Environmental contaminants in freshwater fish and their risk to piscivorous wildlife based on a national monitoring program

Organochlorine chemical residues and elemental concentrations were measured in piscivorous and benthivorous fish at 111 sites from large U.S. river basins. Potential contaminant sources such as urban and agricultural runoff, industrial discharges, mine drainage, and irrigation varied among the sampling sites. Our objectives were to provide summary statistics for chemical contaminants and to determine if contaminant concentrations in the fish were a risk to wildlife that forage at these sites. Concentrations of dieldrin, total DDT, total PCBs, toxaphene, TCDD-EQ, cadmium, chromium, mercury, lead, selenium, and zinc exceeded toxicity thresholds to protect fish and piscivorous wildlife in samples from at least one site; most exceedences were for total PCBs, mercury, and zinc. Chemical concentrations in fish from the Mississippi River Basin exceeded the greatest number of toxicity thresholds. Screening level wildlife risk analysis models were developed for bald eagle and mink using no adverse effect levels (NOAELs), which were derived from adult dietary exposure or tissue concentration studies and based primarily on reproductive endpoints. No effect hazard concentrations (NEHC) were calculated by comparing the NOAEL to the food ingestion rate (dietary-based NOAEL) or biomagnification factor (tissue-based NOAEL) of each receptor. Piscivorous wildlife may be at risk from a contaminant if the measured concentration in fish exceeds the NEHC. Concentrations of most organochlorine residues and elemental contaminants represented no to low risk to bald eagle and mink at most sites. The risk associated with pentachloroanisole, aldrin, Dacthal, methoxychlor, mirex, and toxaphene was unknown because NOAELs for these contaminants were not available for bald eagle or mink. Risk differed among modeled species and sites. Our screening level analysis indicates that the greatest risk to piscivorous wildlife was from total DDT, total PCBs, TCDD-EQ, mercury, and selenium. Bald eagles were at greater risk to total DDT and total PCBs than mink, whereas risks of TCDD-EQ, mercury, and selenium were greater to mink than bald eagle.     

The contamination of fish with chlorinated hydrocarbons in Portugal: continental coast and Azores islands

In a baseline study, muscle and liver from important commercial fish belonging to different trophic levels were analysed for organochlorines. Samples of sole, sardine and hake were collected from seven locations off the Continental coast and greater forkbeard and horse mackerel off two Azores islands. Residues of ppDDT, ppDDE and PCBs were present in all muscle and liver samples. ppDDD occurred in all liver samples and in most muscle samples, except in sole where it occurred in 29% of the samples. Dieldrin was detected less frequently and did not occur in samples from the Azores. The residue levels were generally similar to those detected in related species from the North Sea, except for samples of sole collected between the Tagus and Sado estuaries where much higher residues were obtained. In view of the low consumption of insecticides in the Azores, it is proposed that long-range transport of organochlorines by winds and/or marine currents is responsible for their presence in this area. The organochlorine residues found in these fish showed no relationship with their position in the food chain but the values did increase with the quantity of lipids present. An unknown compound analysed by GC-MS interfered with DDE quantification in one sample of greater forkbeard.     

Distribution of HCH and DDT in the coastal marine environment of Mumbai,India

Organochlorine pesticides (OCPs) in sediment, water and biota samples from the coastal marine environment of Mumbai were analysed to elucidate their distribution in various environmental compartments. HCH isomers, dichlorodiphenyltrichloroethane (DDT) and its metabolites were the predominantly identified compounds in all the samples. High ratios of DDT to dichlorodiphenyldichloroethylene (DDE) were found in seawater samples. This indicates the presence of a significant source of DDT in this region. In sediment samples, the gamma-isomer contributed almost 55% to the total HCH, indicating a high affinity of the gamma-isomer towards the sediment. The levels of organochlorines in fish obtained from this region were found to be lower than the levels of organochlorines in fish in temperate regions.     

Use of the p,p'-DDD: p,p'-DDE Concentration Ratio to Trace Contaminant Migration from a Hazardous Waste Site

For approximately 50 years, beginning in the 1920s, hazardous wastes were disposed in an 11-hectare area of the Marine Corps Base (MCB) Quantico, Virginia, USA known as the Old Landfill. Polychlorinated biphenyls (PCBs) and DDT compounds were the primary contaminants of concern. These contaminants migrated into the sediments of a 78-hectare area of the Potomac River, the Quantico Embayment. Fish tissue contamination resulted in the MCB posting signs along the embayment shoreline warning fishermen to avoid consumption. In this paper, we interpret total PCB (t-PCBs) and total DDT (t-DDT, sum of six DDT, DDD, and DDE isomers) data from monitoring studies. We use the ratio of p,p'-DDD to p,p'-DDE concentrations as a tracer to distinguish site-related from regional contamination. The median DDD/DDE ratio in Quantico Embayment sediments (3.5) was significantly higher than the median ratio (0.71) in sediments from nearby Powells Creek, used as a reference area. In general, t-PCBs and t-DDT concentrations were significantly higher in killifish (Fundulus diaphanus) and carp (Cyprinus carpio) from the Quantico Embayment compared with Powells Creek. For both species, Quantico Embayment fish had mean or median DDD/DDE ratios greater than one. Median ratios were significantly higher in Quantico Embayment (4.6) than Powells Creek (0.28) whole body carp. In contrast, t-PCBs and t-DDT in channel catfish (Ictalurus punctatus) fillets were similar in Quantico Embayment and Powells Creek collections, with median ratios of 0.34 and 0.26, respectively. Differences between species may be attributable to movement (carp and killifish being more localized) and feeding patterns (carp ingesting sediment while feeding). We recommend that environmental scientists use this ratio when investigating sites with DDT contamination.     

Levels and distribution of persistent organochlorine pesticide residues in water and sediments of Gomti River (India)—a tributary of the Ganges River

This study reports the concentration levels and distribution pattern of the persistent organochlorine pesticide (OCPs) residues in the water and bed-sediments of the Gomti River collected seasonally over a period of 2 years. The water and bed-sediment samples were collected from eight different sites and analyzed for aldrin, dieldrin, endrin, HCB, HCH isomers, DDT isomers/metabolites, endosulfan isomers (alpha and beta), endosulfan sulfate, heptachlor and its metabolites, alpha-chlordane, gamma-chlordane and methoxychlor. In the river water and sediments SigmaOCPs residues ranged between 2.16 and 567.49 ng l(-1) and 0.92 and 813.59 ng g(-1), respectively. The results, further, suggested that source of DDT contamination is from the aged and weathered agricultural soils with signature of recently used DDT in the river catchments. To assess any adverse effect of OCPs contamination on river's biological component, the threshold effect level (TEL) was used. The results revealed that bed-sediments of the Gomti River are contaminated with lindane, endrin, heptachlor epoxides and DDT, particularly at site-4 and may contribute to sediment toxicity in the freshwater ecosystem of the river.     

Use of preserved museum fish to evaluate historical and current mercury contamination in fish from two rivers in Oklahoma, USA

We examined the effects of a commonly used preservation technique on mercury concentration in fish tissue. After fixing fish muscle tissue in formalin followed by preservation in isopropanol, we found that mercury concentration in fish muscle tissue increased by 18%, reaching an asymptote after 40 days. We used formalin–isopropanol-preserved longear sunfish (Lepomis megalotis) from the Sam Noble Oklahoma Museum of Natural History to examine historical changes and predict current mercury concentrations in fish from two rivers in southeastern Oklahoma. Glover River was free-flowing, while Mountain Fork River was impounded in 1970 and a coldwater trout fishery was established upstream from the collection site in 1989. Mercury concentrations in longear sunfish from Glover River showed no historical changes from 1963 to 2001. Mercury concentrations in longear sunfish from Mountain Fork River showed no change from 1925 to 1993 but declined significantly from 1993 to 2003. We also compared mercury concentrations of the most recently collected longear sunfish in the museum to mercury concentrations of unpreserved fish collected from the rivers in 2006. Concentrations of mercury in museum fish were not significantly different from mercury concentrations in unpreserved fish we collected from the rivers. Our study indicates that preserved museum fish specimens can be used to evaluate historical changes and predict current levels of mercury contamination in fish.     

Use of Central Stonerollers (Cyprinidae: Campostoma anomalum) from Tennessee as a Bioindicator of Metal Contamination

We compared the levels of arsenic, cadmium, chromium, lead, manganese, mercury and selenium in a small species of fish (Central stonerollers, Campostoma anomalum) collected from East Fork Poplar Creek (EFPC) and a reference site in eastern Tennessee. Stonerollers are minnows in the Cyprinidae family that serve as prey for many carnivores in aquatic systems. Fish were collected from East Fork Poplar Creek within the U.S. Department of Energy's Y-12 National Security Complex, part of the Oak Ridge Reservation, and from a reference stretch of the Little River in East Tennessee. Whole fish were homogenized for analysis. Concentrations of all metals (except arsenic) were significantly higher in stonerollers from EFPC compared to the reference site. Mercury levels in minnows from EFPC averaged 0.4 ppm (μg/g), four times higher than the average for fish in the U.S. in general. This was higher than levels in fish from the nearby Clinch River and higher than fillets of white bass (Morone chrysops) from the same creek. Most metal levels were inversely related to size and weight of the stonerollers, perhaps due to growth dilution.     

Freshwater leeches (Hirudinea) as a screening tool for detecting organic contaminants in the environment

In earlier work, we found that leeches from an industrially polluted creek bioaccumulated chlorophenols to much higher concentrations than other resident benthic invertebrates and fish. We suggested that leeches may have significant potential as biomonitors for these and other organic contaminants in the environment. In this study, we compared the bioaccumulation and depuration of 16 organic compounds, including eight chlorophenols (CPs), lindane, DDT and four derivatives, benzothiazole (BT) and 2-(Methylthio)benzothiazole (MMBT) for three species of leeches. Dina dubia had the highest bioaccumulation capacity for most contaminants, but residues persisted longest in Erpobdella punctata. Helobdella stagnalis appeared capable of degrading some compounds. Half lives of CPs, DDT and DDT derivatives were generally longer than one month. In contrast, half lives were only 1 day for lindane, 1–2.5 days for MMBT and 7 days for BT despite very high initial tissue concentrations of the latter two compounds. Bioconcentration factors for contaminants in leeches were higher than those reported for other aquatic organisms. Half lives for lindane, DDT and DDT derivatives were consistent with the literature for other organisms, but half lives for CPs were much longer. The results suggest that leeches would be excellent biomonitors of both continuous and intermittent contamination of a waterway with CPs and DDT, as they retain these compounds for long periods after exposure. Their usefulness as a screening tool for lindane and benzothiazoles would be limited to chronically contaminated environments.     

Total mercury levels in nine species of freshwater fish from two hydroelectric reservoirs and a crater lake in Ghana

Total mercury (Hg) concentrations were determined in the muscle tissue of fish from three reservoirs in Ghana, namely, Lake Bosomtwi, Kpong and Akosombo Hydroelectric Reservoirs. A total of 165 fish samples covering nine species were collected and analysed for total mercury. A mixture of HNO3, H2SO4 and HClO4 were used for complete oxidation of organic tissues. Hg was detected by the Cold Vapour Atomic Absorption Spectrometry technique using an automatic mercury analyzer. Total mercury concentrations in microg g(-1) (wet weight) ranged from below 0.001 to 0.070 for fish from Lake Bosomtwi, 0.010 to 0.275 for fish from Kpong Reservoir and from below 0.001 to 0.042 for fish from Akosombo Reservoir. All the results obtained are below the World Health Organization limit of 0.5 microg g(-1). The low levels of total mercury obtained in this study suggest that the three aquatic environments have not been significantly impacted by mercury contamination.     

Organochlorines and polybrominated diphenyl ethers in four geographically separated populations of Atlantic salmon (Salmo salar)

Atlantic salmon (Salmon salar) populations from four locations, two from isolated Swedish lake systems, one of the Baltic Sea and one of the North Atlantic, were analyzed to determine the concentrations and spatial variations of polybrominated diphenyl ethers (PBDEs) and organochlorines (DDT, PCB and HCH). Levels in both liver and muscle were in the same range as previously reported in Atlantic salmon, except for elevated concentrations found per lipid weight (lw) in the muscle samples of salmon from the North Atlantic ( summation PBDE 263 ng g(-1) lw, summation PCB 3262 ng g(-1) lw, summation DDT 4063 ng g(-1) lw summation HCH 131 ng g(-1)). In general, elevated concentrations in the muscles compared to the liver were observed, especially in lipid depleted migrating salmon, possibly caused by a faster lipid depletion compared with the redistribution of PBDEs, PCBs and DDTs. These findings indicated that the life stage and thereby the lipid dynamics of the fish must be considered prior to comparison based on lipid weight, especially as Atlantic salmon experience large variations in lipid content during periods of migration. The dominating PBDE congener was BDE-47, representing more than 25% in all fish. The PBDE pattern changed between locations, with a significant separation of the fish from the freshwater and marine environment when analyzed using principal component analysis.     

Mercury, cadmium, lead, and selenium in fish from a Norwegian fjord and off the coast, the importance of sampling locality

Hepatic levels of mercury, cadmium, lead, and selenium and levels of mercury and selenium in muscle tissue were analysed in tusk from the Nordfjord in Norway. With the exception of selenium in the muscle tissue, the metal levels were significantly higher in the fjord fish than in fish caught off the coast. No local source is known to explain the difference in levels, and this indicates that the fjord efficiently accumulates atmospheric contaminants. The present results demonstrate the importance of sampling area when determining levels of metals in marine organisms far from point sources. The liver was increasingly used as a storage compartment for mercury and selenium with increasing exposure.     

Temporal trends of contaminants in Arctic char (Salvelinus alpinus) from a small lake, southwest Greenland during a warming climate

Hg and legacy POPs were analysed in muscle tissue of a landlocked Arctic char (Salvelinus alpinus) population from a small lake in southwest Greenland. Hg concentrations were available for six years and OC concentrations for five years during the period 1994 to 2008. For two years, stable isotope values of nitrogen (δ(15)N) were analysed in muscle tissue in order to infer trophic effects. Hg, Σ10-PCB, ΣDDT and trans-nonachlor concentrations (OC on wet weight basis) showed an increase with increasing fish length, which had to be accounted for when assessing temporal trends. δ(15)N values had a narrow range, and there was no indication of increasing δ(15)N values with char length confirming the sampled char did not vary in trophic morphs as often seen in Arctic lakes. Length-adjusted Hg concentrations showed a significantly increasing trend during the period 1994 to 2008, while Σ10-PCB, ΣDDT, ΣHCH and trans-nonachlor showed a significantly decreasing trend when expressed on wet weight, and decreasing but not significantly when expressed on lipid weight. The reason for this was that the lipid content of muscle showed a significantly decreasing trend with time. The sum of mean monthly air temperature during May to August measured at a nearby meteorological station showed an increasing trend during the study period, and changing temperature conditions probably influenced the temporal trend of especially Hg concentrations and the lipid content.     

Status and effect of pesticide residues in soils under different land uses of Andaman Islands, India

Pesticides are shown to have a great effect on soil organisms, but the effect varies with pesticide group and concentration, and is modified by soil organic carbon content and soil texture. In the humid tropical islands of Andaman, India, no systematic study was carried out on pesticide residues in soils of different land uses. The present study used the modified QuEChERS method for multiresidue extraction from soils and detection with a gas chromatograph. DDT and its various metabolites, α-endosulfan, β-endosulfan, endosulfan sulfate, aldrin, and fenvalerate, were detected from the study area. Among the different pesticide groups detected, endosulfan and DDT accounted for 41.7 % each followed by aldrin (16.7 %) and synthetic pyrethroid (8.3 %). A significantly higher concentration of pesticide residues was detected in rice–vegetable grown in the valley followed by rice–fallow and vegetable–fallow in the coastal plains. Soil microbial biomass carbon is negatively correlated with the total pesticide residues in soils, and it varied from 181.2 to 350.6 mg?kg^?1. Pesticide residues have adversely affected the soil microbial populations, more significantly the bacterial population. The Azotobacter population has decreased to the extent of 51.8 % while actinomycetes were the least affected though accounted for 32 % when compared to the soils with no residue.     

Changing patterns of organochlorine pesticide residues in raw bovine milk from Haryana, India

Bovine milk samples were collected and analyzed during 1992 and 1998 from rural areas of 14 different districts of Haryana state for the presence of HCH and DDT residues. The study revealed that the mean residues of ΣHCH in raw bovine milk have declined by 67.5% while mean levels of ΣDDT have decreased by 92.8% during six years gap. The obtained results reveal that during 1992 p,p'-DDT was the main component followed by p,p'-DDD, α-HCH and β-HCH while in 1998, p,p'-DDE and β-HCH followed by p,p'-DDT were relatively more as compared to other isomers and metabolites of these pesticides.     

Determination and Assessment of HCHs and DDTs Residues in Sediments from Lake Dongting, China

The contamination of organochlorine pesticides hexachlorocyclohexane (HCH) and Dichlorodiphenyltrichloroethane (DDT) and their eco-environmental assessment in surface sediments from Lake Dongting, the second-largest freshwater lake in China, were studied. Concentrations of ∑HCH (=α-HCH + β-HCH + γ-HCH +δ-HCH) were 0.21--9.59 ng/g dry weight and those of ∑ DDT = p,p'-DDD+p,p'-DDE+o,p'-DDT+p,p'-DDT) ranged from under detectable limit to 10.15 ng/g dry weight. The ratios of α-HCH to γ-HCH were above 7 at most sampling sites while no or a small amount of β-HCH were found at all sites, suggesting the degradation of HCH used in the history and possibly current use of HCH in the region. The low ratios (below 2.0 in most cases) of (p,p'-DDE+p,p'-DDD) to p,p'-DDT and high levels of individual isomers of DDT at some sites also suggested that there have still been fresh inputs of DDT into Lake Dongting. Through the comparison between concentrations of HCH and DDT residues in sediments of Lake Dongting and those from other places in China and also from the results of our eco-environmental assessment, it can be concluded that Lake Dongting is the water body with high contamination of both HCH and DDT in its sediments in comparison with other water bodies in China.     

Residues of organochlorine pesticides in water and suspended particulate matter from the Yangtze River catchment of Wuhan, China

The residues of 13 organochlorine pesticides (OCPs) in surface water and HCHs and DDTs in suspended particulate matter (SPM) from rivers and lakes in Yangtze River catchment of Wuhan, China, were investigated. The concentration of total OCPs in surface water varied from 1.01 to 46.49 ng l⁻¹ (mean 10.55 ng l⁻¹). The levels of total HCHs (ΣHCH) and total DDTs (ΣDDT) in surface water were in the range of 0.55–28.07 ng l⁻¹ and lower than detection limit to 16.71 ng l⁻¹, respectively, which was lower than Chinese standards on the whole. For OCPs residues in SPM, the mean levels varying from 0.20 to 34.72 ng l⁻¹ and 0.46 to 2.72 ng l⁻¹ for ΣHCH and ΣDDT, respectively, which ranked the relatively higher levels among Chinese studied rivers. Results from this investigation showed that previous excessive usage of technical OCPs was the main reason for the residues of HCHs and DDTs both in surface water and SPM, although some new sources were likely to occurred in the region. Apart from the OCPs in SPM originated from upstream in flood season, one of the important sources of OCP residues both in water and SPM in Yangtze River was supposed to be the inputs of its tributaries. Additionally, in situ water-SPM phase distributions of OCPs indicated that HCHs tended totransport with water as well as DDTs was prone to combine with SPM in Yangtze River catchment of Wuhan.     

Development of a new method for the determination of residues of the neonicotinoid insecticide imidacloprid in juvenile chinook (Oncorhynchus tshawytscha) using ELISA detection

The neonicotinoid insecticide imidacloprid (IMI) has been proposed as an alternative to carbaryl for controlling indigenous burrowing shrimp on commercial oyster beds in Willapa Bay and Grays Harbor, Washington. A focus of concern over the use of this insecticide in an aquatic environment is the potential for adverse effects from exposure to non-target species residing in the Bay, such as juvenile Chinook (Oncorhynchus tshawytscha) and cutthroat trout (O. clarki). Federal registration and State permiting approval for the use of IMI will require confirmation that the compound does not adversely impact these salmonids following field applications. This will necessitate an environmental monitoring program for evaluating exposure in salmonids following the treatment of beds. Quantification of IMI residues in tissue can be used for determining salmonid exposure to the insecticide. Refinement of an existing protocol using liquid-chromatography mass spectrometry (LC-MS) detection would provide the low limits of quantification, given the relatively small tissue sample sizes, necessary for determining exposure in individual fish. Such an approach would not be viable for the environmental monitoring effort in Willapa Bay and Grays Harbor due to the high costs associated with running multiple analyses, however. A new sample preparation protocol was developed for use with a commercially available enzyme-linked immunosorbent assay (ELISA) for the quantification of IMI, thereby providing a low-cost alternative to LC-MS for environmental monitoring in Willapa Bay and Grays Harbor. Extraction of the analyte from the salmonid brain tissue was achieved by Dounce homogenization in 4.0 mL of 20.0 mM Triton X-100, followed by a 6 h incubation at 50-55 °C. Centrifugal ultrafiltration and reversed phase solid phase extraction were used for sample cleanup. The limit of quantification for an average 77.0 mg whole brain sample was calculated at 18.2 μg kg(-1) (ppb) with an average recovery of 79%. This relatively low limit of quantification allows for the analysis of individual fish. Using controlled laboratory studies, a curvelinear relationship was found between the measured IMI residue concentrations in brain tissue and exposure concentrations in seawater. Additonally, a range of IMI brain residue concentrations was associated with an overt effect; illustrating the utility of the IMI tissue residue quantification approach for linking exposure with defined effects.     

Ground water contamination by organochlorine insecticide residues in a rural area in the indo-gangetic plain

Residues of several organochlorine insecticides were monitored in the ground water from a rural area near Farrukhabad in the vicinity of the Ganga River in northern India for one year (1991–1992). Almost all the samples were found to be contaminated with residues of Hexachlorocyclohexane (HCH) and Dichloro-diphenyl-trichloroethane (DDT). Residues of Aldrin, endosulfan and heptachlor were also detected in a large number of samples. The concentrations of aldrin residues greatly exceeded the WHO guideline value for drinking water, concentrations of heptachlor and DDT residues also occasionally exceeded the specified limits. Migration of pollutants through ground water recharge with polluted Ganga River water and monsoon rains carrying undergraded residues downwards from the soil surface are throught to be important sources of insecticide contamination of ground water in the region.     

Organochlorine Pesticides and PCBs in Wild Boars from Calabria (Italy)

At present, there are no specific studies on the evaluation of environmental toxicological risks in Calabria (south of Italy) and on the presence of contaminants in the fauna of this region. The aim of the present research was to investigate the levels of contamination by OC pesticides and PCBs in some organs and tissues of wild boars (utilized as 'biological indicator') from various areas of Calabria. Quantitative determinations of organochlorines were carried out using GC-ECD and confirmed with GC-MS in 154 samples from wild boars (heart, liver, lung, kidney, muscle tissue and spleen) during the hunting season from 2000 to 2002. The results indicate the low residual levels of DDE in 8 samples and DDT in 4 samples and PCBs residues (Aroclor 1232) below the detection limits were found. Therefore, these results show that the Calabria region is not at contamination risk from organochlorines and moreover is free from health problems for the consumer of boar meat.     

气相色谱法测定赤水河中段水体中14种有机氯农药的残留

建立了用正己烷萃取,气相色谱—电子捕获（GC—ECD）测定水体中有机氯农药痕量残留的方法。结果表明：六氯苯、α-HCH、β-HCH、γ-HCH、δ-HCH、p,p′-DDD、p,p′-DDE、p,p′-DDT、艾氏剂、狄氏剂、异狄氏剂、七氯、环氧七氯、o,p′-DDT 14种农药在14 min内有较好的分离;2个不同浓...