Characterization of Toxaphene by High Resolution Gas Chromatography Combined with High Resolution Mass Spectrometry and Tandem Mass Spectrometry

Santos, F.J.; Galcerán, M.T.; Caixach, Josep; Rivera, J.; Huguet, X.

doi:10.1002/(sici)1097-0231(19970228)11:4<341::aid-rcm832>3.0.co;2-n

Cited by 10 publications

(5 citation statements)

References 34 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Despite these developments, some chromatographic problems still remain, as observed for polychlorinated terphenyls (PCTs) and toxaphenes, which include over 8557 and 670 compounds in total, respectively. To avoid intrinsic interferences, HRGC-HRMS or HRGC-HRMS-MS, with magnetic sector coupled to quadrupole and resolution higher than 20,000, has been reported [21,22]. Coupling with two-dimensional GC is another way of improving sensitivity and selectivity.…”

Section: Environmental Applications Of Gc-hrmsmentioning

confidence: 99%

Current use of high-resolution mass spectrometry in the environmental sciences

et al. 2012

View full text Add to dashboard Cite

Section: Environmental Applications Of Gc-hrmsmentioning

confidence: 99%

Current use of high-resolution mass spectrometry in the environmental sciences

et al. 2012

View full text Add to dashboard Cite

“…Such inferences can often be identified by a distorted GC signal with an extended baseline. As can be seen from Figure 2B, MS/MS eliminates (11). c Skopp and Oehme (18) Detection Limits.…”

Section: Resultsmentioning

confidence: 93%

“…The loss of 34 u by exchange of Cl by H followed by an elimination of HCl is typical for chlorinated aromatics, even for those not containing H as, for example, the EI mass spectrum of hexachlorocyclopentadiene shows. Both parent ions are generally present in the EI mass spectra of polychlorobornanes independent of the degree of chlorination (3,11,17). Often, a general cleanup procedure is used for toxaphene analysis of biota.…”

Section: Resultsmentioning

confidence: 99%

Analysis of “Total Toxaphene” and Selected Single Congeners in Biota by Ion Trap HRGC−EI−MS/MS Using Congener-Optimized Parent Ion Dissociations

Skopp

Oehme

Chu

et al. 2002

Environ. Sci. Technol.

View full text Add to dashboard Cite

A method for the quantification of selected toxaphene congeners as well as "total toxaphene" was developed based on electron ionization (EI) tandem (MS/MS) ion trap mass spectrometry (MS) and a combination of fragment ion dissociations. Congeners were separated by highresolution gas chromatography. Compared to conventional EI low-resolution MS, a 5-20-fold gain in sensitivity could be obtained for octa-or nonachlorinated compounds such as toxaphene #26 and #62 (according to Parlar nomenclature), allowing for their detection in the low picogram range in biota. In addition, response factors for important congeners such as #26, #32, #40/41, #42, #44, #50, and #62 deviated not more than a factor of 2, which is much less as compared to negative ion chemical ionization. This reduces the risk for systematic errors when determining total toxaphene on the basis of a limited number of reference compounds or the technical mixture. Furthermore, chlordanes and polychlorinated biphenyls did not interfere when applying the proposed MS/MS technique. The applicability of the method was tested by determining both total toxaphene and levels of selected congeners in six Arctic wildlife samples collected from Nunavut, Canada, as well as by repetitive analyses of the SRM 1588 certified reference material.

show abstract

“…Several GC/ECNI-MS spectra of B8-1413 (Parlar #26) have been published 5,21,22 and they showed a different [M-Cl] À to [M-HCl] À ratio. While Santos et al 22 did not record a significant [M-HCl] À fragment ion using high resolution ECNI-MS with isobutane as the reagent gas we found a highly abundant [M-HCl] À fragment ion for B8-1413 (Parlar #26) with the present method. The intensity of the [M-HCl] À fragment ion in the ECNI-MS full scan spectrum of B8-1413 (Parlar #26) was 30% of the [M-Cl] À fragment ion (see Fig.…”

Section: Resultsmentioning

confidence: 99%

On the significance of [M−HCl]− fragment ions in gas chromatography/electron capture negative ionization mass spectra of octachloro compounds of technical toxaphene

Vetter

Luckas

1998

Rapid Commun. Mass Spectrom.

View full text Add to dashboard Cite

À fragment ions in the ECNI mass spectra of octachlorobornanes was studied by monitoring m/z 374 in standards and technical toxaphene. This technique is an interesting tool to identify B8-1413 in complex mixtures. # 1998 John Wiley & Sons, Ltd. Received 23 December 1997; Revised 19 January 1998; Accepted 21 January 1998 Rapid Commun. Mass Spectrom. 12, 312-316 (1998 Toxaphene is one of the world's most produced synthetic pesticides derived from chlorinated hydrocarbons. Extensive use of toxaphene since the 1940s to combat insect pests in combination with its high persistence led to the fact that it is a major organochlorine contaminant in the biosphere. 1Due to its persistence and tendency to accumulate in lipids, toxaphene was banned in the 1970s in Western Europe and in the 1980s in Northern America. 2The complex technical mixture is synthesized by the exhaustive chlorination of camphene. Technical toxaphene contains several hundred compounds with C 10 À backbone, mostly polychlorinated bornanes. 3In 1992 two major recalcitrant compounds of technical toxaphene (CTTs) were isolated from blubber of marine mammals. 4,5 The year after these two compounds and further CTTs were gained as single standards 6 which are now commercially available.First congener specific analyses by GC/ECNI-MS, a high selective and sensitive technique for the quantitation of CTTs, showed that the response factors differed over a wide range 7-9 . CTTs with exclusive 2,2,5,5-substitution in the six-membered ring (C-1 to C-6) had a particularly low response factor. 8,9 This fact aggravates the quantitation of unknown peaks in samples in case of a biomatrix with a changed CTT-pattern such as seal blubber. In a recent publication isolation and structure elucidation of the persistent octachlorobornane 2-endo,3-exo,5-endo, 6-exo,8,8,9,10-octachlorobornane (B8-1412) was described. 10High abundance of B8-1412 was reported in seal blubber, cod livers, harbor porpoise and adelie penguin.10 However, the CTT-patterns of GC/ECNI-MS and GC/ECD chromatograms were significantly different. Particularly, the high abundance of B8-1412 in ECNI-MS was not so pronounced in ECD if compared with the major abundant octachlorobornane 2-endo,3-exo,5-endo,6-exo,8,8,10,10-octachlorobornane (B8-1413 or Parlar #26). Consequently, we studied the structure and response factors of B8-1412, B8-1413 (Parlar #26) and further octachloro-CTT standards and toxaphene. EXPERIMENTAL ChemicalsToxaphene was from Promochem (Wesel, Germany). CTT single standards and standard mixtures were from Dr. Ehrenstorfer (Augsburg, Germany) or Promochem (Wesel, Germany). Structures and abbreviations of the polychlorinated bornanes in this study are listed in Table 1. InstrumentalGC/ECNI-MS investigations were carried out with an HP 5989B MS Engine connected to an HP 5890 II plus gas chromatograph (Hewlett-Packard). Methane (quality 5.0; Linde, Germany) was used as CI reagent gas at an ion source pressure of 1.6 mbar. The system was optimized by manual tuning using m/z 312, m/z 414 and m/z 464 of...

show abstract

Characterization of Toxaphene by High Resolution Gas Chromatography Combined with High Resolution Mass Spectrometry and Tandem Mass Spectrometry

Cited by 10 publications

References 34 publications

Current use of high-resolution mass spectrometry in the environmental sciences

Current use of high-resolution mass spectrometry in the environmental sciences

Analysis of “Total Toxaphene” and Selected Single Congeners in Biota by Ion Trap HRGC−EI−MS/MS Using Congener-Optimized Parent Ion Dissociations

On the significance of [M−HCl]− fragment ions in gas chromatography/electron capture negative ionization mass spectra of octachloro compounds of technical toxaphene

Contact Info

Product

Resources

About