theoretical chronic daily intakes (CDIs) of PeBDE, OBDE, and DBDE by five different age groups: 0-2, 2-6, 6-12, 12-18, and 18-70 years. Sources of exposure included air, drinking water, consumption of fish, vegetables, meat and dairy products, and ingestion of breast milk by infants. In addition to a deterministic analysis, the risk assessment included a probabilistic analysis to derive the probability density functions describing the range of plausible exposures associated with eight different pathways, as well as aggregate lifetime exposures for each age group. The results were compared to CDI point estimates calculated by the European Chemicals Bureau as part of the European Commissions Existing Substances Programme. The major sources of uncertainties are discussed, including environmental sources, levels in different environmental compartments, toxicity, and human exposure. This paper also discusses the limitations in the current state-of-the-science and provides recommendations for improving the scientific relevance and accuracy of future environmental risk assessments of PBDEs.

Scientific derivation of environmental quality benchmarks for the protection of aquatic ecosystems: challenges and opportunities

In recent decades, the paradigm of water quality management has shifted from complete prohibition of pollutant discharge (i.e. zero tolerance) to permitting limited discharge of pollutants to receiving water bodies based on the results of a risk-based assessment approach. This approach assumes that the aquatic ecosystem is able to cope with certain levels of pollutants without harming aquatic life and the health of local communities who rely on the water body for food, drinking water and enjoyment. A risk-based approach also assumes that safe levels can be defined for pollutants that do not cause unacceptable disruptions of the structure and function of the aquatic ecosystem. This approach acknowledges the presence of uncertainty associated with the current understanding of substance-specific ecotoxicity, the behaviour of chemical mixtures in the environment, ecology of the receiving waters and the ability to measure chemical contaminants in effluents and receiving waters accurately. Furthermore, a risk-based approach acknowledges that the most serious water pollutants in terms of human health worldwide may not be man-made chemicals, but rather the pathogenic organisms originating from untreated or improperly treated human wastes. In developed countries, pollutioncontrol technologies have reduced or eliminated most of sources of pathogens in inland surface waters, thereby affording attention on other contaminants in water such as industrial chemicals, metals, and agricultural chemicals. The situation, however, is quite different in less-developed countries. In 2012, it was estimated that 37 % of the world’s population still lack adequate sanitation while 11 % of the global population could not gain access to clean drinking water (WHO 2012). From this perspective, the use of a riskbased approach that is able to focus attention on the largest water quality challenges and can confidently direct scarce financial resources to actions that will affect the largest results for protection of clean drinking water is of paramount importance. Scientists and environmental authorities are confronted with the realities facing less-developed countries, the nature of current scientific uncertainties and recognition that zero tolerance of water pollutants will likely have unacceptable economic consequences for societies striving to improve quality of life. It is self-evident, therefore, that the derivation of risk-based environmental quality guidelines, threshold values, limits, objectives and benchmarks by national regulatory authorities is gaining widespread acceptance as an appropriate foundation for national and international water quality management.

A mixing model for polychlorinated dibenzo-p-dioxins and dibenzofurans in surface sediments from Newark Bay, New Jersey using polytopic vector analysis

The identity and relative contributions of various sources of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) to recently deposited sediments collected in Newark Bay and its major tributaries were determined using polytopic vector analysis (PVA), a multivariate statistical technique relatively new in the chemometric literature. The concentrations of 2,3,7,8-substituted PCDD/Fs were assayed in eighty-one surface and near-surface sediment samples collected from the Passaic River, Hackensack River, Arthur Kill, Elizabeth River, Kill Van Kull, Port Elizabeth, and Port Newark navigation channels and Robins Reef, which is located in New York Harbor. PVA modeling revealed five predominant 2,3,7,8-substituted PCDD/F fingerprint patterns in geographically plausible distributions throughout the estuary. This was consistent with the current understanding of hydrodynamic and sedimentation conditions reported in the literature for Newark Bay. Three patterns contained 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD), which is alleged to originate from a single industrial source on the lower Passaic River. One of the fingerprints containing 2,3,7,8-TCDD was present in moderate proportions (10–20%) in surface sediments near the site, but was generally observed in low abundance (<5%) elsewhere in the estuary. A fingerprint pattern characteristic of PCDD/F profiles in effluents from municipal sewage and waste water treatment plants was widely distributed in the estuary, but reached its highest relative proportions in the Elizabeth River. A third fingerprint pattern was highest in the Arthur Kill and lower Passaic River and closely matched the residue patterns found in several types of combustion sources. A fourth finger-print pattern in Hackensack River and lower Passaic River sediment matched the PCDD/F profile reported in PCB Aroclor® formulations. A fifth fingerprint pattern matched the profile in recycled pulp and paper mill effluents and was highest in Kill van Kull and upper Passaic River sediment. The majority of PCDD/Fs in sediment from Reaches B, C, and D of Port Newark and Port Elizabeth were attributable to sediments transported via the Arthur Kill and the Kill Van Kull. These results are consistent with those previously reported using principal components analysis, which indicated that 2,3,7,8-substituted PCDD/F patterns in the sediments of Newark Bay are consistent with discharges from multiple sources.

Principal components analysis of potential sources of polychlorinated dibenzop-dioxin and dibenzofuran residues in surficial sediments from Newark Bay, New Jersey

The distributions of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) measured in surficial sediments from the lower Passaic River and Newark Bay, New Jersey, USA, were compared to those reported in various industrial process residues and effluents, contaminated soils, chemical formulations, and municipal waste disposal activities that are known or suspected to be sources of these compounds in the aquatic environment. Comparisons were conducted using data from published literature to determine whether the composition of tetra through octachlorinated congeners and 2,3,7,8-substituted residues reported in a broad range of potential environmental sources could explain the presence of these compounds in Newark Bay. Pattern similarities and differences between congener groups and isomers were obtained by principal components analysis. The congener and isomer fingerprint patterns found in surficial sediments appear to be the result of releases from several industrial and municipal sources commonly found in heavily industrialized and populated urban environments, including municipal sewage sludge, municipal solid waste incinerator fly ash, pentachlorophenol, sodium pentachlorophenate, newsprint, scrap metal reclamation incinerators, combustion engines, and pulp and paper mill black liquor recovery furnaces. The variations among the PCDD and PCDF residue and congener patterns were largely explained by the distributions of the hexa- and octachlorinated compounds and by 2,3,7,8,-TCDD, 2,3,7,8,-TCDF, and the penta-substituted isomers. Although it has been claimed that a single industrial source is responsible for the presence of these compounds in the sediments of Newark Bay, the available evidence indicates that the vast majority of the PCDDs and PCDFs are the result of contributions from several industries. There is no evidence from this analysis to indicate that a single source is responsible for the contamination.

Accumulation of metals, polychlorinated biphenyls, and polycyclic aromatic hydrocarbons in sediments from the lower Passaic River, New Jersey

Thirteen sediment cores of 1.5–6 m depth were collected from the lower Passaic River in Newark, New Jersey and assayed for metals, total petroleum hydrocarbons, polycyclic aromatic hydrocarbons (PAHs), and Aroclor® and coplanar polychlorinated biphenyls (PCBs). Chronological profiles of chemical concentrations at specified depths and sediment accumulation rates in each core were determined by 137Cs and 210Pb radioisotope measurements. Temporal concentrations of these chemicals were compared to available benchmark sediment toxicity values to assess historic and current toxic hazards to aquatic organisms. Elevated concentrations of several metals, including copper, lead, mercury, nickel, and zinc, were found in surface and buried sediments at concentrations that greatly exceeded Long and Morgan (1991) Effects Range-Low (ER-L) and Effects Range-Median (ER-M) values. Aroclors® 1242, 1248, and 1254 and several PAHs were also found at concentrations exceeding Long and Morgan (1991) benchmark toxicity values. In general, the highest metal and PAH concentrations were found in sediment deposited prior to the 1960s. Elevated PCB concentrations were found in sediment deposited between 1950 and 1980. The results indicate that the lower Passaic River is heavily contaminated due to recent and historical municipal and industrial discharges from local and up-stream sources. The primary sources of PCBs, PAHs, and metals appear to be discharges of industrial effluents either directly into the waterway or through combined sewer overflows. Additional inputs are probably from urban runoff entering through combined sewer overflows and storm drains.

Distribution and possible sources of polychlorinated biphenyls in dated sediments from the Newark Bay estuary, New Jersey

Two hundred and forty-six sediment samples from Newark Bay, New Jersey and its tributaries (the Passaic River, Hackensack River, Kill van Kull, and Arthur Kill and its tributaries, the Elizabeth River and Rahway River) were assayed for commercial Aroclor® mixtures and non-ortho and mono-ortho coplanar polychlorinated biphenyls (PCBs) between 1990 and 1993. In addition, chronological profiles of PCBs in sediments from pre-1940 to the present were determined using radioisotope activities of 210Pb and 137Cs. The objectives of this study were to (a) determine the spatial and temporal distributions of PCBs in sediments, (b) identify their possible sources, and (c) evaluate the potential for sediment toxicity within the Newark Bay Estuary. Aroclors® 1248 and 1254 were detected in surface and buried sediments in each waterway. The highest concentrations occurred primarily in buried sediments from the Passaic River and Newark Bay at depths corresponding to historical deposition during the 1960s and 1970s, the peak manufacturing period for Aroclors®. In surface sediments, the highest concentrations were measured in the Passaic River, Rahway River, Kill Van Kull, and ship berths at Port Elizabeth and Port Newark in Newark Bay. Coplanar PCBs were detected throughout the estuary at much lower concentrations than the Aroclors. Results from the Passaic River indicate that the lower reach is contaminated with relatively high levels of PCBs, in part due to a relatively high depositional environment and the accumulation of PCB-contaminated sediments from local and upstream sources. Comparisons to available benchmark sediment quality values and calculated toxicity equivalent concentrations raise a concern that Aroclors® 1248 and 1254 and coplanar PCBs, respectively, may adversely effect aquatic organisms in the estuary.

DDT, DDD, and DDE contamination of sediment in the Newark Bay estuary, New Jersey

Two hundred and forty-six surface and buried sediment samples from Newark Bay, New Jersey, and its major tributaries (Passaic River, Hackensack River, Newark Bay, Arthur Kill, Elizabeth River, and Kill Van Kull) were assayed for p,p′-dichlorodiphenyltrichloroethane (p,p′-DDT), p,p′-dichlorodiphenyldichloroethane (p,p′-DDD), and p,p′-dichlorodiphenylchloroethylene (p,p′-DDE) between February 1990 and March 1993. Chronological profiles in sediments from pre-1940 to the present were determined by radioisotope activities of 210Pb and 137Cs. The concentrations of these chemicals were compared to National Oceanic and Atmospheric Administration (NOAA) benchmark sediment values (Long and Morgan 1991). The objectives were to (a) determine the spatial and temporal distributions of DDT compounds in sediments, (b) identify possible sources, and (c) assess the potential for sediment toxicity within the estuary. Mean concentrations in surface sediments in individual waterways ranged from 5 to 473 μg/kg for p,p′-DDT, 18 to 429 μg/kg for p,p′-DDD, and 5 to 111 μg/kg for p,p′-DDE. A regional background mean concentration of approximately 100–300 μg/kg Σp,p′-DDT (sum of p,p′-DDT, p,p′-DDD, and p,p′-DDE) was measured in surface sediments throughout the estuary, with the exception of the Arthur Kill, where mean concentrations exceeded 700 μg/kg. The elevated concentrations found in recently deposited surface sediments in the Arthur Kill may be due to the presence of ongoing sources. The highest concentrations in buried sediments occurred in the lower Passaic River at depths corresponding to historical deposits from 1940 to 1970, the peak time period for production and usage of DDT in the United States. Comparisons to NOAA benchmark sediment toxicity values indicate that p,p′-DDT, p,p′-DDD, and p,p′-DDE concentrations in surface sediments may pose a potential hazard to fish, shellfish, and other benthic and demersal organisms in some portions of the estuary, particularly in the upper and lower Arthur Kill.