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.     

Studies of toxaphene in technical standard and extracts of background air samples (Point Petre, Ontario) using multidimensional gas chromatography-electron capture detection (MDGC-ECD)

MDGC-ECD procedures have been used to provide insight into the compositional complexity of some of the specific peaks or clusters observed in the gas chromatographic analysis of a technical toxaphene standard, with reference to individual toxaphene congeners (Parlar # components) that are flow commercially available. These investigations have focussed initially upon those peaks and clusters recently identified (Shoeib. M., Brice, K.A., Hoff, R., 1999. Chemosphere 39, 849-871) as dominant constituents of background ambient air. Multiple electron-capturing components have been found to be present in all the species studied: the available individual toxaphene congeners have been matched against these components where possible. In similar fashion, the responses obtained in equivalent gas chromatographic elution windows from the analysis of typical processed air sample extracts have been investigated, with the results showing clear differences relative to the patterns found in the technical toxaphene standard. In most cases, the air sample shows reduced complexity with fewer components present in the cluster. Also, the presence of interfering responses (due to PCBs and other organochlorines) is quite apparent and significant, showing that major problems and errors could arise when using single-column GC-ECD procedures for quantitation of toxaphene in environmental samples. The presence of certain of the Parlar species in the air samples has been confirmed and in most cases these represent the dominant toxaphene component found in the targeted cluster. Furthermore, the persistence of certain congeners in the atmospheric samples appears to be strongly dependent upon chemical structure, since the congeners in question possess an alternating exo-endo chlorine substitution pattern around the six-membered ring in the bornane skeleton. Such persistence is probably the result of lower metabolization of toxaphene residues in soils, water and sediments leading to a similar pattern in the atmosphere following volatilization.     

Total toxaphene and specific congeners in fish from the Yukon, Canada

Toxaphene is one of the major persistent organic pollutants with global environmental impacts. We have measured total toxaphene and specific congeners concentrations in 19 fish samples collected from the Yukon, Canada using gas chromatography coupled to ion trap MS/MS. The total toxaphene concentrations ranged from 42 to 242 ng/g (mean = 107+/-61 ng/g). The sum of the three specific congeners (Parlar 26, 50 and 62) was within 10-55 ng/g. The ratio of the sum of the three congeners to the total toxaphene varied between 8% and 25% in the fish samples but the ratio may be species specific. Our results suggest that consumption of these Yukon fish should have minimal risk of toxaphene exposure.     

Levels of toxaphene congeners in fish from Danish waters

The levels of toxaphene congeners, in addition to PCB congeners and organochlorine pesticides, were determined in various fish samples from different Danish waters. While PCB-153 and p,p'-DDE show different levels depending on the fishing area, with highest levels in fish from the Western Baltic Sea, toxaphene was detected in all the samples investigated at a more constant level. The distribution of the three toxaphene congeners Parlar #26, #50 and #62 depends on the fishing area, with the Western Baltic Sea being different from the other waters by having almost equal levels of toxaphene congeners #26 and #50.     

NMR and molecular modeling in environmental chemistry: prediction of 13C chemical shifts in selected C10-chloroterpenes employing DFT/GIAO theory

Accurate predictions of 13C NMR chemical shifts (standard error approximately 1.7 ppm) are achieved for a subset of chlorinated bornanes by empirical scaling of shifts from GIAO calculations with geometries obtained from HF/6-31G* calculations. The optimized molecular geometries were compared with X-ray structures for three of the toxaphene components most frequently detected in environmental samples (Parlar nos. 26, 50 and 62), and the concordance between the experimental and calculated values was found to be satisfactory. Taken overall, the results indicate that theoretical methods hold great promise for rationalizing 13C NMR chemical shifts in organohalogen compounds. However, it appeared that the DFT/GIAO shifts need to be empirically scaled to achieve good numerical agreement with experimental shifts in chlorinated bornanes. Obviously, there is a need to develop new computational methods to describe the large deshielding effects of chlorine atoms properly.     

Structure elucidation of the three most important toxaphene congeners by X-ray analysis

Three of the most frequently detected toxaphene components in environmental samples are the chlorobornanes 2-exo,3-endo,5-exo,6-endo,8b,8c,10a,10b-octachlorobornane (Parlar No. 26); 2-exo,3-endo,5-exo,6-endo,8b,8c,9c,10a,10b-nonachlorobornane (Parlar No. 50), and 2,2,5,5,8b,8c,9c,10a,10b-nonachlorobornane (Parlar No. 62), whose structures could not be completely elucidated by spectroscopical methods. This paper now describes the X-ray structure analysis of the three compounds and presents their exact crystal structure.     

The role of biotic and abiotic degradation processes during the formation of typical toxaphene peak patterns in aquatic biota.

Toxaphene residues in cod liver and fish oil samples from different countries have been analyzed by HRGC-ECD and HRGC-MS as well as with multidimensional gas chromatography. The results have been compared to patterns obtained by photolysis and microbial degradation of selected single chlorobornanes and technical toxaphene. Enantiomeric ratios of the components Parlar #44 and #62 showed significant deviations from 1, indicating metabolism in cod fish and perhaps other species at least for some congeners. Parlar #50 was found to be a racemate, which corresponds to its known stability under biotic and abiotic conditions.     

Study of the enantioselective elimination of four toxaphene congeners in rat after intravenous administration by high resolution gas chromatography negative ion mass spectrometry

This study was performed to investigate the possible enantioselective metabolism of the four chlorinated bornanes: #26, #32, #50 and #62 (according to the Parlar nomenclature) by rats. Rats were exposed to a mixture of these toxaphenes by a single intravenous injection. Enantiomer ratios (ER) as well as the enantiomer fractions (EF) were determined in brain, adipose tissue and liver samples at six time intervals by high resolution gas chromatography (HRGC) coupled to negative ion chemical ionization (NICI) mass spectrometry (MS). Capillaries coated with heptakis-(2,3,6-O-tert-butyldimethylsilyl)-beta-cyclodextrin (TBDMS-CD) or octakis-(2,3,6-tri-O-ethyl)-gamma-cyclodextrin (TEG-CD) were used for the enantioselective separations. Significant time-dependent changes of ER and EF were found in all the three tissues for #26, #50 and #62. Greatest deviations from racemic composition were found in the liver, which is known to be the major metabolizing organ for toxaphenes. #32 was metabolized the fastest, but showed no changes in ER. Brief information is also included about the possible reasons for the different behaviors of the four congeners in the studied tissues.     

The determination of toxaphene in environmental samples by negative ion electron capture high resolution mass spectrometry

A method is described for the analysis of toxaphene in environmental samples by high resolution gas chromatography high resolution mass spectrometry in selected ion electron capture negative ion mode. Toxaphene is detected by monitoring [M-Cl]- fragments ions of chlorobornanes (Cl6-Cl10) and chlorobornenes (Cl6-Cl7) using formal ion ratio criteria. The method shows high sensitivity and excellent specificity for the detection of chlorobornanes with negligible interference from of a wide range of common environmental organochlorines including chlordanes, PCBs and PCB-oxygen adducts. The analytical scheme is applicable to sediment and biological tissue samples and typically provide sample detection limits of less than 0.2 ng/g technical toxaphene for a 10 g sample.     

Toxaphene congeners in the Canadian Great Lakes basin: temporal and spatial food web dynamics

Samples of a top predator fish species, lake trout (Salvelinus namaycush) and predominant forage species including smelt (Osmerus mordax), alewife (Alosa pseudoharengus), slimy sculpin (Cottus cognatus), deepwater sculpin (Myoxocephalus quadricornis) and lake herring (Coregonus artedii) were, collected from throughout 4 of the 5 Great Lakes (Superior, Huron, Erie and Ontario) (Fig. 1). Lake trout were also collected from three isolated lake systems (Lakes Nipigon, Simcoe and Opeongo), all located within the basin. All the samples were analysed for body burdens of total toxaphene and 22 toxaphene congeners. In addition, from each of the Great Lakes sites samples of major invertebrate dietary items, which included Mysis relicta, Diporeia hoyi and plankton, were similarly analysed. Whole lake trout samples, archived at -80 degrees C, were reanalysed to determine historical trends of toxaphene congeners plus carbon and nitrogen stable isotope signatures. The Lake Superior food web consistently had the highest levels of total toxaphene of all the Great Lakes monitored. The primary source of toxaphene to Lake Superior has been identified as atmospheric transport and deposition from sites in the southern US, Mexico and Central America (Hoff, R.M., Strachan, W.M.J., Sweet, C.W., Chan, C.H., Shackelton, M., Bidleman, T.F., Brice, K.A., Burnison, D.A., Cussion, S., Gatz, D.F., Harlin, K., Schroeder, W.H., 1996. Atmospheric deposition of toxic chemicals to the Great Lakes: A review of data through 1994. Atmospheric Environ. 30, 3505-3527). Of the offsystem lakes surveyed. Lake Nipigon, situated due north of Lake Superior and with a Lake Basin area of about 6% of Lake Superior (Hendendorf, C.E., 1982. J. Great Lakes Res. 8(3), 379-412) had total toxaphene levels in lake trout equivalent to about 50% of those found in lake trout from Lake Superior. Temporal trend toxaphene congener analysis was conducted on archived whole fish samples collected over the period 1980 through to the 1990's. Initially a nonachlorobornane congener (Parlar #50) was predominant, with congeners #40, #62 and #21 being the next most prominent in the 1980 samples. Samples from the 1990's showed a significant decline in the presence of lower chlorinated congeners #40 and #21. Analysis of total toxaphene in food webs, indicated elevated levels in lower trophic level species such as Diporeia and Cottus sp. which have a benthic association. The stable isotope temporal trend 13C signature identified a significant shift in the lake trout diet over the period 1993 to 1996.     

Airborne concentrations of toxaphene congeners at Point Petre (Ontario) using gas-chromatography-electron capture negative ion mass spectrometry (GC-ECNIMS).

A reliable analytical method has been developed using GC-ECNIMS for the determination of individual toxaphene congeners in ambient air. To allow a reasonable comparison with previous data for toxaphene reported by Muir and co-workers using GC-ECD, this method has adopted their approach of focussing upon the identification and quantification of specific peaks or clusters ("T" species) typically observed in environmental samples, with the sum of these "T" species then being reported as "total toxaphene". Technical toxaphene has been used as the analytical standard, but independent response factors have been assigned to the target peaks and clusters. Because of the appreciable variability in ECNIMS response shown by individual toxaphene congeners, this is considered to be a reasonable and potentially more accurate procedure than the application of a "single response factor" used by many other workers. The methodology has been used for the determination of toxaphene in air samples collected over the annual cycle in 1992 and then from October 1995 to September 1997 at Point Petre, Ontario. Of the forty-four calibrated components, only 10 were detected in all of the air samples collected over the latter 2-year period. Airborne concentrations of toxaphene (defined as the sum of the calibrated components) range from 0.9 pg/m3 to 10.1 pg/m3. A clear seasonality has been observed, with a summer-to-winter concentration ratio of about 6.     

Determination of toxaphenes in fish and marine mammals

An analytical method for the determination of toxaphene in biological materials using gas chromatography with an electron capture detector (GC-ECD) has been established and validated for three single congeners (chlorinated bornanes (CHB) 26, 50 and 62). The analytical method was based on a method for determination of PCB, DDT and other chlorinated pesticides. To include toxaphene congeners an extra step, adsorption chromatography on silica columns, was introduced to separate the pesticides from PCB. The recovery of CHB-26, 50 and 62 were 97+/-11%, 94+/-10% and 99+/-12%, respectively. Samples from cod, ringed seal and polar bear from the Norwegian arctic environment have been analysed. The levels of CHB-26 and 50 found were 13-55 ng/g fat in cod, 1.3-7.7 ng/g fat in ringed seal and 0.4-119 ng/g fat in polar bear. The levels of CHB-62 were 2.0-13, 0.8-3.4, 0.2-11 ng/g fat in cod, ringed seal and polar bear, respectively.     

The application of standard methods for the determination of toxaphene in environmental media

In the United States, it is necessary to analyze for toxaphene using approved, validated methods acceptable to the regulatory agencies. As a result of an interlaboratory study and technical exchanges among the US EPA Region IV (EPA), the State of Georgia Environmental Protection Division (EPD), and Hercules Incorporated, guidelines for the application of SW-846 Method 8080 were developed. Results of analyses for sludge, soil, and water samples agreed within a percent relative standard deviation (% RSD) range of 6.9-20%. Through continued technical interchanges, guidance for the application of SW-846 Method 8081 has been developed. The results of analyses of fourteen split samples of soil and sediment produced a percent relative standard deviation that ranged from 1.6% to 127%, with an average of 38%. When two unusually divergent results were removed from consideration, the average % RSD reduced to 26%. The results of analyses of split samples show agreement between the EPA laboratory and a Hercules contract laboratory. Therefore, the guidance has achieved its purpose of producing agreement among data from different laboratories so that data reviewers may have assurance that the analytical method has been applied correctly and consistently for the determination of toxaphene in environmental samples.     

Polychlorinated camphenes (toxaphenes), polybrominated diphenylethers and other halogenated organic pollutants in glaucous gull (Larus hyperboreus) from Svalbard and Bjørnøya (Bear Island)

The levels of polychlorinated camphenes (toxaphenes) were investigated in liver samples from 18 glaucous gulls (Larus hyperboreus) from Bj?rn?ya (74 degrees N, 19 degrees E) and four individuals from Longyearbyen (78 degrees N, 15 degrees E). Additionally brominated flame retardants (BFRs), PCBs and chlorinated pesticides were investigated in liver and intestinal contents of 15 of the glaucous gulls from Bj?rn?ya. Of the analysed BFRs only 2,2',4,4'-tetra- and 2,2',4,4',5-pentabrominated diphenylethers (PBDE 47 and 99) could be detected. The concentrations ranged between 2 and 25 ng/g ww. In addition, high resolution measurements with GC/HRMS revealed the existence of several, not quantified, PBDEs and polybrominated biphenyls (PBBs) congeners in the samples. B9-1679 and B8-1413 were the dominating toxaphenes with median concentrations of 8 and 15 ng/g ww. Concentrations of toxaphenes and PBDEs were up to 100-times lower than the concentrations of PCB and some of the pesticides. PCB and p,p/-DDE constituted 90% of the contaminants found.     

Temporal trends of organochlorine contamination in Black Guillemots in Iceland from 1976 to 1996

The levels of several different persistent organochlorines (OCs) in Black Guillemots Cepphus grylle, collected during the summers of 1976-1996 at Breioafj?rour in W-Iceland, were investigated. The levels of about 40 different organochlorines (PCBs, DDTs, chlordanes, toxaphenes, HCH, HCB) were compared with respect to age, sex, fat content, and year of collection. The levels of PCBs correlated very closely with those of DDE, indicating long-range transport as the major source of these contaminants in Iceland, with the ratio PCBs/DDE mostly in the range of 2-5. Unlike the Gyrfalcon Falco rusticolus, the organochlorine levels did not seem to accumulate substantially with age, neither in males nor females. The variation in the levels of OCs at the age of 2 years was even greater than the variation in OC levels over an age range of 12 years. In immature birds the levels of PCBs, DDE, HCB and beta-HCH declined very slowly (T(1/2) from 12 to 20 years) over the years 1976-1996, whereas the levels of alpha-HCH and p,p'-DDT declined much faster. The levels of trans-nonachlor, alpha-chlordane, gamma-chlordane, oxychlordane, and toxaphene did not correlate with the year of collection. As the Black Guillemot is mostly a resident seabird, feeding mainly on small fish and invertebrates, this investigation should give a good indication of the temporal trends of organochlorine pollution at Breioafj?rour, Iceland, during this 20 year period and is likely to reflect baseline trends in the marine environment of the North-Atlantic Ocean.     

Toxaphene in standard solutions and cleaned biota extracts--results of the first QUASIMEME interlaboratory studies. Quality Assurance of Information for Marine Environmental Monitoring in Europe

Two interlaboratory studies on individual toxaphene congeners have been organised by the project Quality Assurance of Information for Marine Environmental Monitoring in Europe (QUASIMEME). Fifteen laboratories analysed two standard solutions in the first study and 13 laboratories analysed a standard solution and two cleaned biota extracts in the second study. The coefficients of variation obtained for the standard solutions were 6-21% and for the cleaned extracts 16-39%. Although the results were comparable to those of other studies, further improvement in the level of agreement between the participating laboratories was considered possible.     

Toxaphene residues from cotton fields in soils and in the coastal environment of Nicaragua

Toxaphene (camphechlor) was intensively used in the cotton growing fields of Nicaragua for decades with application rates as high as 31 kg ha(-1) in 1985. Although the use of this compound has recently been discontinued in the country, its intensive use in the past and its long persistence in soil allowed for the build up of large reservoirs of toxaphene in agriculture soils and a wide dispersal of residues in the environment. Measurements of toxaphene in coastal areas on the coast of the Pacific Ocean show that environmental concentrations are particularly high in the district of Chinandega, the traditional cotton growing region. Toxaphene residues measured in soils attained 44 microg g(-1) (dry weight) while concentrations in lagoon sediments attained 6.9 microg g(-1) (dry weight) near the mouth of the rivers flowing across the agricultural region. Measurements in aquatic biota showed concentrations as high as 1.6 microg g(-1) (dry weight) in the soft tissues of clams. The toxaphene reservoir in soils combined with the obvious persistence of this compound in soils and lagoon sediments allows predicting that toxaphene will remain in the coastal ecosystem at relatively high concentrations for many years. Toxic effects in lagoon fauna are likely to be observed especially in benthic species that may recycle this compound from sediments. Consumption of seafood, in particular of clams (Anadara spp.) from the more contaminated areas, may expose the population to unacceptably high intake of toxaphene, 30 microg d(-1) per person, with the diet.     

Toxaphene in minke whales (Balaenoptera acutorostrata) from the North Atlantic

Toxaphene contamination of minke whales (Balaenoptera acutorostrata) from North Atlantic waters was examined for the first time. Total toxaphene and SigmaCHB (sum of 11 chlorobornanes) concentrations in blubber samples ranged from 170+/-110 and 41+/-39 ng/g lipid weight (l.w.) for female minke whales from southeastern Greenland to 5800+/-4100 and 1100+/-780 ng/g l.w. for males from the North Sea, respectively. Very large variations in toxaphene concentrations among sampling areas were observed suggesting a spatial segregation of minke whales. However, much of the apparent geographical discrimination was explained by the seasonal fluctuation of animal fat mass. Patterns of CHBs in males revealed that recalcitrant CHBs were in higher proportions in animals from the more easterly areas than in animals from the more westerly areas. This trend may be influenced by the predominance of the US, over the European, input of toxaphene to North Atlantic waters.     

Induction of rat hepatic microsomal enzymes by toxaphene pretreatment

Abstract

The effects of pretreatment of rats with toxaphene on hepatic drug metabolizing enzymes and several other parameters of the mixed function oxidase system were investigated. Adult male Sprague‐Dawley rats were fed diets containing 0, 50, 100, 150 and 200 ppm of toxaphene for 14 days. The body weight gain was unaltered as well as the food consumption in all the toxaphene fed groups. There was no change in the weights of brain, kidney, heart, and testes but the liver weight was significantly increased. The thymus weight in all the toxaphene fed groups was decreased. Hydroxylation of pentobarbital and aniline was significantly enhanced in rats exposed to toxaphene. Ethylmorphine‐N‐demethy‐lase activity in the toxaphene treated rats was also elevated. Enhanced hydroxylation of pentobarbital was also evident from the decreased sleeping time following pentobarbital administration. Exposure to toxaphene increased cytochrome P‐450, NADPH‐cytochrome c‐reductase and dehydrogenase in hepatic microsomal fractions. The binding of aniline and hexobarbital to microsomes was also enhanced, suggesting that the intermediate steps in the electron‐transfer system were increased. In conclusion, pretreatment of rats with toxaphene for fourteen days resulted in the induction of the hepatic mixed function oxidase system.     

Residues of organochlorine pesticides in Alabama soils

A survey was made of 36 Alabama agricultural soils to assess residues of formerly used organochlorine pesticides. Compounds determined comprised alpha- and gamma-hexachlorocyclohexane, heptachlor, heptachlor-exo-epoxide, trans- and cis-chlordane, trans-nonachlor, dieldrin, toxaphene, DDT and DDE. Concentrations varied by several orders of magnitude among farms and appeared to be log-normally distributed. Highest concentrations (ng g(-1) dry soil, arithmetic means) were found for toxaphene (285+/-390) and DDTs (p,p'-DDE, 22.7+/-21.4; p,p'-DDT, 24.6+/-30.5; o,p'-DDT, 4.00+/-5.86; p,p'-DDD, 2.40+/-2.41) which were once heavily used in the southern USA. Pesticide residues were not proportional to soil organic carbon content indicating that residue concentrations were a reflection of pesticide application history and dissipation rates rather than air-soil equilibrium. Mean ratios of DDT/DDE in six regions of the state ranged from 0.39 to 1.5, and compound ratios for chlordanes and toxaphene were different from those in the technical mixtures.