Fish bioaccumulation and biomarkers in environmental risk assessment: a review

Commercial polychlorinated biphenyls (PCBs) and environmental extracts contain complex mixtures of congeners that can be unequivocally identified and quantitated. Some PCB mixtures elicit a spectrum of biochemical and toxic responses in humans and laboratory animals and many of these effects resemble those caused by 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) and related halogenated aromatic hydrocarbons, which act through the aryl hydrocarbon (Ah)-receptor signal transduction pathway. Structure-activity relationships developed for PCB congeners and metabolites have demonstrated that several structural classes of compounds exhibit diverse biochemical and toxic responses. Structure-toxicity studies suggest that the coplanar PCBs, namely, 3,3',4,4'-tetrachlorobiphenyl (tetraCB), 3,3',4,4',5-pentaCB, 3,3',4,4',5,5'-hexaCB, and their monoortho analogs are Ah-receptor agonists and contribute significantly to the toxicity of the PCB mixtures. Previous studies with TCDD and structurally related compounds ...

Polychlorinated Biphenyls (PCBs): Environmental Impact, Biochemical and Toxic Responses, and Implications for Risk Assessment

Twenty healthy adult humans had serum samples drawn on four occasions within a 24-hr period: after a 12 hr overnight fast, 4-5 hr after a high fat breakfast, at midafternoon, and the next morning after another 12 hr fast. Nonfasting samples had 22% to 29% higher mean concentrations (p less than 0.05) than did fasting samples for polychlorinated biphenyls (PCBs, 4.81 vs 3.74 ng/g serum wt), hexachlorobenzene (HCB, 0.163 vs 0.134 ng/g serum wt), and p,p'-dichlorodiphenyl-dichloroethylene (p,p'-DDE, 6.74 vs 5.37 ng/g serum wt) measured by electron capture gas liquid chromatography. Total serum lipids were estimated from measurements of total cholesterol, free cholesterol, triglycerides, and phospholipids and were 20% higher in nonfasting samples than in fasting samples (7.05 g/L vs 5.86 g/L). When PCBs, HCB, and p,p'-DDE concentrations were corrected by total serum lipids, results from fasting and non-fasting samples were not statistically different. Because of the differences in these chlorinated hydrocarbon concentrations observed with different sample collection regimens, meaningful comparison of analytical results requires standardizing collection procedures or correcting by total serum lipid levels.

Chlorinated hydrocarbon levels in human serum: effects of fasting and feeding.

Polychlorinated biphenyls (PCBs) as environmental contaminants often cannot be adequately described by reference to Aroclors or to total PCBs. Although there are 209 possible PCB configurations (congeners), perhaps half that number account for nearly all of the environmental contamination attributable to PCBs. Still fewer congeners are both prevalent and either demonstrably or potentially toxic. If potential toxicity, environmental prevalence, and relative abundance in animal tissues are used as criteria, the number of environmentally threatening PCB congeners reduces to about thirty-six. Twenty-five of these account for 50 to 75% of total PCBs in tissue samples of fish, invertebrates, birds, and mammals. A few PCB congeners that are sterically similar to 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) are directly toxic. Other PCB congeners, as well as those that are directly toxic, may also be involved in toxicity indirectly by stimulating the production of (inducing) bioactivating enzyme systems. The most consequential of these have the ability to induce aryl hydrocarbon metabolizing mixed-function oxidases (MFOs). A result can be an increased capacity for bioactivation of otherwise nontoxic foreign compounds such as certain polynuclear aromatic hydrocarbons (PAH) to cytotoxic or genotoxic metabolites. The effectiveness of specific PCB congeners as inducers of different types of cytochrome P-450-dependent MFO systems is determined by their stereochemistry. Although MFO induction is not a proximate cause, it is a strong correlate of certain kinds of toxicities. Structural patterns can thus be used to discriminate among PCB congeners on the basis of toxic potential, if not entirely on toxicity per se. Congeners that demonstrate 3-methylcholanthrene-type (3-MC-type) and mixed-type MFO induction have the greatest toxic potential. These congeners most closely resemble 2,3,7,8-TCDD in their structures and in their toxic effects. The larger group of phenobarbital-type (PB-type) inducers have considerably less potential for contributing to toxic effects. Weak inducers and noninducing congeners have the least potential for toxicity. Using the rationale described in this paper, we assigned the most evironmentally threatening PCB congeners to four groups. Congeners assigned to Group 1 are considered most likely to contribute to adverse biological effects attributable to PCBs in an environmental sample. Group 1A contains the three most potent (pure 3-MC-type inducer) congeners, IUPAC numbers 77, 126, and 169. Six congeners, numbers 105, 118, 128, 138, 156, and 170, are assigned to Group 1B. These congeners are mixed-type inducers that have been reported frequently in environmental samples.(ABSTRACT TRUNCATED AT 400 WORDS)

Environmental occurrence, abundance, and potential toxicity of polychlorinated biphenyl congeners: considerations for a congener-specific analysis.

Statistical Models in Engineering

The polychlorinated biphenyl (PCB) residues in the aquatic sediments from six PCB spill sites showed changes in PCB isomer and homolog (congener) distribution that indicated the occurrence of reductive dechlorination. The PCB dechlorinations exhibited several distinct congener selection patterns that indicated mediation by several different localized populations of anaerobic microorganisms. The higher (more heavily chlorinated) PCB congeners that were preferentially attacked by the observed dechlorination processes included all those that are either pharmacologically active or persistent in higher animals. All the lower (less heavily chlorinated) PCB congeners formed by the dechlorinations were species that are known to be oxidatively biodegradable by the bacteria of aerobic environments.

https://science.sciencemag.org/content/sci/236/4802/709.full.pdf

Polychlorinated Biphenyl Dechlorination in Aquatic Sediments

The polychlorinated biphenyls (PCBs) in sediment and/or fish samples from at least five different locations show changes in gas chromatographic (GC) peak distribution indicative of reductive dechlorination. Several different dechlorination processes, each presumably mediated by a different population of anaerobic bacteria with its own distinctive pattern of PCB congener selectivity, appear to be operating. Six of these processes have been characterized in detail as to the changes occurring in each of the 126 individual PCB congeners or isomer groups detectable by capillary GC or GC-MS on a DB-1 column. The patterns of congener reactivity indicate that the observed transformation processes fall into two broad categories: o,m,p-dechlorinations, which remove chlorine atoms from ortho, meta, and para positions, with congener reactivities primarily determined by reduction potential; and m,p-dechlorinations, which take chlorines from meta and para positions only, with relative reactivities determined mainly by molecular shape. Both types of dechlorination preferentially remove PCB congeners of toxicological concern, and both produce lower congeners that are biodegradable by environmental aerobes. Thus, dechlorination in anaerobic sediments permits the detoxification and eventual degradation of environmental PCBs.

Environmental dechlorination of PCBs

Comprehensive, quantitative, congener-specific analyses of eight aroclors and complete PCB congener assignments on DB-1 capillary GC columns

Congener-specific analyses of the PCBs in Acushnet Estuary (New Bedford, MA) sediments and waters were undertaken to identify the PCB alteration and transport processes occurring in coastal marine sediments. These analyses indicated that (a) the PCBs deposited at the sediment sites sampled had originally consisted of Aroclors 1242 and 1254, in widely varying proportions; (b) these PCBs had undergone vertical movement within the sediments, rather than remaining stratified, but not horizontal translocation between sites; (c) they had also undergone extraction into the water, albeit at declining rates, with some consequent changes in composition but (d) the major compositional change was caused by a previously unreported type of reductive dechlorination process, designated Process H. This presumably anaerobic microbial process, subsequently identified at several other locations as well, had selectively removed non-ortho chlorines from most of the higher PCB congeners, especially those associated with acute toxic effects. It appeared to have begun near the upper end of the estuary and not yet reached its lower portions, thus providing a marker for tracing the origin of the PCBs in estuarine water samples.

PCB movement, dechlorination, and detoxication in the acushnet estuary

It has been recently suggested that variabilities in the partitioning of chronically retained lipophilic xenobiotics between adipose tissue and serum may be relatable to variations in the lipid content of the serum. Here, the authors present theoretical considerations and experimental data showing that this is indeed the case for polychlorinated biphenyls (PCBs) in humans. At equilibrium, in the absence of active transport, any lipophilic substance must distribute itself among body tissues in such a way that its chemical activity and also its chemical potential are the same at all points. In order to verify the theoretical relationships, three sorts of data relating to serum PCB levels in a human population were examined.

John F. Brown

Papers

Polychlorinated Biphenyl Dechlorination in Aquatic Sediments

Environmental dechlorination of PCBs

Comprehensive, quantitative, congener-specific analyses of eight aroclors and complete PCB congener assignments on DB-1 capillary GC columns

PCB movement, dechlorination, and detoxication in the acushnet estuary

Polychlorinated biphenyl (PCB) partitioning between adipose tissue and serum.