HRGC-ECD and HRGC-ECNI-SIM-HRMS quantification of toxaphene residues by six environmentally relevant chlorobornanes as standard

Kimmel, Lenka; Angerhöfer, Daniela; Gill, U. S.; Coelhan, Mehmet; Parlar, Harun

doi:10.1016/s0045-6535(98)00070-8

Cited by 20 publications

(5 citation statements)

References 20 publications

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“…The biotic matrices were similarly described by the congener standard, at ∼55-65% of the total toxaphene peak area. These values are somewhat lower than those reported by others (23), who found that six toxaphene congeners accounted for at least 80-85% of the total toxaphene response. We suggest that this high percentage may be due to a large number of minor components falling below the instrument detection limit.…”

Section: Resultscontrasting

confidence: 71%

Comparison of an Individual Congener Standard and a Technical Mixture for the Quantification of Toxaphene in Environmental Matrices by HRGC/ECNI-HRMS

Braekevelt

Tomy

Stern

2001

Environ. Sci. Technol.

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Both a technical standard and a recently commercially available standard containing 25 congeners were used to quantify toxaphene in a variety of environmental matrices, using high-resolution gas chromatography/electron capture negative ion high-resolution mass spectrometry (HRGC/ ECNI-HRMS). The purpose was to examine the differences between the two standards and to assess how well the congener standard describes the total toxaphene profile. At a resolving power of approximately 11,000 no interferences from other organochlorines were observed. Biotic matrices were enriched in octa- and nonachlorobornanes relative to the technical mixture, whereas abiotic matrices were enriched in hexa- and heptachlorobornanes. The hexa- and heptachlorobornanes were generally overestimated by the weighted response of the technical mixture, whereas the nonachlorobornanes were consistently underestimated. The extent to which the technical mixture over- or underestimates total toxaphene concentrations depends on the distribution of congeners among homologue groups and the abundance of particular congeners. The current 25-congener mixture described only approximately 35-75% of the total toxaphene response: more congeners are needed to adequately describe some matrices. Correction factors were developed that will allow laboratories to report reliable concentrations of individual congeners in samples that were quantified using the technical mixture, but they should be applied with caution, as they may be highly instrument dependent.

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Section: Resultscontrasting

confidence: 71%

Comparison of an Individual Congener Standard and a Technical Mixture for the Quantification of Toxaphene in Environmental Matrices by HRGC/ECNI-HRMS

Braekevelt

Tomy

Stern

2001

Environ. Sci. Technol.

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“…Transformation of B9‐1025. The observation that D. multivorans was able to transform all octa‐ and nonachloro‐CTTs led us to investigate the transformation pathway of B9‐1025, which is a major CTT in fish [30,31]. The B9‐1025 carries a total of four gem ‐Cls, two of which are located on primary carbons and two of which are located on secondary carbons.…”

Section: Resultsmentioning

confidence: 99%

Anaerobic transformation of compounds of technical toxaphene. I. Regiospecific reaction of chlorobornanes with geminal chlorine atoms

Ruppe

Neumann

Vetter

2003

Environmental Toxicology and Chemistry

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Technical toxaphene (Melipax) and the single compounds of technical toxaphene (CTTs) 2,2,5-endo,6-exo,8,8,9,10-octachlorobornane (B8-806), 2,2,5-endo,6-exo, 8,9,9,10-octachlorobornane (B8-809), 2,2,5,5,8,9,9,10,10-nonachlorobornane (B9-1025), 2-endo,3-exo,5-endo,6-exo,8,8,9,10,10-nonochlorobornane (B9-1679), 2-endo,3-exo,5-endo,6-exo,8,9,10,10-octachlorobornane (B8-1414), 2-endo,3-exo,5-endo,6-exo,8,8,9,10-octachlorobornane (B8-1412), and 2-exo,3-endo,5-exo,9,9,10,10-heptachlorobornane (B7-1453) were treated with suspensions of the anaerobic bacterium Dehalospirillum multivorans. After 7 d, more than 50% of technical toxaphene was transformed, and the relative amount of early eluting CTTs increased. After 16 d, only 2-exo,3-endo,6-exo, 8,9,10-hexachlorobornane (B6-923), 2-endo,3-exo,5-endo,6-exo, 8,9,10-heptachlorobornane (B7-1001), and a few minor penta- and hexachloro-CTTs were detected in the samples. The result of the transformation was comparable with observations in naturally contaminated sediments and soil. However, the performance with D. multivorans was more simple and reproducible, as well as faster, than use of soil, sediment, or anaerobic sewage sludge. In agreement with reports in the literature, reductive dechlorination at geminal chlorine atoms (gem-C1s) was found to be the major CTT transformation pathway. Experiments conducted with CTTs and gem-C1s at both primary and secondary carbons clarified that the initial C1 --> H substitution takes place at the secondary carbon C2. Furthermore, the 2-endo-C1 position was preferably substituted with hydrogen. In the case of B8-806, the dechlorination at the secondary carbon C2 was approximately 20-fold faster than the subsequent, slow reduction at the primary carbon C8. The three different formerly unknown heptachloro-CTTs, 2-exo,3-endo,6-exo,8,9,9,10-heptachlorobornane (B7-1473), 2-exo, 3-endo,6-endo,8,9,9,10-hepatchlorobornane (B7-1461), and 2-exo, 3-endo,6-exo,8,8,9,10-heptachlorobornane (B7-1470) were found as intermediates of the B8-806/809 transformation. Treatment of B9-1679 with D. multivorans indicated that gem-C1s on the bridge (C8 and C9) are dechlorinated faster than gem-C1s on the bridgehead (C10).

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“…In SLE belugas, P26, P40/41, P44, P50, and P62 were readily detectable (Table 1), suggesting that these congeners were resistant to the biotransformation in the food web. In fact, these CHBs, among few others, are generally predominant in biota (17,26,38,39). However, enantiomer selective analysis revealed that P40, P41, P44, and P62 could be nonracemic in lower trophic level animals such as fish (40)(41)(42).…”

Section: Resultsmentioning

confidence: 99%

Levels and Temporal Trends of Toxaphene Congeners in Beluga Whales (Delphinapterus leucas) from the St. Lawrence Estuary, Canada

Gouteux

Lebeuf

Muir

et al. 2003

Environ. Sci. Technol.

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Environmentally relevant toxaphene congeners were determined in blubber samples of stranded beluga whales (Delphinapterus leucas) from the St. Lawrence Estuary (SLE), Canada. The purpose of this study was to evaluate the levels and the temporal trends (1988-1999) of a suite of six chlorobornanes (P26, P40/41, P44, P50, and P62) in the SLE belugas. P26 and P50 mean concentrations were in the same range as those reported for animals living in the Arctic environment suggesting that the atmospheric transport represents the main input of toxaphene to the SLE. A general exponential decline of chlorobornane concentrations in belugas was observed, except for P26 and P50 in males. On average, concentrations decreased by a factor of two in 8.5 years during the 1988-1999 time period. This rate of decline is similar to the reduction of toxaphene emission from agricultural soils in the southern United States reported over the same time period. Some differences in decline rates were observed among the studied CHB congeners. For instance, P62 decreased more rapidly than P26 and P50 in both male and female belugas. Several hypotheses were advanced to explain these differences such as selective metabolism of specific chlorobornanes by SLE belugas or their prey. However, a most likely explanation is the selective degradation of the technical product in soils and atmosphere in the source region.

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HRGC-ECD and HRGC-ECNI-SIM-HRMS quantification of toxaphene residues by six environmentally relevant chlorobornanes as standard

Cited by 20 publications

References 20 publications

Comparison of an Individual Congener Standard and a Technical Mixture for the Quantification of Toxaphene in Environmental Matrices by HRGC/ECNI-HRMS

Comparison of an Individual Congener Standard and a Technical Mixture for the Quantification of Toxaphene in Environmental Matrices by HRGC/ECNI-HRMS

Anaerobic transformation of compounds of technical toxaphene. I. Regiospecific reaction of chlorobornanes with geminal chlorine atoms

Levels and Temporal Trends of Toxaphene Congeners in Beluga Whales (Delphinapterus leucas) from the St. Lawrence Estuary, Canada

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