Tetrachlorodibenzo-p-dioxins and tetrachlorodibenzofurans in Atlantic coast striped bass and in selected Hudson River fish,waterfowl and sediments

In striped bass samples from the lower Hudson River and its estuary 2,3,7,8-tetrachlorodibenzo-$\text{p}$-dioxin (2,3,7,8-TCDD) was found at concentrations from 16 to 120 pg/g (ppt). Striped bass from two other locations (Rhode Island coastal waters and Chesapeake Bay, Maryland) had <5 ppt, 2,3,7,8-TCDD. The contaminant, 2,3,7,8-tetrachlorodibenzofuran (2,3,7,8-TCDF), was found in striped bass from all three locations with concentrations varying from 6 ppt in Chesapeake Bay to 78 ppt in the Hudson River. Results from a limited number of non-migratory fish (carp and goldfish) and sediments suggest that the upper Hudson River is not a source for 2,3,7,8-TCDD/2,3,7,8-TCDF contamination of striped bass.     

Integrated assessment of the impacts of agricultural drainwater in the Salinas River (California,USA)

The Salinas River is the largest of the three rivers that drain into the Monterey Bay National Marine Sanctuary in central California. Large areas of this watershed are cultivated year-round in row crops and previous laboratory studies have demonstrated that acute toxicity of agricultural drainwater to Ceriodaphnia dubia is caused by the organophosphate (OP) pesticides chlorpyrifos and diazinon. In the current study, we used a combination of ecotoxicologic tools to investigate incidence of chemical contamination and toxicity in waters and sediments in the river downstream of a previously uncharacterized agricultural drainage creek system. Water column toxicity was investigated using a cladoceran C. dubia while sediment toxicity was investigated using an amphipod Hyalella azteca. Ecological impacts of drainwater were investigated using bioassessments of macroinvertebrate community structure. The results indicated that Salinas River water downstream of the agricultural drain is acutely toxic to Ceriodaphnia, and toxicity to this species was highly correlated with combined toxic units (TUs) of chlorpyrifos and diazinon. Laboratory tests were used to demonstrate that sediments in this system were acutely toxic to H. azteca, which is a resident genus. Macroinvertebrate community structure was moderately impacted downstream of the agricultural drain input. While the lowest macroinvertebrate abundances were measured at the station demonstrating the greatest water column and sediment toxicity and the highest concentrations of pesticides, macroinvertebrate metrics were more significantly correlated with bank vegetation cover than any other variable. Results of this study suggest that pesticide pollution is the likely cause of laboratory-measured toxicity in the Salinas River samples and that this factor may interact with other factors to impact the macroinvertebrate community in the system.     

Evaluation of transport and storage of 60Co, 134Cs, 137Cs and 65Zn by river sediments in the lower Susquehanna River

The Peach Bottom Atomic Power Station (PBAPS) has contributed measurable quantities of radioactivity to Conowingo Reservoir, an impoundment of the lower Susquehanna River. As part of an ongoing radiological assessment program, concentrations of plant-related radionuclides in sediments have been monitored in spring and fall since 1980. Mass balance estimates derived from grab samples of surface sediments (< 10 cm) indicate that less than 20% of reactor released (60)Co, (65)Zn, (134)Cs and (137)Cs is present in these sediments. Significant seasonal variations in radionuclide trapping efficiency by the reservoir are not apparent. Deep core samples (c. 200 cm) confirm that some, but not all, of this surface sediment radionuclide inventory remains within the reservoir-trapped in discrete locations by subsequent sediment accumulation. The remaining radionuclide mass, in dissolved or particle-associated form, appears to be transported downstream, through Conowingo Dam, to upper Chesapeake Bay. The detection of PBAPS-derived radionuclides in the sediments of upper Chesapeake Bay, primarily the Susquehanna Flats, confirms the transport of these radionuclides from the lower Susquehanna River.     

Processes driving the short-term variability of polycyclic aromatic hydrocarbons in the Baltimore and northern Chesapeake Bay atmosphere,USA

Polycyclic aromatic hydrocarbons (PAHs) were measured in the Baltimore and adjacent Chesapeake Bay in July 1997. Time series of 4- and 12-h samples were taken at two sites 15 km apart in order to evaluate the influence of a number of processes on the short-term variability of PAH in the Baltimore and northern Chesapeake Bay atmospheres. PAH concentrations were 2–3-fold higher in the Baltimore atmosphere than in the adjacent Chesapeake Bay atmosphere. For example, gas-phase phenanthrene and pyrene concentrations were 12.5 and 2.14 ng m⁻³ in the Baltimore site and 5.57 and 0.548 ng m⁻³ in the Chesapeake Bay, respectively. The influence of wind direction, wind speed and temperature was evaluated by multiple linear regressions which indicated that atmospheric gas-phase PAH concentrations over the Chesapeake Bay were significantly higher when the air mass was from the urban/industrial Baltimore area. Furthermore, the increase of gas-phase low-MW PAH concentrations with temperature and wind speed suggests that volatilization from the bay is an important source of pollutants to the atmosphere, at least when air masses are not influenced by the Baltimore urban and industrial area. Indeed, while on the long-term, the Chesapeake Bay is a receptor of atmospherically deposited PAHs, on the short-term and during appropriate meteorological conditions, the bay acts as a source of pollutants to the atmosphere. Aerosol-phase PAH concentrations and temporal trends showed a strong dependence on aerosol soot content due to the high affinity of PAHs to the graphitic structure of soot. These results confirm the important influence of urban areas as a source of pollution to adjacent aquatic environments and as a driving factor of the short-term variability, either directly by transport of urban-generated pollutants or by volatilization of previously deposited pollutants. Conversely, the complex diurnal trends of gas-phase PAHs at the Baltimore site suggests that degradation processes dominate the diurnal trends of PAHs in urban atmospheres. This conclusion is supported by estimated rate constants for PAH reaction with OH radicals which show good agreement with reported values within a factor of two.     

A multi-parametric study of the interaction between the Parati river and Babitonga Bay in terms of water quality

Abstract

The Parati River contributes to the Babitonga Bay water complex, but the contents of the bay also influence the river during periods of inverted currents. In this study, the water quality along four stretches of the Parati River and Babitonga Bay was evaluated using chemical (physico-chemical and chromatographic analysis), microbiological (fluorescein diacetate hydrolysis) and ecotoxicological (Lumistox) methods to assess the reciprocal influence of the waters of this river-bay system. In addition, the most appropriate type of analysis for the monitoring of the estuarine region of the Parati River was identified. The results of six sampling campaigns showed that the type of contaminants and their levels varied temporally and spatially and thus the water quality also changed. Anthropogenic activity, such as banana cultivation and the release of sewage into the water system, is the primary cause of the contamination that affects the quality of the water in the Parati River estuary, which is a crucial ecological niche for the reproduction of various marine species. The ecotoxicity tests with Aliivibrio fischeri conducted to evaluate the water quality showed an integrative response, and the ecotoxicity data indicated that the Parati River does not have a significant influence on the water quality of Babitonga Bay.     

Hydrophobic organochlorine compounds sequestered in submersed aquatic macrophytes (Hydrilla verticillata (L.F.) Royle) from the tidal Potomac River (USA)

The potential for hydrophobic organochlorine contaminants to be sequestered in submersed aquatic vegetation was evaluated by determining the concentrations of cis- and trans-chlordane, dieldrin, and polychlorinated biphenyls (PCBs) in feral aquatic macrophytes (Hydrilla verticillata (L.f.) Royle) collected from the tidal Potomac River. Similarities in mean dry-weight concentrations of the identified organochlorine compounds in H. verticillata and surrounding alluvial sediments indicated that the extent of sequestration in H. verticillata was of the same magnitude as sorption of these compounds to river sediments, but some qualitative differences in PCB congener profiles existed. The results imply that to some degree H. verticillata can influence downstream fluxes of organic contaminants in fluvial transport in the Potomac River, and, furthermore, identify this species as a viable candidate organism for hydrophobic organochlorine contaminant biomonitoring in the Chesapeake Bay estuary.     

Identifying primary stressors impacting macroinvertebrates in the Salinas River (California, USA): relative effects of pesticides and suspended particles

Laboratory dose-response experiments with organophosphate and pyrethroid pesticides, and dose-response experiments with increasing particle loads were used to determine which of these stressors were likely responsible for the toxicity and macroinvertebrate impacts previously observed in the Salinas River. Experiments were conducted with the amphipod Hyalella azteca, the baetid mayfly Procloeon sp., and the midge Chironomus dilutus (Shobanov, formerly Chironomus tentans). The results indicate the primary stressor impacting H. azteca was pesticides, including chlorpyrifos and permethrin. The mayfly Procloeon sp. was sensitive to chlorpyrifos and permethrin within the range of concentrations of these pesticides measured in the river. Chironomus dilutus were sensitive to chlorpyrifos within the ranges of concentrations measured in the river. None of the species tested were affected by turbidity as high as 1000 NTUs. The current study shows that pesticides are more important acute stressors of macroinvertebrates than suspended sediments in the Salinas River.     

Polychlorinated biphenyls and particulate organic/elemental carbon in the atmosphere of Chesapeake Bay,USA

Polychlorinated biphenyls (PCBs) and particulate organic/elemental carbon (OC/EC) differ as to sources, but are both elevated in major urban areas leading to loadings of proximate terrestrial and aquatic systems. Because of the dramatic difference in speciation, sources, and sinks of these compunds, gas+particulate phase PCBs and particulate OC/EC were measured in urban Baltimore, MD and over Chesapeake Bay at 4 and 12 h frequencies in July 1997. Gas phase ∑PCBs averaged 1180 pg m⁻³ for Baltimore and 550 pg m⁻³ for northern Chesapeake Bay. PCB homolog distributions in the gas phase differed between the land and over-water sites whereby the trichlorobiphenyls were higher in Baltimore compared to Chesapeake Bay. Autocorrelation analysis yielded a diurnal cycle for gas phase PCBs at Baltimore with the lowest concentrations observed during the day. Particulate organic and elemental carbon constituted 12.4% (17.4% organic matter) and 2.8% of total suspended particles (TSP) in Baltimore, and 15.0% (21.0% organic matter) and 5.3% over the Chesapeake Bay, respectively. Variability in PCB concentrations was not related to the variability in OC/EC concentrations. OC/EC ratios suggest that particulate organic carbon was mostly primary aerosol. Emissions of both classes of compounds into the Baltimore atmosphere and vicinity are major sources to the Bay.     

Role of manganese oxides in the exposure of mute swans (Cygnus olor) to Pb and other elements in the Chesapeake Bay, USA

The aims of this study are to estimate exposure of waterfowl to elements in contaminated sediments in the Chesapeake Bay and to consider the potential role of Mn in influencing bioavailability and exposure. Metal concentrations were measured in livers and digesta taken from mute swans living on the Aberdeen Proving Ground, whose sediment had elevated concentrations of Cu, S, Se, Zn, As, Co, Cr, Hg and Pb. Concentrations of only the first four of these elements were elevated in swan digesta. None of the concentrations detected in the digesta or livers of the swans was considered toxic, although the concentrations of Cu and Se were high compared to concentrations of these elements reported in other waterfowl. Lead was found to be scavenged by Mn and Fe oxides from the water and deposited on the surface of vegetation at a reference site. Under some environmental chemical conditions, this is an important route of exposure to Pb in waterfowl, not previously recognized.     

Mitigation of chlorpyrifos runoff using constructed wetlands

Constructed wetlands have been proposed as a potential best management practice (BMP) to mitigate effects of pesticide-associated agricultural runoff. Wetland mesocosms (14 m x 59-73 m) were amended with chlorpyrifos to simulate a storm runoff event at concentrations of 73, 147 and 733 microg/l. Water, sediment and plant samples collected weekly for 12 weeks indicated that chlorpyrifos rapidly sorbed to sediment and plant material, with approximately 47-65% of measured chlorpyrifos mass retained within the first 30-36 m of wetland mesocosms. Of the measured mass, approximately 55% and 25% were retained by sediments and plants, respectively. A field-scale evaluation of a constructed wetland's mitigation capability was performed in the Lourens River watershed of Cape Town, South Africa. Results indicate that the wetland was able to retain and considerably decrease the concentration (and hence toxicity) of chlorpyrifos and suspended sediment entering the receiving waterbody (Lourens River). This research provides fundamental answers concerning constructed wetland capabilities that are necessary for constructing field-scale systems within agricultural watersheds.     

Polybrominated diphenyl ethers in surface sediments of the Yangtze River Delta: Levels, distribution and potential hydrodynamic influence

A total of 32 surface sediments collected from the Yangtze River Estuary, Hangzhou Bay and the Qiantang River were analyzed for polybrominated diphenyl ethers (PBDEs). The concentrations of summation operatorPBDEs (sum of 12 PBDE congeners without BDE 209) and BDE 209 varied from n.d. to 0.55 and from 0.16 to 94.6 ng/g, respectively. The spatial variability of summation operatorPBDEs concentrations indicated that waste discharge from the urban areas might been the main source of PBDEs in the Yangtze River Delta. BDE 209 was the predominant congener (approximately 90-100%) detected among the 13 congeners, consistent with the fact that technical deca-BDE mixtures are presently the dominant technical PBDE mixtures used in China. Compared to published data acquired from other locales, PBDE congeners with less than four bromines were more abundant in the present study area. The hydrodynamic conditions may likely be a significant factor in dictating the observed levels and congener distribution patterns of PBDEs.     

Influence of Baltimore's Urban Atmosphere on Organic Contaminants over the Northern Chesapeake Bay

ABSTRACT

Air and precipitation samples were collected along an urban to over-water to rural transect across the northern Chesapeake Bay as a preliminary investigation into the spatial extent of elevated atmospheric concentrations of urban-derived persistent organic pollutants. Air samples were collected daily from June 3–9, 1996, along the transect as part of the Atmospheric Exchange over Lakes and Oceans project. Total (gas + particle bound) atmospheric polycy-clic aromatic hydrocarbon concentrations [∑-PAH] ranged from 0.4 to 114 ng/m³, and gas phase polychlorinated bi-phenyl concentrations [∑-PCB] ranged from 0.02 to 3.4 ng/m³. Strong concentration gradients were found for both PAHs and PCBs, with the highest concentrations in the city and the lowest at the downwind rural site. Gas and particle bound PAHs varied independently in the city, possibly due to strong but geographically separated emission sources. A precipitation event collected during westerly winds contained fourfold higher ∑-PAH and twelvefold higher ∑-PCB concentrations at the over-water site than at the rural background location, further indicating that the urban plume extends from Baltimore, MD, over the northern Chesapeake Bay over a spatial scale of approximately 30 km.     

Hazard prioritization in ecological risk assessment through spatial analysis of toxicant gradients

The analysis of spatial relationships among the distribution of environmental stressors and observed or predicted adverse effects may be a useful method of prioritizing hazards in regional ecological risk assessment (ERA). Geographic information systems were used to compare the spatial distribution of toxicant concentrations in sediments of Chesapeake Bay with the distribution of areas in the basin where ecological impacts have historically been observed. Toxicants were then prioritized based upon the strength of their spatial association with the high impact areas. This method of hazard identification/prioritization was validated against the Chesapeake Bay Program's lists of toxics of concern and toxics of potential concern (TOC and TOPC, respectively). Of the 18 toxicants on the TOC/TOPC lists that were considered in the current study, 15 (83%) were identified as priority contaminants in the current study, 11 (73%) of which were either of primary or secondary concern. The use of spatial analysis tools in ERA may lead to more rapid and rigorous methods for prioritizing environmental risks.     

EROD and CYP1A protein in channel catfish (Ictalurus punctatus) from an urban estuary relative to that in benzo[a]pyrene-exposed hatchery specimens

Bottom-feeding fish such as flounder and killifish have been widely used in monitoring hepatic monooxygenase induction in polluted water bodies. While channel catfish are often utilized in tissue monitoring of fresh and estuarine water bodies, few data are available on their use in environmental monitoring of hepatic monooxygenase activity. In this project, the presence of CYP1A protein was verified in channel catfish through recognition by Mab 1-12-3, an antibody which recognizes the CYP1A homologue in a variety of teleost species. CYP1A protein levels and 7-ethoxyresorufin-o-deethylase (EROD) activity in laboratory control and benzo-a-pyrene (BaP)-challenged channel catfish were compared to those in feral channel catfish from Back River, an urban estuarine tributary to Chesapeake Bay. Though more variable, mean CYP1A protein levels in the field-collected fish were similar to those of the BaP-induced laboratory fish. However, EROD activity of the Back River fish was less than one half that observed in the BaP-induced laboratory fish. When normalized to CYP1A protein levels, EROD activity was slightly lower in the Back River fish than either the laboratory control or BaP-treated fish. This finding may indicate possible inhibition or inactivation of the CYP1A protein in the feral fish.     

DDT is still a problem in developed countries: the heavy pollution of Lake Maggiore

The Zebra mussel (Dreissena polymorpha), one of the most widely used bioindicators of persistent organic pollutants, trace metals and radionuclides in several worldwide freshwater ecosystems, has been used to monitor DDT contamination trends in Lake Maggiore since 1996, caused by industrial effluents on a tributary of the River Toce, one of the major affluents of the lake. Dreissena specimens were collected at two sampling sites, one within the Baveno Bay, where the River Toce flows, and the other outside (Villa Taranto). Total DDT levels (3119.6 ng/g lipids at Baveno and 1351.2 ng/g lipids at Villa Taranto) in the soft tissues of the Zebra mussel decreased at both stations by about 30-50% in the first year after the closure of the chemical plant reaching an almost steady-state condition. The high concentrations measured in Zebra mussel specimens of Baveno Bay in 2000 (1947 ng/g lipids) and the percentage of pp'DDE in comparison with total DDT concentration, which showed a slight increase in the last years, clearly indicate that a contamination source is still present, deriving probably from the lacustrine sediments and the River Toce. Data show that the environmental risk is very high within the Baveno Bay and the recovery time should be longer than in the other parts of the lake, where DDT levels in Dreissena are presently two times higher than those measured in the other Italian subalpine lakes.     

Improved daily precipitation nitrate and ammonium concentration models for the Chesapeake Bay Watershed

Daily precipitation nitrate and ammonium concentration models were developed for the Chesapeake Bay Watershed (USA) using a linear least-squares regression approach and precipitation chemistry data from 29 National Atmospheric Deposition Program/National Trends Network (NADP/NTN) sites. Only weekly samples that comprised a single precipitation event were used in model development. The most significant variables in both ammonium and nitrate models included: precipitation volume, the number of days since the last event, a measure of seasonality, latitude, and the proportion of land within 8km covered by forest or devoted to industry and transportation. Additional variables included in the nitrate model were the proportion of land within 0.8km covered by water and/or forest. Local and regional ammonia and nitrogen oxide emissions were not as well correlated as land cover. Modeled concentrations compared very well with event chemistry data collected at six NADP/AirMoN sites within the Chesapeake Bay Watershed. Wet deposition estimates were also consistent with observed deposition at selected sites. Accurately describing the spatial distribution of precipitation volume throughout the watershed is important in providing critical estimates of wet-fall deposition of ammonium and nitrate.     

Sorption and bioreduction of hexavalent uranium at a military facility by the Chesapeake Bay

Directly adjacent to the Chesapeake Bay lies the Aberdeen Proving Ground, a U.S. Army facility where testing of armor-piercing ammunitions has resulted in the deposition of >70,000 kg of depleted uranium (DU) to local soils and sediments. Results of previous environmental monitoring suggested limited mobilization in the impact area and no transport of DU into the nation's largest estuary. To determine if physical and biological reactions constitute mechanisms involved in limiting contaminant transport, the sorption and biotransformation behavior of the radionuclide was studied using geochemical modeling and laboratory microcosms (500 ppb U(VI) initially). An immediate decline in dissolved U(VI) concentrations was observed under both sterile and non-sterile conditions due to rapid association of U(VI) with natural organic matter in the sediment. Reduction of U(VI) to U(IV) occurred only in non-sterile microcosms. In the non-sterile samples, intrinsic bioreduction of uranium involved bacteria of the order Clostridiales and was only moderately enhanced by the addition of acetate (41% vs. 56% in 121 days). Overall, this study demonstrates that the migration of depleted uranium from the APG site into the Chesapeake Bay may be limited by a combination of processes that include rapid sorption of U(VI) species to natural organic matter, followed by slow, intrinsic bioreduction to U(IV).     

Chlorpyrifos degradation in a biomixture of biobed at different maturity stages

The biomixture is a principal element controlling the degradation efficacy of the biobed. The maturity of the biomixture used in the biobed affects its overall performance of the biobed, but this is not well studied yet. The aim of this research was to evaluate the effect of using a typical composition of Swedish biomixture at different maturity stages on the degradation of chlorpyrifos. Tests were made using biomixture at three maturity stages: 0 d (BC0), 15 d (BC15) and 30 d (BC30); chlorpyrifos was added to the biobeds at final concentration of 200, 320 and 480 mg kg⁻¹. Chlorpyrifos degradation in the biomixture was monitored over time. Formation of TCP (3,5,6-trichloro-2-pyrinidol) was also quantified, and hydrolytic and phenoloxidase activities measured. The biomixture efficiently degraded chlorpyrifos (degradation efficiency >50%) in all the evaluated maturity stages. However, chlorpyrifos degradation decreased with increasing concentrations of the pesticide. TCP formation occurred in all biomixtures, but a major accumulation was observed in BC30. Significant differences were found in both phenoloxidase and hydrolytic activities in the three maturity stages of biomixture evaluated. Also, these two biological activities were affected by the increase in pesticide concentration. In conclusion, our results demonstrated that chlorpyrifos can be degraded efficiently in all the evaluated maturity stages.     

Distribution of mono- through hexa-chlorobenzenes in floodplain soils and sediments of the Tittabawassee and Saginaw Rivers,Michigan

Introduction  

Chlorobenzenes are used as solvents or as feedstocks in the production of pesticide formulations, dyes, room deodorizers, moth-proofing agents, and de-inking solvents. Chlorobenzenes were produced by the Dow Chemical Company in Midland, Michigan, for several decades. In this study, concentrations of 12 chlorobenzene (CBz) congeners, from mono- to hexachlorobenzenes, were measured in more than 150 floodplain soil (FPS), surface sediment, and sediment core (SC) samples collected during 2002–2004 from the Pine River, Tittabawassee River, Shiawassee River, Saginaw River, and Saginaw Bay, Michigan.     

Persistence and runoff losses of 3 herbicides and chlorpyrifos from a corn field in the Lake Balaton watershed of Hungary

Corn is intensively cultivated in western Hungary in the basin of Lake Balaton, one of the most important water resources in eastern Europe. Pesticide runoff was measured in 1996 and 1997 from a typical corn field near Zalaegerszeg, Hungary, which drains into the Zala River, an important water source of Lake Balaton. Three herbicides, namely atrazine, acetochlor, and propizochlor, and the insecticide chlorpyrifos were applied to bare soil in a field with 5% slope and soil and runoff water pesticide concentrations were monitored. In 1997, a rainfall-runoff simulation experiment was conducted on a small sub-plot in order to measure pesticide runoff under reasonable worst-case conditions. Under natural rainfall almost all losses occurred in a large runoff event in 1996 one month after application in which 3% of atrazine and 1% of acetochlor was transported off the field. Propizochlor and chlorpyrifos losses in the same event were much lower: 0.2% and <0.01%, respectively, because of these chemicals' shorter persistence times in near-surface soil. The rainfall simulation produced only trace amounts of losses even though 4.1 cm was applied in 2 hours; the soil was extremely dry and only 0.2 cm runoff occurred containing less than 0.01% of all chemicals applied. The results suggest that intensive use of corn herbicides, which have been found to result in widespread contamination of water resources elsewhere, may be expected to have the same impact in the Balaton watershed depending on the amounts and intensities used in the basin.