Sorption and competition of two persistent organic pesticides onto marine sediments: Relevance to their distribution in aquatic system.

Sorption is a key process in the distribution of substances between environmental compartments in marine ecosystems. Two persistent organic pesticides, also known as toxaphene congeners, namely B8-1413 (P26) and B9-1679 (P50), are of special interest because they are not detected in sediments while relatively concentrated in marine mammals. Sorption-desorption, entrapment and competition behaviors of these pesticides onto marine sediments were studied to explain their environmental distribution. Data obtained under marine experimental conditions were fitted to sorption models to evaluate sorption coefficients and to assess the degree of B8-1413/B9-1679 entrapment of the two toxaphene congeners in sediments. Carbon normalized sorption coefficients (Koc) of both congeners were similar under in cold (2°C) marine (30 psu) conditions with high values ranging from 1.53×10(5) to 3.28×10(5) mL g(-1)indicative of a strong affinity to marine sediments However, the sorption-desorption investigations indicate that B8-1413/B9-1679 were on average 2.5 times less entrapped in sediments compared to B7-1450, a toxaphene congener known to accumulate predominantly in sediments. These results suggest that the low entrapment of B8-1413 and B9-1679 favor their availability and transfer to biological matrices.

Model predictions of toxaphene degradation in the atmosphere over North America.

Technical toxaphene, a broad-spectrum pesticide mixture, degrades in the environment, resulting in potential changes in toxicity. The present study uses a multimedia model that the authors developed to estimate toxaphene degradation in the atmosphere over North America. The predicted degradation has strong spatial and temporal variability determined by processes such as emission and transport of technical toxaphene, as well as the complex interactions among many species (e.g., toxaphene, hydroxyl [OH] radicals, and ozone). More toxaphene is degraded in warmer months due to higher concentrations of technical toxaphene (primarily due to higher technical toxaphene emissions in the southeastern United States and transport to other regions) and OH radicals. In the model, OH radicals are created primarily through the reactions of water vapor with the excited oxygen atom, O(¹D), generated by the photolysis of ozone, which is produced primarily by reactions of volatile organic compounds and nitrogen oxides (NOx) in the presence of sunlight. The higher OH concentrations in warmer months are primarily the result of higher solar radiation and ozone concentrations. The spatial distribution of degradation depends on the distribution of technical toxaphene soil residues as well as atmospheric transport and chemistry; significant chemical degradation occurs in the southeastern United States where soils are most heavily contaminated by past applications of toxaphene.

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.

The effect of co-occurring polychlorinated biphenyls on quantitation of toxaphene in fish tissue samples by gas chromatography negative ion mass spectrometry.

Determinative methods based on gas chromatography-negative chemical ionization mass spectrometry (GC-NCI/MS) provide improved sensitivity and specificity for toxaphene in environmental samples, but are subject to misidentification due to oxygen reaction in the presence of polychlorinated biphenyls (PCBs). The goal of this study was to quantify the impact of co-occurring PCBs in fish tissue samples when utilizing single quadrupole instruments to implement this method. Mixtures of PCB congeners and technical toxaphene, and extracts of fish tissue with varying concentrations of PCBs were analyzed for individual congener and total toxaphene concentrations by GC-NCI/MS. The contribution of co-injected PCB 204 ranged from 23% to 88% of the total peak area for the Cl-9 toxaphene homolog quantitation ion, a contribution that increased as the ratio of technical toxaphene to PCB 204 decreased. PCB interferences in fish tissue extracts, including a standard reference material, were subtracted using a three-step procedure featuring spectral analysis of isotopic patterns for target peaks. Total toxaphene concentrations without PCB subtraction in three fish tissue samples with low, intermediate and high co-occurring PCBs were overestimated by 33, 55 and 745%, respectively, underscoring the need for practical strategies to account for PCB interferences in GC-NCI/MS based protocols. In contrast, no appreciable interference or resulting positive bias in concentrations was observed for quantitation of eight common toxaphene residue congeners.

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).

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.

Modeling toxaphene behavior in the Great Lakes.

Chlorinated camphenes, toxaphene, are persistent organic pollutants of concern in the Great Lakes since elevated concentrations are found in various media throughout the system. While concentrations have decreased since their peak values in the 1970s and 80s, recent measurements have shown that the rate of this decline in Lake Superior has decreased significantly. This modeling study focused on toxaphene cycling in the Great Lakes and was performed primarily to determine if elevated water and fish concentrations in Lake Superior can be explained by physical differences among the lakes. Specifically, the coastal zone model for persistent organic pollutants (CoZMo-POP), a fugacity-based multimedia fate model, was used to calculate toxaphene concentrations in the atmosphere, water, soil, sediment, and biota. The performance of the model was evaluated by comparing calculated and reported concentrations in these compartments. In general, simulated and observed concentrations agree within one order of magnitude. Both model results and observed values indicate that toxaphene concentrations have declined in water and biota since the 1980s primarily as the result of decreased atmospheric deposition rates. Overall the model results suggest that the CoZMo-POP2 model does a reasonable job in simulating toxaphene variations in the Great Lakes basin. The results suggest that the recent findings of higher toxaphene concentrations in Lake Superior can be explained by differences in the physical properties of the lake (primarily large volume, large residence time and cold temperatures) compared to the lower lakes and increased recent inputs are not needed to explain the measured values.

Offline coupling of high-speed counter-current chromatography and gas chromatography/mass spectrometry generates a two-dimensional plot of toxaphene components.

High-speed counter-current chromatography (HSCCC), a separation technique based solely on the partitioning of solutes between two immiscible liquid phases, was applied for the fractionation of technical toxaphene, an organochlorine pesticide which consists of a complex mixture of structurally closely related compounds. A solvent system (n-hexane/methanol/water 34:24:1, v/v/v) was developed which allowed to separate compounds of technical toxaphene (CTTs) with excellent retention of the stationary phase (S(f) = 88%). Subsequent analysis of all HSCCC fractions by gas chromatography coupled to electron-capture negative ion mass spectrometry (GC/ECNI-MS) provided a wealth of information regarding separation characteristics of HSCCC and the composition of technical toxaphene. The visualization of the large amount of data obtained from the offline two-dimensional HSCCC-GC/ECNI-MS experiment was facilitated by the creation of a two-dimensional (2D) contour plot. The contour plot not only provided an excellent overview of the HSCCC separation progress, it also illustrated the differences in selectivity between HSCCC and GC. The results of this proof-of-concept study showed that the 2D chromatographic approach involving HSCCC facilitated the separation of CTTs that coelute in unidimensional GC. Furthermore, the creation of 2D contour plots may provide a useful means of enhancing data visualization for other offline two-dimensional separations.

Long-range atmospheric transport of three toxaphene congeners across Europe. Modeling by chained single-box FATEMOD program.

BACKGROUND, AIMS, AND SCOPE: Since toxaphene (polychlorocamphene, polychloropinene, or strobane) mixtures were applied for massive insecticide use in the 1960s to replace the use of DDT, some of their congeners have been found at high latitudes far away from the usage areas. Especially polychlorinated bornanes have demonstrated dominating congeners transported by air up to the Arctic areas. Environmental fate modeling has been applied to monitor this phenomenon using parallel zones of atmosphere around the globe as interconnected environments. These zones, shown in many meteorological maps, however, may not be the best way to configure atmospheric transport in air trajectories. The latter could also be covered by connecting a chain of simple model boxes. We aim to study this alternative approach by modeling the trajectory chain using catchment boxes of our FATEMOD model. Polychlorobornanes analyzed in biota of the Barents Sea offered one case to study this modeling alternative, while toxaphene has been and partly still is used massively at southern East Europe and around rivers flowing to the Aral Sea. MATERIALS AND METHODS: Pure model substances of three polychlorobornanes (toxaphene congeners P26, P50, and P62) were synthesized, their environmentally important thermal properties measured by differential scanning calorimetry, as evaluated from literature data, and their temperature dependences estimated by the QSPR programs VPLEST, WATSOLU, and TDLKOW. The evaluated property parameters were used to model their atmospheric long-range transport from toxaphene heavy usage areas in Ukraine and Aral/SyrDarja/AmuDarja region areas, through East Europe and Northern Norway (Finnmarken) to the Barents Sea. The time period used for the emission model was June 1997. Usual weather conditions in June were applied in the model, which was constructed by chaining FATEMOD model boxes of the catchment's areas along assumed maximal air flow trajectories. Analysis of the three chlorobornanes in toxaphene mixtures function as a basis for the estimates of emission levels caused by its usage. High estimate (A) was taken from contents in a Western product chlorocamphene and low estimate (B) from mean contents in Russian polychloroterpene products to achieve modeled water concentrations. Bioaccumulation to analyzed lipid of aquatic biota at the target region was estimated by using statistical calculation for persistent organic pollutants in literature. RESULTS: The results from model runs A and B (high and low emission estimate) for levels in sea biota were compared to analysis results of samples taken in August 1997 at Barents Sea. The model results (ng g(-1) lw): 4-95 in lipid of planktovores and 7-150 in lipid of piscivores, were in fair agreement with the analysis results from August 1997: 21-31 in Themisto libellula (chatka), 26-42 in Boreocadus saida (Polar cod), and 5-27 in Gadus morhua (cod) liver. DISCUSSION: The modeling results indicate that the application of chained simple multimedia catchment boxes on predicted trajectory is a useful method for estimation of volatile airborne persistent chemical exposures to biota in remote areas. For hazard assessment of these pollutants, their properties, especially temperature dependences, must be estimated by a reasonable accuracy. That can be achieved by using measurements in laboratory with pure model compounds and estimation of properties by thermodynamic QSPR methods. The property parameters can be validated by comparing their values at an environmental temperature range with measured or QSPR-estimated values derived by independent methods. The chained box method used for long-range air transport modeling can be more suitable than global parallel zones modeling used earlier, provided that the main airflow trajectories and properties of transported pollutants are predictable enough. CONCLUSIONS: Long-range air transport modeling of persistent, especially photo-resistant organic compounds using a chain of joint simple boxes of catchment's environments is a feasible method to predict concentrations of pollutants at the target area. This is justified from model results compared with analytical measurements in Barents Sea biota in August 1997: three of six modeled values were high and the other three low compared to the analysis results. The order of magnitude level was similar in both modeled (planktovore and piscivore) and observed (chatka and polar cod) values of lipid samples. The obtained results were too limited to firm validation but are sufficient to justify feasibility of the method, which prompts one to perform more studies on this modeling system. RECOMMENDATIONS AND PERSPECTIVES: For assessment of the risk of environmental damages, chemical fate determination is an essential tool for chemical control, e.g., for EU following the REACH rules. The present conclusion of applicability of the chained single-box multimedia modeling can be validated by further studies using analyses of emissions and target biota in various other cases. To achieve useful results, fate models built with databases having automatic steps for most calculations and outputs accessible to all chemical control professionals are essential. Our FATEMOD program catchments at environments and compound properties listed in the database represent a feasible tool for local, regional, and, according our present test results, for global exposure predictions. As an extended use of model, emission estimates can be achieved by reversed modeling from analysis results of samples corresponding to the target area.

Modeling the effects of methanol on iron dechlorination of a complex chlorinated NAPL.

Research was conducted to examine the effects of various fractions of cosolvent solutions on dechlorination of toxaphene by zero-valent iron (Fe(0)). Experimental results showed that toxaphene degradation in solution was found to be the result of dechlorination at the Fe(0) surface. The rate of toxaphene dechlorination was also found to reduce with the increase of cosolvent in solution, as the cosolvent presence caused a reduction in toxaphene adsorption to Fe(0) surfaces. Toxaphene sorption to Fe(0) was found to correspond to a Freundlich nonlinear sorption equation and indicated that the linearity of this isotherm in the presence of cosolvent was related to the saturation of solution, which was the ratio of aqueous concentration to the solubility (C(a)/S(c)). When C(a)/S(c)>0.2, the sorption isotherm was almost linear and the concept of cosolvency power can be applied mathematically to describe this process. A mathematical model detailing the sorption and dechlorination of toxaphene by Fe(0) was developed, and showed that experimental data agreed with the theoretically derived data. Overall, results indicated that dechlorination of complex chlorinated substances, such as toxaphene, by Fe(0) can be greatly dependent upon adsorption to the iron surface.

Evaluation of tumour promoting potency of fish borne toxaphene residues, as compared to technical toxaphene and UV-irradiated toxaphene.

In this study the potential impact of food chain-based biotransformation and physico-chemical weathering of toxaphene on its tumour promoting potential was investigated in vitro and in vivo. Human exposure to toxaphene is mainly through consumption of contaminated fish, therefore fish-borne residues of toxaphene (cod liver extract, CLE) were prepared by exposing cod to technical toxaphene (TT) for 63 days. UV-irradiated toxaphene (uvT) was included to represent a physico-chemical weathered toxaphene mixture. In vitro, TT, uvT and CLE all showed a dose- and time-dependent inhibition of gap junctional intercellular communication (GJIC) with a relative potency of CLE>TT=uvT. Tumour promoting potency was further studied in vivo in a medium term two-stage initiation/promotion bioassay in female Sprague-Dawley rats, using an increase in altered hepatic foci positive for glutathione-S-transferase-P (AHF-GST-P) as read out. No increase in AHF-GST-P occurred following exposure to either TT, uvT, or CLE, except for the positive control group (2,3,7,8-TCDD). Based on this study the no observed adverse effect level (NOAEL) for tumour promoting potency is at least 12.5mg/kg/week, or higher for CLE. Considering current human exposure levels in Europe it is doubtful that consumption of fish at current levels of toxaphene contamination give rise to human health risk.

Investigations on the sorption of a toxaphene model congener, the B7-1450, on marine sediments.

Sorption is a natural process that takes place in sediments or soils and changes the mobility and availability of hydrophobic organic compounds, such as toxaphene pesticide in the environment. The sorption of the 2-exo,3-endo,5-exo,8,9,10,10-heptachlorobornane (B7-1450), used as a model compound of the toxaphene heptachlorobornane congeners found in sediments, was investigated for the first time through a series of batch sorption experiments. The losses of B7-1450 due to adsorption onto glass walls and to evaporation occurring during analytical treatment steps were corrected. The study showed that these specific losses ranged from 2% to 3.5% for the glass walls adsorption and can be as high as 15% for the evaporation treatment. The sorption coefficients, K(d) and K(oc), of B7-1450 could be overestimated by >30%, particularly for low-concentration samples, if the losses were not corrected. Loss correction equations were established, validated and applied to determine sorption coefficients for the B7-1450 congener. The K(oc) values for B7-1450 determined over a gradient of concentrations ranged from 3.5x10(4) to 6.5x10(4)mlg(-1), revealing a strong affinity of B7-1450 for marine sediments.

Assessing the relationship between extensive use of organochlorine pesticides and cooling trend during the mid-20th century in the southeastern United States.

In contrast to global warming, temperatures in the southeastern United States have exhibited a decreasing trend of up to 1-2 degrees C over the last century. We investigated the relationship between this cooling trend and the extensive use of organochlorine pesticides--particularly dichloro-diphenyl-trichloroethane (DDT) and toxaphene--in the southeastern U.S. from the mid-1940s through the 1970s. Based on annual use and soil residue estimates, it is shown that enthalpies associated with the endothermic evaporation of pesticides from soil resulted in surface temperature decreases of up to -0.2 degrees C. This is the first study to show the inverse correlation between surface air temperature and pesticide use. These findings highlight the potential contribution of the extensive use of organochlorine pesticides to changes in the surface air temperature, especially in regions of intensive agriculture and pesticide use.

Toxaphene chemistry: separation and characterisation of selected enantiomers of the Polychloropinene mixtures.

The primary goal for the study presented here was the preparation and characterisation of enantiomeric pure chlorobornane standards (Toxaphene). In this context, we partially modeled the procedure for Polychloropinene production in the former USSR. The initial reaction was ionic addition of hydrogen chloride to (1S)-alpha-pinene resulting predominantly in (1S)-2-endo-chlorobornane. Further photochlorination gave mixtures of chlorinated terpenes with different average content of Cl per molecule. The resulting mixtures were separated on a silica-gel column and a number of known hepta to decachlorobornanes were identified in fractions with the help of NMR and GC (using electron capture and mass spectrometric detection)--but in very unusual ratios as compared to the technical Toxaphene mixture formerly produced by Hercules (USA). Also several previously unknown congeners were isolated or detected. Three of the isolated congeners were obtained in crystalline state and X-ray crystallography showed their enantiomeric purity.

Determination of toxaphene enantiomers by comprehensive two-dimensional gas chromatography with electron-capture detection.

Comprehensive two-dimensional gas chromatography with micro electron-capture detection (GC x GC-microECD) has been evaluated for the enantioseparation of five chiral toxaphenes typically found in real-life samples (Parlar 26, 32, 40, 44 and 50). From the two enantioselective beta-cyclodextrin-based columns evaluated as first dimension column, BGB-176SE and BGB-172, the latter provided the best results and was further combined with three non-enantioselective columns in the second dimension: HT-8, BPX-50 and Supelcowax-10. The combination BGB-172 x BPX-50 was finally selected because it provided a complete separation among all enantiomers. A satisfactory repeatability and reproducibility of the retention times in both the first and the second dimension were observed for all target compounds (RSDs below 0.8%, n = 4). Linear responses in the tested range of 10-200 pg/microl and limits of detection in the range of 2-6 pg/microl were obtained. The repeatability and reproducibility at a concentration of 100 pg/microl, evaluated as the RSDs calculated for the enantiomeric fraction (EF), was better than 11% (n = 4) in all instances. The feasibility of the method developed for real-life analyses was illustrated by the determination of the enantiomeric ratios and concentration levels of the test compounds in four commercial fish oil samples. These results were compared to those obtained by heart-cut multidimensional gas chromatography using the same enantioselective column.

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.

Establishing a chromium-reactor design for measuring delta2H values of solid polyhalogenated compounds using direct elemental analysis and stable isotope ratio mass spectrometry.

2H/1H isotope ratios of polyhalogenated compounds were determined by elemental analysis and isotope ratio mass spectrometry (EA-IRMS). Initial measurements with standard EA-IRMS equipment, which used high-temperature pyrolysis to convert the organic compounds into hydrogen, did not achieve significant signals for polychlorinated pesticides and related compounds, presumably due to the formation of HCl instead of hydrogen. To reverse this problematic reaction, a chromium reactor was incorporated into the element analyzer system, which scavenged Cl, forming chromium chloride and releasing hydrogen again in the form of H2. The optimized system therefore allowed the delta2H values of polyhalogenated compounds to be determined. A quality assurance program was developed based on several parameters. (i) Each compound was analyzed using a sequence of five injections, where the first measurement was discarded. (ii) Recovery of H (when calculated relative to acetanilide) had to be >90% for all replicates in a sequence. (iii) All delta-values within a sequence had to vary by less than 10/1000. (iv) Results had to be reproducible on another day with a different sample scheme. Once this reproducibility had been established, variabilities in the delta2H values of organohalogen standards were investigated using the technique. The highest delta2H value of +75/1000 was found for o,p'-DDD, whereas the strongest depletion in deuterium was found for Melipax (-181/1000). The most important results for comparable compounds were as follows. DDT-related compounds gave delta2H values of between +59 and +75/1000 (technical DDT, o,p'- and p,p'-DDD) or in the range of approximately -1/1000, indicative of the different sources/methods of producing this compound. Four HCH isomers from the same supplier showed relatively similar hydrogen isotope distributions, whereas two lindane (gamma-HCH) standards from other sources had 39/1000 less deuterium. This difference is likely due to different purification steps during the isolation of pure lindane from the technical HCH mixture. An even greater difference was observed between the delta2H values of Toxaphene (US product dating from 1978) and Melipax (product from the former East Germany, dating from 1979), which gave delta2H values of -101/1000 and -181/1000, respectively, meaning that both products were easily distinguished via delta2H-IRMS. Fractioning of hydrogen isotopes in the atmospheric water cycle was suggested as one reason for the different values. In this theory, the water (which had different delta2H values depending on where it was taken from) was incorporated during the biosynthesis of camphene, which is the natural product used to produce both products. These results indicate that hydrogen isotope-specific analysis can be a valuable tool for tracing the origins of a compound in certain cases.

Enantioselective determination of chiral toxaphene congeners in laying hens and eggs using multidimensional high-resolution gas chromatography.

A total of 22 chiral toxaphene congeners were analyzed in organ tissues and eggs of laying hens after they had been fed with food spiked with technical toxaphene. For the analysis, multidimensional high-resolution gas chromatography using a chiral column coated with randomly silylated heptakis(O-tert-butyldimethylsilyl)-beta-cyclodextrin, electron capture detection, and valveless "live column switching" technique was applied. The analytical results were additionally confirmed with mass spectral data, recorded in electron-capture negative ionization mode with selected-ion monitoring mass spectrometry. During both the feeding period of the laying hens with toxaphene-contaminated food (38 weeks, accumulation phase) and the following subsiding period without toxaphenes (another 14 weeks, decontamination phase), organs (liver, kidney, skin/fat), blood, meat, and eggs of the hens served as model matrices for toxaphene uptake. The enantiomeric ratios (ERs) of congeners 26, 31, 32, 40, 41, 42(a+b), 44, 50, and 62--known as the most important components of technical toxaphene occurring in the environment--could be analytically determined. Significant differences were observed with respect to their initial racemic ratios. On the basis of their chemical structures, the metabolic pathways of some congeners could be explained. Astonishingly, some of the toxaphenes applied as racemates could merely be found as single enantiomers at the end of the feeding program, for example, congener 32 in blood and meat samples or congener 44, especially in organ tissues, which showed ERs of zero or infinity. The findings of this study impressively emphasize that it is essential to isolate and analyze individual toxaphene enantiomers in food and biota tissues to be capable of evaluating their toxicity and metabolization more specifically.

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.