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

Abstract

We examined the use of high resolution gas chromatography-electron ionization high resolution mass spectrometry (HRGC/EI-HRMS) in determining the toxaphene homologue distribution. Operating parameters such as electron energy, trap current and source temperature were optimized in order to obtain the maximum signal of the [M-C] + and [M-HCl] + • fragment ions of each homologue group. Internal interferences due to the fragment ions from the homologues with one and two additional chlorine atoms were eliminated using EI-HRMS at a resolving power of 10 000 or higher. Tandem mass spectrometry (EI-MS/MS) was used in the fragmentation studies. HRGC/EI-HRMS-selected ion monitoring (SIM) at a resolving power of 10 000 was used to determine the homologue distribution of a commercial toxaphene mixture. This technique gave detection limits of ppb level. The performance of HRGC/EI-HRMS-SIM was compared to HRGC/ECNI-MS using isobutane as a moderating gas.

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

“…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.…”

“…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.…”

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

“…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.…”

“…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.…”

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

“…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.…”

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

“…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.…”

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

“…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.…”

“…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.…”

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

“…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.…”

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

“…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.…”

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

“…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.…”

“…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.…”

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

“…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.…”

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

“…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.…”