Organochlorine residues in finfish from Maryland waters 1976–1980

Abstract

Organochlorine pesticide and herbicide levels were monitored in samples of a variety of edible finfish harvested from the Maryland section of the Chesapeake Bay and its tributaries over a five‐year period (1976–80). Qualitative and quantitative information was obtained for the various polychlorinated biphenyls (PCB's), heptachlor, α‐BHC, chlordane, DDD, DDE, DDT, dieldrin, endrin, heptachlor‐epoxide, lindane, mirex, methoxychlor, aldrin, toxaphene, hexachlorobenzene, kepone and dacthal.

In addition to analyses of the flesh of the animals, organochlorine residue levels were determined in roe or gonad tissue of several samples. Striped bass, white perch and yellow perch samples showed significantly higher concentrations of certain of these substances in roe or gonad tissue, especially PCB's, chlordane, DDD and dieldrin. Significantly higher levels of six organochlorine residues were found in the gonad tissue of striped bass; however, similar studies on gonad tissue of American Shad, harvested from the same region, show no such enhancement. Rather, the reverse is true; levels of certain organochlorine residues are higher in flesh tissue.

All mean values, and virtually all individual values of organochlorine concentrations in the edible portion of the fish were within the U.S. Food and Drug Administration guideline, where such guidelines have been established.     

Physico-chemical interactions and bioconcentration of zinc and lead in the industrially polluted Husainsagar Lake, Hyderabad, India

This paper deals with the interactions of different physico-chemical parameters in the water profile, and the bioconcentration of zinc and lead in Husainsagar Lake, India. The concentrations of both the metals are within the permissible limits (Indian Council of Medical Research, New Delhi, India (1975). Manual of Standards of Quality for Drinking Water Supplies. ICMR Special Report, p. 44). The concentration of Zn and Pb in the vertical profile were highest in the bottom stratum of the lake and least in the surface stratum. Their concentrations were two to three thousand-fold more in surficial sediments than in the overlying water column. The concentration of Zn increased with increasing trophic level from nanoplankton to zooplankton, but not to fish, and the concentration of Pb decreased with increasing trophic level: nanoplankton --> phytoplankton --> zooplankton --> fish, illustrating no bioconcentration of metals in the classic sense of the term as has been noted for mercury and chlorinated hydrocarbons (DDT).     

Comparison of arsenate and cadmium toxicity in a freshwater amphipod (Gammarus pulex)

Cadmium is largely documented on freshwater organisms while arsenic, especially arsenate, is rarely studied. The kinetic of the LC50s values for both metals was realized on Gammarus pulex. Physiological [i.e. metal concentration in body tissues, bioconcentration factor (BCF)] effects and behavioural responses (via pleopods beats) were investigated after 240-h exposure. Arsenate LC50 value was 100 fold higher than Cd-LC50 value after 240-h exposure, while concentrations in gammarids were similar for both metals at their respective LC50s. BCF decreased with increasing cadmium concentration while BCF remained stable with increasing arsenate concentration. Moreover, BCF was between 148 and 344 times lower for arsenate than cadmium. A significant hypoventilation was observed for cadmium concentrations exceeding or close to the 240h-LC50(Cd), while gammarids hyperventilated for the lowest arsenate concentrations and hypoventilated for the highest arsenate concentrations. We discussed the relationships between potential action mechanisms of these two metals and observed results.     

Butyltin compounds in sediment and molluscs from the shipping strait between Denmark and Sweden

The distribution of tributyltin (TBT) contamination in the subtidal zone of the waters between Denmark and Sweden was investigated in relation to major international shipping lanes. Sediment and different benthic molluscs were sampled in transects along and perpendicularly to the shipping lanes in the Sound (?resund) and the Kattegat/Skagerrak region. The samples were analysed for TBT and its degradation products, dibutyltin (DBT) and monobutyltin (MBT), using GC-PFPD. In sediments, the TBT concentration ranged from <1 to 19 ng g(-1) dry weight (dw) with a strong correlation between the TBT concentration and the organic fraction in sediment (r(2)=0.90) in the samples collected in the Sound, where the highest concentrations were found. This relationship was not observed in the samples from the Kattegat because the TBT concentration in most sediment samples was below the limit of detection. In the molluscs, TBT and its degradation products were detected in all samples from the entire area with concentrations ranging from 8.1 ng g(-1) dw in Buccinum undatum to 1316 ng g(-1) dw in Nuculana pernula. The deposit-feeding bivalve N. pernula was found to have a particularly high accumulation potential for TBT. In addition, a strong correlation between TBT concentrations in sediment and N. pernula was found. Therefore this species seems to be an ideal organism for monitoring sediment contamination. The TBT concentration in N. pernula was found to decrease gradually along the shipping lanes from the Sound, through the Kattegat and into the Skagerrak.     

Aquatic fate assessment of the polycyclic musk fragrance HHCB. Scenario and variability analysis in accordance with the EU risk assessment guidelines

By means of the environmental fate and distribution models laid down in the Technical Guidance Documents (TGD) and implemented in the European Union System for the Evaluation of Substances (EUSES) environmental concentrations of the polycyclic musk fragrance HHCB (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-[g]-2- benzopyrane; trade name: e.g. Galaxolide) were calculated for the aquatic environment under consideration of various scenarios. The results were then compared to monitoring data from the region of North Rhine-Westphalia (River Ruhr). An uncertainty analysis was carried out to determine sensitive parameters, to integrate environmental variability and to confirm the model's calculations. The standard scenario of EUSES overestimates the measured concentrations, which confirms the conservative nature of the calculations. The regional-specific scenarios lead to lower deviations from the measured values than the standard scenario. Deviations range from one to two orders of magnitude in the effluent of sewage treatment plants; they amount to one order of magnitude for surface water concentrations on a local scale and conform to monitoring data on a regional scale. The use of measured bioconcentration factors for fish instead of estimated ones reduces deviations remarkably. The investigation reveals that unrealistic worst-case calculations of HHCB can at best be ameliorated by the application of more realistic emission rates and measured bioconcentration factors. The use of regional-specific parameters also diminishes the deviations of the calculations from the measured concentrations.     

Organochlorine pesticides and polychlorinated biphenyls in human milk during lactation

Organochlorine residue levels were determined in human milk samples of 5 women. The contaminants analyzed were: α-, β-, and δ-hexachlorocyclohexane (HCH), hexachlorobenzene (HCB), p,p′-DDT, p,p′-DDE, and polychlorinated biphenyls (PCB's). The variation of residue levels in human milk during lactation was investigated for each woman individually. Month-mix samples composed of weekly collected breast milk samples were analyzed over a lactation period between 5 and 9 months. No essential changes in organochlorine residue levels in human milk occurred over the lactation periods investigated; the concentration remained either relatively constant or showed fluctuations with no observable trend.     

Copper regulation and homeostasis of Daphnia magna and Pseudokirchneriella subcapitata: influence of acclimation

This study aimed to evaluate (1) the capacity of the green alga Pseudokirchneriella subcapitata and the waterflea Daphnia magna to regulate copper when exposed to environmentally realistic copper concentrations and (2) the influence of multi-generation acclimation to these copper concentrations on copper bioaccumulation and homeostasis. Based on bioconcentration factors, active copper regulation was observed in algae up to 5 microg Cu L(-1) and in daphnids up to 35 mug Cu L(-1). Constant body copper concentrations (13+/-4 microg Cu g DW(-1)) were observed in algae exposed to 1 through 5 microg Cu L(-1) and in daphnids exposed to 1 through 12 microg Cu L(-1). At higher exposure concentrations, there was an increase in internal body copper concentration, while no increase was observed in bioconcentration factors, suggesting the presence of a storage mechanism. At copper concentrations of 100 microg Cu L(-1) (P. subcapitata) and 150 microg Cu L(-1) (D. magna), the significant increases observed in body copper concentrations and in bioconcentration factors may be related to a failure of this regulation mechanism. For both organisms, internal body copper concentrations lower than 13 microg Cu g DW(-1) may result in copper deficiency. For P. subcapitata acclimated to 0.5 and 100 microg Cu L(-1), body copper concentrations ranged (mean+/-standard deviation) between 5+/-2 microg Cu g DW(-1) and 1300+/-197 microg Cu g DW(-1), respectively. For D. magna, this value ranged between 9+/-2 microg Cu g DW(-1) and 175+/-17 microg Cu g DW(-1) for daphnids acclimated to 0.5 and 150 microg Cu L(-1). Multi-generation acclimation to copper concentrations >or =12 microg Cu L(-1) resulted in a decrease (up to 40%) in body copper concentrations for both organisms compared to the body copper concentration of the first generation. It can be concluded that there is an indication that P. subcapitata and D. magna can regulate their whole body copper concentration to maintain copper homeostasis within their optimal copper range and acclimation enhances these mechanisms.     

Bioconcentration and depuration of endosulfan sulfate in mosquito fish (Gambusia affinis)

Endosulfan is an insecticide which has been widely used in agriculture. The technical grade material consists of two isomers (alpha and beta). Under natural environmental conditions, endosulfan is metabolized through oxidation and the main metabolite in the environment is endosulfan sulfate. Most ecotoxicology research has been conducted with technical grade endosulfan to determine effects on non-target aquatic organisms. Little data on the effects of endosulfan sulfate on aquatic organisms are available in the literature. This study characterizes endosulfan sulfate bioconcentration and depuration in mosquito fish (Gambusia affinis). During the study, G. affinis was exposed to an environmentally relevant endosulfan sulfate concentration of 0.25 μg L⁻¹ for 5 weeks (uptake phase) followed by a 3-week period (depuration phase) in clean water. This study found that G. affinis bioconcentrated endosulfan sulfate. During the exposure phase, fish tissue concentrations of endosulfan sulfate increased with time up to 730 μg kg⁻¹ dw or 215 μg kg⁻¹ ww. The bioconcentration data followed Michaelis-Menten kinetics better than the one-compartment first order kinetics (1-CFOK). Using these models, the bioconcentration factors for endosulfan sulfate-exposed G. affinis were from 687 to 888  L kg⁻¹ in wet weight or 2263 to 2936 L kg⁻¹ in dry weight. During the depuration phase, endosulfan sulfate concentrations in tissue significantly decreased and the data followed first order kinetics. The half-life of endosulfan sulfate in G. affinis was about 9 d. There was no significant difference in standard length or weight between control and exposed fish. The growth data followed the von Bertalanffy growth model. However, the condition factor of exposed fish increased with time during the exposure phase.     

Influence of dispersants on bioconcentration factors of seven organic compounds with different lipophilicities and structures

Seven compounds with different lipophilicities and structures—1,3,5-trichlorobenzene, pentachlorobenzene, acenaphthylene, 1,4-dimethyl-2-(1-methylphenyl)benzene, 4-ethylbiphenyl, 4,4′-dibromobiphenyl, and 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane—were subjected to bioconcentration tests in carp at concentrations below the water solubilities of the compounds in the presence or absence of a dispersant (either an organic solvent or a surfactant). The bioconcentration factors (BCFs) of the compounds were on the order of 10²–10⁴. The BCF values remained in the range of 15–49% for all the compounds, whether or not a dispersant was present, i.e., the BCF values in the presence of an organic solvent or a surfactant at a concentration below the critical micelle concentration were not significantly smaller than the BCF values in the absence of the solvent or surfactant. This result indicates that the dispersants had no influence on the evaluation of the bioconcentration potential of these test substances.     

Comparisons of PCBs dechlorination occurrences in various contaminated sediments

A comparison was made of reductive dechlorination occurrences of polychlorinated biphenyls (PCBs) by microorganisms collected from contaminated sediments including Er-Jen River (Tainan, Taiwan), Hudson River (Ft. Edward, NY), Silver Lake (Pittsfield, MA) and Puget Sound (Washington State). Comparisons was made in terms of chromatographic data (referring to the biological activity, including microbial availability) and thermodynamic data (demonstrating the selectivity of anaerobic microorganisms in the dechlorination of chlorinated compounds). Chromatographic data was established in terms of difference in relative retention time (delta ln RRT) and thermodynamic data was estimated as heat of reaction (delta H(r)0). Both were calculated and correlated to occurrences of dechlorination reactions. Observed dechlorination reactions for individually introducing PCB congener had delta ln RRT levels measured as >0.47 (Er-Jen River), >0.29 (Hudson River), >0.36 (Silver Lake) and >0.45 (Puget Sound, for Aroclor 1254 dechlorination). Critical of delta H(r)0 and delta ln RRT values showed that Hudson River and Silver Lake microorganisms were capable of dechlorinating PCBs through reactions with larger H(r)0 value (lower levels of released energy) and smaller delta ln RRT value compared with those found in Er-Jen River and Puget Sound sediments. Differences in the critical delta ln RRT values of these sediments may be due to differences in their levels of PCB contamination.     

Determination of bioconcentration potential of tetrachloroethylene in marine algae by 13C

The use of stable isotope of organic-carbon, organic-¹³C, as a tracer for the determination of the concentration of tetrachloroethylene (PCE), C_A, in Heterosigma akashiwo and Skeletonema costatum was examined. C_A determined by the ¹³C and GC methods showed good agreement with each other. This suggests that it is reasonable and reliable to determine the bioconcentration potentail of PCE in marine algae. Fitting values of bioconcentration potentail parameters, including uptake rate constant k₁, elimination rate constant k₂ and bioconcentration factor on the basis of dry weight BCF_D, were done not only to the time course for PCE uptake by the algae with the bioconcentration model, but also to experimental data for “percent inhibition(%)∼exposure concentration of PCE∼time” with the combined bioconcentration and probability model. The values obtained from the bioconcentration model were consistent with those from the combined bioconcentration and probability model. With the parameters (such as k₁, k₂, growth rate constant k_G, critical concentration of HOCs in the organism resulting in growth inhibition C_A¹ and spread factor S) the variability in toxicity (such as EC₁₀, EC₅₀, EC₇₀) can be estimated from the combined bioconcentration and probability model, which fits well with the experimental observations.     

Measuring bioconcentration factors and rate constants of chemicals in aquatic organisms under conditions of variable water concentrations and short exposure time

A novel method, based on iterative numerical integration, is presented for deriving bioconcentration factors and rate constants of chemicals in aquatic organisms from experimental data of bioconcentration tests in which the chemical concentration in the water is variable over time and the test duration is too short to reach steady-state. The method is applied to reported data from fish and plant bioconcentration tests. The results demonstrate that this method can derive bioconcentration factors and rate constants with considerably less experimental error than other methods currently used, thus reducing uncertainty and variability in bioconcentration measurements.     

Distribution and fractionation of heavy metals in the Tisa (Tisza) River sediments

Introduction In this work, sediments of the River Tisa (Tisza) are studied to assess their environmental pollution levels for some major heavy metals, as well as to predict the investigated elements’ mobility on the basis of their association type with the substrate. The Tisa River catchments area is a subbasin of the River Danube. Part of this river, 166 km long, belongs to the Serbian province of Vojvodina, before it flows into the Danube. It has been chosen for our investigation, because it has been exposed to intense pollution in the last decades. Materials and Methods The river sediment samples were collected at 32 locations. The proportions of sand, silt and clay fractions were determined. The sequential extraction procedure following a modified Tessier method was applied for speciation of the metal forms in the collected samples. The metal concentrations of Zn, Cd, Pb, Ni, Cu, Cr, Fe and Mn in extracts were determined by atomic absorption spectroscopy. Results and Discussion Granulometric analysis showed that some 50% of the Tisa River sediments were silt and clay, while the rest was sand with quartz, as the main constituent. The average metal content of the surface river sediment samples for every fraction of sequential extraction was presented and discussed in relation to pH, Eh and metal fractionation. The average metal content from the Tisa River sediments, obtained as an average of the metal’s concentration released in all five sequential extraction fractions was compared with: average metal contents of the Tisa River sediments in Hungary, metal content in soils formed on the Tisa River alluvium of Vojvodina, average metal content in soils of Vojvodina, and average metal content in soils of Hungary. An assessment of metal pollution levels in Tisa River sediments was made by comparing mean values for obtained results for the Tisa River sediments with the freshwater sediment’s Quality Guidelines as published by US EPA, Environment Canada and soil standards for Serbia. Conclusion According to US EPA and Canadian Quality Guidelines for freshwater sediments, the concentration of heavy metals in Tisa sediments were: (a) much higher than defined concentrations below which harmful effects on river biota are unlikely to be observed, (b) below defined concentrations above which harmful effects on river biota are likely to be observed. The concentration levels of Pb, Ni, Cu and Cr in Tisa River sediments are safe when compared with Serbian MAQ (Maximum Allowed Quantity) standards for soils, but they are unsafe in the case of Zn and Cd. Recommendations and Outlook The quality of sediments in the Tisa River was on the border line between potentially polluted and polluted. This line could very easily be exceeded since the quality of sediments in the Tisa River in Hungary was already worse than in Serbia. These results indicated the need for further monitoring of heavy metals in that locality.     

Bioconcentration and biokinetics of heavy metals in the earthworm

This study examines the steady state and non-steady state kinetics of five metals, cadmium, copper, lead, nickel, and zinc in earthworms. The steady state kinetics are based on field studies in which worms from contaminated and uncontaminated sites were collected and measurements were made of concentrations in the earthworms and soils. For each of the metals, evidence suggests that bioconcentration depends on the metal concentrations in the soil; bioconcentration is greater at lower soil concentrations. The studies of non-steady state kinetics involve uptake and elimination experiments in which worms are transferred from an uncontaminated soil to a contaminated soil (uptake studies) or from a contaminated soil to an uncontaminated soil (elimination studies). The voiding time is shown to be an important experimental variable in determining the measured levels of metal in earthworms because experimental measurements are usually made on a worm-soil complex (i.e. the soft tissue of the worm and the soil in the gut of the worm). Thus, for metals that are bioconcentrated in worm tissue, increasing the voiding period increases the concentration of the metal in the worm-soil complex. Conversely, for metals that are not bioconcentrated, increasing the voiding time leads to a decrease in concentrations in the worm-soil complex.     

Sub-chronic exposure to fluoxetine in juvenile oysters (<Emphasis Type="Italic">Crassostrea gigas</Emphasis>): uptake and biological effects

The bioconcentration potential of fluoxetine (FLX) and its biological effects were investigated in juvenile Pacific oyster exposed for 28 days to environmentally relevant concentrations of FLX (1 ng L^?1, 100 ng L^?1 and up to 10 μg L^?1). FLX bioaccumulated in oyster flesh resulting in 28-day bioconcentration factors greater than 2,000 and 10,000 by referring to wet and dry weights, respectively. Nevertheless, FLX did not induce oyster mortality, delayed gametogenesis, or lead to adverse histopathological alterations. At the two highest concentrations, despite non-optimal trophic conditions, FLX stimulated shell growth but only in a transient manner, suggesting a role of serotonin in the regulation of feeding and metabolism in bivalves. Those high concentrations seemed to drive bell-shaped responses of catalase and glutathione S-transferase activities throughout the exposure period, which may indicate the activation of antioxidant enzyme synthesis and then an enhanced catabolic rate or direct inhibition of those enzymes. However, no clear oxidative stress was detected because no strong differences in thiobarbituric acid-reactive substance (TBARS) content (i.e. lipid peroxidation) were observed between oyster groups, suggesting that cellular defence mechanisms were effective. These results demonstrate the importance of considering additional biomarkers of oxidative stress to obtain a comprehensive overview of the FLX-induced changes in marine bivalves exposed under realistic conditions. Considering the battery of biomarkers used, FLX appears to induce little or no effects on oyster physiology even at a concentration of 10 μg L^?1. These results do not confirm the lowest observed effect concentration (LOEC) values reported by some authors in other mollusc species.     

POP bioaccumulation in macroinvertebrates of alpine freshwater systems

This study serves to investigate the uptake of POPs in the different trophic levels (scrapers, collectors, predators, shredders) of macroinvertebrate communities sampled from a glacial and a non-glacial stream in the Italian Alps. The presented results show that the contaminant concentrations in glacial communities are generally higher compared to those from non-glacial catchments, highlighting the importance of glaciers as temporary sinks of atmospherically transported pollutants. Moreover, the data also suggests that in mountain systems snow plays an important role in influencing macroinvertebrate contamination. The main chemical uptake process to the macroinvertebrates is considered to be bioconcentration from water, as similar contaminant profiles were observed between the different trophic levels. The role of biomagnification/bioaccumulation is thought to be absent or negligible. The enrichment of chemicals observed in the predators is likely to be related to their greater lipid content compared to that of other feeding groups.     

Bioconcentration of n-dodecane and its highly branched isomer 2,2,4,6,6-pentamethylheptane in fathead minnows

Petroleum products are complex mixtures of hydrocarbons. They are important as constituents of fuels and lubricants, and as key raw materials for the chemicals industry. Since there is a potential for accidental releases to the aquatic environment, bioaccumulation of higher hydrocarbons is of concern. Here, the bioconcentration behaviour of two representative hydrocarbons, the dodecane isomers n-dodecane and 2,2,4,6,6-pentamethylheptane (PMH), was investigated in fathead minnows at concentrations in water below their maximum aqueous solubility. The concentration of n-dodecane in fish did not exceed our method limit of detection of 60 μg/kg. In contrast, PMH could be quantified in fish. No significant increase in the ratio of PMH concentrations in fish to water could be detected indicating that an exposure time of 4–10 days is sufficient to approach steady-state. For n-dodecane the upper limit of the bioconcentration factor (BCF) is estimated by dividing the method limit of detection by the exposure concentration and a value of 240 l/kg is derived. For PMH the bioconcentration factor, estimated as the average fish/water concentration ratio during the steady-state part of the experiment, ranges between 880 and 3500 l/kg. The BCFs of both compounds are small compared to their hydrophobicity. Given that both linear and branched hydrocarbons are known to be biotransformed by fish, it appears that efficient metabolism of the test compounds in fathead minnows prevents bioaccumulation.     

Fate and effects of anthropogenic chemicals in mangrove ecosystems: a review

The scientific literature for fate and effects of non-nutrient contaminant concentrations is skewed for reports describing sediment contamination and bioaccumulation for trace metals. Concentrations for at least 22 trace metals have been reported in mangrove sediments. Some concentrations exceed sediment quality guidelines suggesting adverse effects. Bioaccumulation results are available for at least 11 trace metals, 12 mangrove tissues, 33 mangrove species and 53 species of mangrove-habitat biota. Results are specific to species, tissues, life stage, and season and accumulated concentrations and bioconcentration factors are usually low. Toxicity tests have been conducted with 12 mangrove species and 8 species of mangrove-related fauna. As many as 39 effect parameters, most sublethal, have been monitored during the usual 3 to 6 month test durations. Generalizations and extrapolations for toxicity between species and chemicals are restricted by data scarcity and lack of experimental consistency. This hinders chemical risk assessments and validation of effects-based criteria.     

Challenges in understanding the sources of bioaccumulated metals in biota inhabiting turbid river systems

Bioaccumulation of As, Cd, Cu, Pb and Zn by Macrobrachium prawns was observed to occur in the Strickland River downstream of a gold mine at Porgera, Papua New Guinea. This was despite the total metal concentrations of waters and sediments indicating no difference from reference sites within tributaries. To provide information on potential sources and bioavailability of metals to prawns, an extensive range of analyses were made on waters, suspended solids, deposited sediments and plant materials within the river system. Dissolved metal concentrations were mostly sub-micrograms per liter and no major differences existed in concentrations or speciation between sites within the Strickland River or its tributaries. Similarly, no differences were detected between sites for total or dilute acid-extractable metal concentrations in bed sediments and plant materials, which may be ingested by the prawns. However, the rivers in this region are highly turbid and the dilute acid-extractable cadmium and zinc concentrations in suspended solids were greater at sites in the Strickland River than at sites in tributaries. The results indicated that mine-derived inputs increased the proportion of these forms of metals or metalloids in the Strickland River. These less strongly bound metals and metalloids would be more bioavailable to the prawns via the dietary pathway. The results highlighted many of the difficulties in using routine monitoring data without information on metal speciation to describe metal uptake and predict potential effects when concentrations are low and similar to background. The study indicated that the monitoring of contaminant concentrations in organisms that integrate the exposure from multiple exposure routes and durations may often be more effective for detecting impacts than intermittent monitoring of contaminants in waters and sediments.