Evidence for cometabolic transformation of weathered toxaphene under aerobic conditions using camphor as a co-substrate.

AIMS: Toxaphene is a persistent organic pollutant, composed of approximately 1000 highly chlorinated bicyclic terpenes. The purpose of this study was to evaluate if camphor, a structural analogue of toxaphene, could stimulate aerobic biotransformation of weathered toxaphene. METHODS AND RESULTS: Two enrichment cultures that degrade camphor as the sole carbon source were established from contaminated soil and biosolids. These cultures were used to evaluate aerobic transformation of weathered toxaphene. Only the biosolids culture could transform compounds of technical toxaphene (CTTs) in the presence of camphor, while no transformation was observed in the presence of glucose or with toxaphene as a sole carbon source. The transformed toxaphene had lower concentration of CTTs with longer retention times, and higher concentration of compounds with lower retention times. Gas chromatography with electron capture negative ion mass spectrometry (GC/ECNI-MS) showed that aerobic biotransformation mainly occurred with Cl8 - and Cl9 -CTTs compounds. The patterns of Cl6 - and Cl7 -CTTs were also simplified albeit to a much lesser extent. Seven camphor-degrading bacteria were isolated from the enrichment culture but none of them could degrade toxaphene. CONCLUSION: Camphor degrading culture can aerobically transform CCTs via reductive pathway probably by co-metabolism using camphor as a co-substrate. SIGNIFICANCE AND IMPACT OF THE STUDY: Since camphor is naturally produced by different plants, this study suggests that stimulation of aerobic transformation of toxaphene may occur in nature. Moreover plants, which produce camphor or similar compounds, might be used in bioremediation of contaminated soils.

Genotoxicity in fishes environmentally exposed to As, Se, Hg, Pb, Cr and toxaphene in the lower Colorado River basin, at Mexicali valley, Baja California, México.

The environmental exposure to As, Se, Hg, Pb, Cr and toxaphene was assessed for 11 freshwater fish species in irrigation channels, agricultural return flow drains, a drain collecting lagoon and sections of the Colorado River at the Mexicali valley in Baja California, México, during August 2015-April 2016. Arsenic (2.90 ng ml-1) and Se (1.41 ng ml-1) in water had the highest concentrations in the return flow drains (Hardy River and Xochimilco Lagoon, respectively). However, fish axial muscle tissue had the highest concentration of Se (8.3 µg g-1) and Hg (0.36 µg g-1) in Colorado River fresh water, while As (1.7 µg g-1) in Hardy River fish was highest. Selenium concentrations in all fishes and toxaphene in Cyprinus carpio and Ameiurus natalis are above the safe levels for human consumption (0.3 µg g-1 and 180 ng g-1 respectively). Toxaphene was detected in the fish axial tissue, having the highest concentrations in Poecilia latipinna (690 ng g-1) in the Colorado River. The low proportion of the 8-Cl toxaphene congeners in fish suggests degradation of this pollutant. Tilapia. sp. cf. zillii had the most genotoxic damage with 7.4 micronucleated erythrocytes per 10,000 erythrocytes in Xochimilco Lagoon and 2 in Hardy River. The genotoxicity in all the fish species studied was significantly correlated to the concentrations of As and Se in water.

Toxaphene in the aquatic environment of Greenland.

The octa- and nonachlorinated bornanes (toxaphene) CHBs 26, 40, 41, 44, 50 and 62 were analysed in Arctic char (Salvelinus alpinus), shorthorn sculpin (Myoxocephalus scorpius), ringed seal (Pusa hispida) and black guillemot eggs (Cepphus grylle) from Greenland. Despite their high trophic level, ringed seals had the lowest concentrations of these species, with a Σ6Toxaphene median concentration of 13-20 ng/g lipid weight (lw), suggesting metabolisation. The congener composition also suggests transformation of nona- to octachlorinated congeners. Black guillemot eggs had the highest concentrations (Σ6Toxaphene median concentration of 971 ng/g lw). Although concentrations were higher in East than in West Greenland differences were smaller than for other persistent organic pollutants. In a circumpolar context, toxaphene had the highest concentrations in the Canadian Arctic. Time trend analyses showed significant decreases for black guillemot eggs and juvenile ringed seals, with annual rates of -5 to -7% for Σ6Toxaphene. The decreases were generally steepest for CHBs 40, 41 and 44.

Levels and trends of toxaphene and chlordane-related pesticides in peregrine falcon eggs from South Greenland.

Peregrine falcon eggs were collected in South Greenland between 1986 and 2003 and analysed for 6 congeners of toxaphene and 5 chlordane-related pesticides (cis-chlordane, trans-chlordane, cis-nonachlor, trans-nonachlor and oxychlordane). Oxychlordane had the highest median concentration of 1448 ng/g lipid weight (lw) or 79 ng/g wet weight (ww) of all compounds. Of the toxaphene congeners, CHB-50 was the predominant congener, with a median concentration of 215 ng/g lw (15.5 ng/g ww). Chlordane-related concentrations were comparable with results from the USA, but lower than those from Canada and Norway. Toxaphene was considerably higher than in eggs of Norwegian peregrine falcon eggs, possibly reflecting different toxaphene usage in the areas of peregrine falcon migration. Toxaphene information in birds of prey is limited and comparisons with other species indicate differences in concentrations and organochlorine pattern. Temporal trends showed significant log-linear decreases for cis-chlordane and trans-chlordane, but no significant trends for other chlordanes or the toxaphene congeners, probably affected by the large variation between eggs, also of the same bird. Correlations between chlordanes and toxaphene in the Greenland peregrine falcon eggs might suggest similar sources of exposure.

Using quantitative structural property relationships, chemical fate models, and the chemical partitioning space to investigate the potential for long range transport and bioaccumulation of complex halogenated chemical mixtures.

Some substances are mixtures of very large number of constituents which vary widely in their properties, and thus also in terms of their environmental fate and the hazard that they may pose to humans and the environment. Examples of such substances include industrial chemicals such as the chlorinated paraffins, technical pesticides such as toxaphene, and unintended combustion side products, such as mixed halogenated dibenzo-p-dioxins and dibenzofurans. Here we describe a simple graphical superposition method that could precede a more detailed hazard assessment for such substances. First, partitioning and degradation properties for each individual constituent of a mixture are estimated with high-throughput quantitative structure-property relationships. Placed in a chemical partitioning space, i.e. a coordinate system defined by two partitioning coefficients, the mixtures appear as 'clouds'. When model-derived hazard assessment metrics, such as the potential for bioaccumulation and long range transport, are superimposed on these clouds, the resulting maps identify the constituents with the highest value for a particular parameter and thus potentially the greatest hazard. The maps also indicate transparently how the potential for long range transport and bioaccumulation is dependent on structural attributes, such as chain length, and the degree and type of halogenation. In contrast to previous approaches, in which the mixture is represented by a single set of properties or those of a few selected constituents, the whole range of environmental fate behaviors displayed by the constituents of a mixture are being considered. The approach is illustrated with three sets of chemical substances.

Dechlorination of the dietary nona-chlorinated toxaphene congeners 62 and 50 into the octa-chlorinated toxaphene congeners 44 and 40 in zebrafish (Danio rerio) and Atlantic salmon (Salmo salar).

The relative feed-to-fish accumulation and possible biotransformation of the nona-chlorinated toxaphene congeners currently included in EU-legislation (CHB-50 and -62) and the octa-chlorinated congeners recommended by the European Food Safety Authority to be included in future surveillance of fish samples (CHB-40, 41, and 44) were investigated in the present study. Model fish Danio rerio were fed either (a) diets spiked with a combination as well as the pure individual toxaphene congeners CHB-50 or 62 or (b) diets spiked with the combination of CHB ∑50+62 and/or CHB ∑40+41+44. In addition, seawater adapted Atlantic salmon smolts were fed technical toxaphene enriched feeds for 62 days. Zebrafish fed a diet containing CHB-50 and CHB-62 accumulated newly formed CHB-40&41 and CHB-44, respectively. The biomagnifications factors (BMF) of the toxaphene congeners in Atlantic salmon muscle from the feeds spiked with technical toxaphene were significantly correlated with their relative lipophilicity (expressed as logK(ow)). An exception was CHB-44 which had a higher BMF than could be expected from its specific logK(ow), reflecting that CHB-44 is a metabolite formed under dietary exposure to CHB-62. This paper reports the in vivo dechlorination of nona-chlorinated toxaphene congeners into octa-chlorinated congeners in feeding trials with a model fish (zebrafish) and an oily food fish (Atlantic salmon).

Persistent organic pollutants in ringed seals from the Russian Arctic.

Organochlorine compounds total DDT (ΣDDT), total HCH isomers (ΣHCH), toxaphenes (sum of Parlar 26, 50, 62), mirex, endrin, methoxychlor, total chlorinated benzenes (ΣCBz), total chlordane compounds (ΣCHL), polychlorinated biphenyls (total of 56 congeners; ΣPCBs), polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), and polybrominated diphenyl ethers (sum of 7 tri- to hepta congeners; ΣPBDEs) were analysed in the blubber of adult ringed seals from the four areas of the Russian Arctic (White Sea, Barents Sea, Kara Sea and Chukchi Sea) collected in 2001-2005. Ringed seals from the south-western part of the Kara Sea (Dikson Island - Yenisei estuary) were the most contaminated with ΣDDTs, ΣPCBs, ΣCHL, and mirex as compared with those found in the other three areas of Russian Arctic, while the highest mean concentrations of ΣHCHs and PCDD/Fs were found in the blubber of ringed seals from the Chukchi Sea and the White Sea, respectively. Among all organochlorine compounds measured in ringed seals from the European part of the Russian Arctic, concentrations of ΣDDT and ΣPCBs only were higher as compared with the other Arctic regions. Levels of all other organochlorine compounds were similar or lower than in seals from Svalbard, Alaska, the Canadian Arctic and Greenland. ΣPBDEs were found in all ringed seal samples analysed. There were no significant differences between ΣPBDE concentrations found in the blubber of ringed seals from the three studied areas of the European part of the Russian Arctic, while PBDE contamination level in ringed seals from the Chukchi Sea was 30-50 times lower. ΣPBDE levels in the blubber of seals from the European part of the Russian Arctic are slightly higher than in ringed seals from the Canadian Arctic, Alaska, and western Greenland but lower compared to ringed seals from Svalbard and eastern Greenland.

Geographical variation of persistent organic pollutants in eggs of threatened loggerhead sea turtles (Caretta caretta) from southeastern United States.

Persistent organic pollutants (POPs) are recognized manmade threats to sea turtle populations, but substantial uncertainty exists surrounding their exposure to contaminants and their sensitivity to toxic effects. This uncertainty creates difficulty for conservation managers to make informed decisions for the recovery of these threatened species. To provide baseline concentrations and spatial comparisons, we measured a large suite of POPs in loggerhead sea turtle (Caretta caretta) egg yolk samples collected from 44 nests in three distinct U.S. locations: North Carolina (NC), eastern Florida (E FL), and western Florida (W FL). The POPs included polychlorinated biphenyls (PCBs), organochlorine pesticides such as dichlorodiphenyltrichloroethanes (DDTs), chlordanes, mirex, dieldin, hexachlorocyclohexanes (HCHs), hexachlorobenzene, and toxaphene congeners, as well as polybrominated diphenyl ether congeners (PBDEs). Persistent organic pollutant concentrations were lowest in W FL, intermediate in E FL, and highest in NC egg samples, with several statistically significant spatial differences. This increasing gradient along the southeast coast around the Florida peninsula to North Carolina was explained partly by the foraging site selection of the nesting females. Data from previous tracking studies show that NC nesting females feed primarily along the U.S. eastern coast, whereas W FL nesting females forage in the Gulf of Mexico and Caribbean Sea. The E FL nesting females forage in areas that overlap these two. The foraging site selection also results in exposure to different patterns of POPs. An unusual PBDE pattern was seen in the NC samples, with nearly equal contributions of PBDE congeners 47, 100, and 154. These findings are important to managers assessing threats among different stocks or subpopulations of this threatened species.

Hydroxylated polychlorobornanes--synthesis and characterization of new potential toxaphene metabolites.

For decades, toxaphene had been used as a major chloropesticide. Degradation of the multicomponent mixture in the environment was mainly reported to be due to anaerobic dechlorination and hydrodechlorination. Little was known about oxidative transformation processes and the potential hydroxylated metabolites were not available as standard compounds. For this reason we synthesized hydroxylated polychlorobornanes by the UV-induced photochlorination of 2-endo-bornyl acetate with sulfuryl chloride followed by hydrolysis of the acetate moiety. The released polychlorinated 2-endo-hydroxybornanes were slightly higher chlorinated the longer the reaction was maintained. After 8h, the main products were pentachlorinated hydroxybornanes followed by hexa- and heptachlorinated homologues. Traces of octachlorinated hydroxybornanes were also observed. The GC/ECNI-MS spectra of the products were characterized by the molecular ions and the [M-Cl]⁻ fragment ions. The molecular ions of the polychlorinated hydroxybornanes are isobaric with those of polychlorinated biphenyls. E.g. hexachlorohydroxybornanes (C10H12Cl6O) and hexachlorobiphenyls (C12H4Cl6) show the molecular ion at m/z 358. Based on fractionation experiments on silica with the synthesis products it might be possible that OH-CTTs if present in samples will elute into a more polar fraction usually discarded or not collected. Both problems might explain why these compounds have not been more frequently described in the scientific literature.

Persistent organic pollutants, heavy metals and parasites in the glaucous gull (Larus hyperboreus) on Spitsbergen.

The prediction of a higher parasite infection as a consequence of an impaired immune system with increasing persistent organic pollution (POP) and heavy metal levels were investigated in adult glaucous gull (Larus hyperboreus) from Svalbard. The levels of chlorinated pesticides, polychlorinated biphenyls (PCBs), toxaphenes and polybrominated diphenyl ethers (PBDEs) were measured in liver. Copper, cadmium, lead, mercury, selenium and zinc were measured in kidney samples. An elevated ratio of PCB-118 was found, suggesting that local contamination from the settlement was detectable in the glaucous gull. Eight cestodes, four nematodes, two acanthocephalan and three trematode helminth species were found in the intestine. A positive correlation was found between cestode intensities and selenium levels and between acanthocephalan intensities and mercury levels. No correlation was found between parasite intensities and POP concentrations. It is concluded that the contaminant levels found in glaucous gulls do not cause immune suppression severe enough to affect parasite intensity.

Concentrations, patterns and metabolites of organochlorine pesticides in relation to xenobiotic phase I and II enzyme activities in ringed seals (Phoca hispida) from Svalbard and the Baltic Sea.

The present study investigates the concentrations and patterns of organochlorine pesticides (OCPs) and their metabolites in liver and plasma of two ringed seal populations (Phoca hispida): lower contaminated Svalbard population and more contaminated Baltic Sea population. Among OCPs, p,p'-DDE and sum-chlordanes were the highest in concentration. With increasing hepatic contaminant concentrations and activities of xenobiotic-metabolizing enzymes, the concentrations of 3-methylsulfonyl-p,p'-DDE and the concentration ratios of pentachlorophenol/hexachlorobenzene increased, and the toxaphene pattern shifted more towards persistent Parlar-26 and -50 and less towards more biodegradable Parlar-44. Relative concentrations of the chlordane metabolites, oxychlordane and -heptachlorepoxide, to sum-chlordanes were higher in the seals from Svalbard compared to the seals from the Baltic, while the trend was opposite for cis- and trans-nonachlor. The observed differences in the OCP patterns in the seals from the two populations are probably related to the catalytic activity of xenobiotic-metabolizing enzymes, and also to differences in dietary exposure.

Experiments directed to the compound-specific determination of the stable carbon isotope ratios of the Toxaphene congener B8-1413 in two technical mixtures and Antarctic Weddell seal.

The carbon stable isotope ratio (delta(13)C value) of an environmentally-relevant Toxaphene congener in technical products and a biological sample from a remote region was in the focus of this work. For this reason, the major octachlorobornane residue of the multicomponent pesticide Toxaphene in biological samples, 2-endo,3-exo,5-endo,6-exo,8,8,10,10-octachlorobornane (B8-1413 or P26), was quantitatively enriched from two technical Toxaphene mixtures (Toxaphene and Melipax) in duplicates as well as from an Antarctic Weddell seal sample. Normal phase followed by reversed-phase high-performance liquid chromatography (HPLC) with three columns, respectively, coupled in series was used for this purpose. Four of the five fractionated samples fulfilled the requirement of an interference-free GC-elution for subsequent determination of the delta(13)C value by gas chromatography interfaced to an isotope ratio mass spectrometer (GC-IRMS). B8-1413 in Toxaphene (n=1) was more depleted in (12)C than in Melipax (n=2), which agrees with previous results obtained for the entire mixtures. The B8-1413 isolate from a Weddell seal sample from the Antarctic showed a delta(13)C value between the two technical products. Although a source appointment to the one or the other product was not possible, this example indicates that long range transport to the Antarctic and by uptake and food-chain bioaccumulation of B8-1413 in seals did not change the delta(13)C value significantly. The observed differences in one duplicate sample indicate that statistic evaluation of samples used for isotope ratio MS measurements is an important issue.

Levels of toxaphene congeners in white whales (Delphinapterus leucas) from Svalbard, Norway.

This study reports concentrations of three pesticide toxaphene congeners (CHBs; CHB-26, -50 and -62) from the blubber of ten adult, male white whales (Delphinapterus leucas) from Svalbard, Norway. The CHB congeners that occurred at the highest levels in the blubber of the white whales were, as expected, CHB-26 (4636+/-1992 (SD) ng/g l.w.) and CHB-50 (6579+/-2214 ng/g l.w.); CHB-62 (232+/-231 ng/g l.w.) was also present, but at much lower concentrations. The mean level of the sum of the three CHBs (SigmaCHBs = 11,447+/-4208 ng/g l.w.) in this study is more than twice the mean concentrations of the well-known organochlorine (OC) pollutants SigmaDDTs (sum of pp'-DDT, pp'-DDE, pp'-DDD) and SigmaPCBs (sum of 27 PCB congeners) previously reported from the same individual white whales. The concentrations of CHBs in white whales from Svalbard are at the high end of the range for concentrations of these compounds compared to other Arctic white whale populations. Additionally, the contribution of CHBs to the overall OC burden is larger in white whales from Svalbard compared with their counterparts from other areas in the Arctic. Male white whales from Svalbard have several orders of magnitude higher concentrations of SigmaCHBs compared to seals and polar bears (Ursus maritimus) from the same area. The high levels of CHBs in these whales, and their dominance in the OC pattern, suggests that white whales in Svalbard are exposed to high levels of this group of contaminants. Further studies are needed to investigate possible effects of CHBs and other OC contaminants on the white whale population in Svalbard.

Degradation of toxaphene in aged and freshly contaminated soil.

Degradation of toxaphene in soil from both newly contaminated (from Sweden) and aged spills (from Nicaragua) were studied. The newly contaminated soil contained approximately 11 mg kg(-1) toxaphene while the aged Nicaraguan soil contained approximately 100 mg kg(-1). Degradation was studied in anaerobic bioreactors, some of which were supplied with lactic acid and others with Triton X-114. In this study we found that the lower isomers Parlar 11, 12 were degraded while the concentration of isomer Parlar 15 increased. This supported an earlier evaluation which indicated that less chlorinated isomers are formed from more heavily isomers. Lactic acid when added to the soil, interfere with the degradation of toxaphene. Lactic acid was added; several isomers appeared to degrade rather slowly in newly contaminated Swedish soil. The Swedish soil, without any external carbon source, showed the slowest degradation rate of all the compounds studied. When Triton X-114 at 0.4 mM was added, the degradation rate of the compounds increased. This study illustrates that biodegradation of toxaphene is a complex process and several parameters have to be taken into consideration. Degradation of persistent pollutants in the environment using biotechnology is dependent on bioavailability, carbon sources and formation of metabolites.

Degradation of toxaphene by Bjerkandera sp. strain BOL13 using waste biomass as a cosubstrate.

The white-rot fungus Bjerkandera sp. strain BOL13 was capable of degrading toxaphene when supplied with wood chips, wheat husk or cane molasses as cosubstrates in batch culture experiments. Approximately 85% of toxaphene was removed when wheat husk was the main substrate. The production of lignin peroxidase was only stimulated when wheat husk was present in the liquid medium. Although xylanase was always detected, wheat husk supported the highest xylanase production. A negligible amount of beta-glucosidase and cellulase were found in the batch culture medium. To the best of our knowledge, this is the first reported case of toxaphene degradation by white-rot fungi.

A toxaphene-degrading bacterium related to Enterobacter cloacae, strain D1 isolated from aged contaminated soil in Nicaragua.

Enterobacter sp. strain D1 is a facultative anaerobic, Gram-negative heterotrophic bacterium isolated from toxaphene-contaminated soil. This organism was identified and characterized through phylogenetic and taxonomic studies. Based on 16S rDNA analysis, the strain D1 was clustered closely with the species Enterobacter cloacae subsp. dissolvens (LMG 2683) and E. cloacae (ATCC 13047T). Strain D1 resembled these E. cloacae strains with respect to various biochemical and nutritional characteristics, but also exhibited differences. Moreover, strain D1 is able to grow and survive with toxaphene supplied in the medium in the range 3-96 mg/L. Amongst the chemical components of toxaphene, octachlorocamphenes, nonachlorobornanes and decachlorobornanes were seen to be rapidly metabolized, although levels of hexachlorocamphenes and heptachlorobornanes were found to be slowly degraded, and subsequently accumulated during the last stage of the cultivation.

Investigations of the potential influence of environmental contaminants on the thymus and spleen of harbor porpoises (Phocoena phocoena).

Harbor porpoises from the German North and Baltic Seas exhibit a higher incidence of bacterial infections compared to whales from less polluted arctic waters. The potential adverse effect of environmental contaminants such as polychlorinated biphenyls (PCBs) and heavy metals on the immune system and the health status of marine mammals is still discussed controversially. The aim of the present study was to investigate the possible influence of PCB, polybrominated diphenyl ether (PBDE), toxaphene, (p,p'-dichlorodiphenyl)trichlorethane (DDT), and (p,p'-dichlorodiphenyl)dichlorethene (DDE) on the immune system of harbor porpoises. Lymphoid organs are influenced by a variety of factors, and therefore special emphasis was given to separating the confounding effect of age, health status, nutritional state, geographical location, and sex from the effect of contaminant levels upon thymus and spleen. Contaminant analysis and detailed pathological examinations were conducted on 61 by-caught and stranded whales from the North and Baltic Seas and Icelandic and Norwegian waters. Stranded harbor porpoises were more severely diseased than by-caught animals. Thymic atrophy and splenic depletion were significantly correlated to increased PCB and PBDE levels. However, lymphoid depletion was also associated with emaciation and an impaired health status. The present report supports the hypothesis of a contaminant-induced immunosuppression, possibly contributing to disease susceptibility in harbor porpoises. However, further studies are needed to determine if lymphoid depletion is primarily contaminant-induced or secondary to disease and emaciation in this cetacean species.

Temperature and congener structure affect the enantioselectivity of toxaphene elimination by fish.

Recent advances in enantioselective separation techniques have enabled scientists to investigate environmental fate processes of chiral pollutants. In this study, congener- and enantiomer-specific toxaphene residues were monitored in captive, naturally contaminated fish (Fundulus heteroclitus) to characterize the effect of temperature and compound structure on the enantioselectivity of the elimination process. A previous study performed under warm water conditions (Tmean = 25 degrees C) demonstrated relatively rapid (t(1/2) approximately = 7-14 d) and enantioselective elimination of the reductive dechlorination metabolites 2-exo,3-endo,6-exo,8,9,-10-hexachlorobornane (B6-923 or Hx-Sed) and 2-endo,3-exo,5-endo,6-exo,8,9,10-heptachlorobornane (B7-1001 or Hp-Sed). As expected, repetition of this experiment at cooler water temperatures (Tmean = 15 degrees C) resulted in a decrease in overall (i.e., both enantiomers) first-order elimination rate constants. Enantiomer fractions or ratios (EFs/ERs) during elimination, however, varied by congener, ranging from racemic for very rapidly eliminated Cl5 homologues to increasingly nonracemic for selected Cl6-Cl8 homologues (including 86-923, several unknown Cl7 compounds, B8-1414, and B8-1945). As a result, we propose a classification to describe the environmental persistence of chiral toxaphene pollutants based on congener-specific elimination kinetics and susceptibility to biotransformation as measured by EFs/ERs.

Residues of toxaphene in insectivorous birds (Petrochelidon spp.) from the Rio Grande, Texas.

Although it has been documented that wildlife in the Rio Grande Valley (RGV) contain increased concentrations of organochlorine (OC) contaminants, particularly DDE, little has been published on residues of toxaphene throughout this major North American watershed. In this study, 28 liver composites from adult swallows (Petrochelidon spp.) collected along the Rio Grande from 1999 through 2000 were analyzed for toxaphene residues using congener-specific gas chromatography-electron-capture negative ionization-mass spectrometry. Estimated total toxaphene concentrations ranged from 12 to 260 ng/g wet wt and were highest in samples from the lower RGV near Llano Grande Lake in Hidalgo and Cameron counties (Texas). Toxaphene congener profiles were relatively invariant throughout the watershed and were dominated by 2,2,5-endo,6-exo,8,8,9,10-octachlorobornane (P-42a or B8-806) with lesser amounts of several other Cl(7)-Cl(9) compounds, many of which remain unidentified. Petrochelidon spp. liver profiles appear to be intermediate in complexity between those in invertebrates and fish (more complex) and mammals (less complex) and differs somewhat from those reported for other avian species. In addition to other legacy OC contaminants, toxaphene residues were most concentrated in the lower RGV and accumulated at up to hundreds of parts per billion in these insect-eating birds, underscoring their utility as avian bioindicators of persistent organic pollutants.

Genotoxic activity of a technical toxaphene mixture and its photodegradation products in SOS genotoxicity tests.

Toxaphene (CAS No. 800-35-2) is a complex mixture of several hundred components that was used worldwide primarily as an agricultural pesticide with insecticide effects in the second half of the 20th century. In vitro investigations of the genotoxicity and mutagenicity of toxaphene were generally described in the literature, but they provided somewhat equivocal results. We re-evaluated the genotoxicity of technical toxaphene in two prokaryotic systems. The SOS Chromotest showed high sensitivity to toxaphene: three concentrations (40, 20 and 10 mg/l) were clearly positive and the dose-response effect was evident. In the umuC assay, a dose-dependent increase in genotoxic activity was observed at toxaphene concentrations from 2.5 to 40.0 mg/l, but these results were found to be not significant. The genotoxicity of toxaphene and its photodegradation products after UV-irradiation (3-6-9 h) at concentrations ranging from 7.5 to 60.0 mg/l was also examined in this study. An irradiated solution of technical toxaphene after 3 h showed no significant evidence of bacterial growth inhibition. However, exposure of Salmonella to 6 h UV-irradiated toxaphene showed a toxic effect compared with the negative control. After 9 h irradiation, a decrease of bacterial growth was observed. Activity of beta-galactosidase in the presence of a toxaphene solution was significantly increased after 6 and 9 h irradiation, reaching values that were 2.4- and 3.1-fold higher, respectively, than the control, which exceeded the criteria of significant genotoxicity. These results show that while technical toxaphene is a weak, direct-acting mutagen in some bacterial tests, a dose-dependent toxicity and genotoxicity of its photoproducts could be conclusively demonstrated by the umuC test.