Electron ionization mass spectral fragmentation study of sulfation derivatives of polychlorinated biphenyls
<p>Abstract</p> <p>Background</p> <p>Polychlorinated biphenyls are persistent organic pollutants that can be metabolized via hydroxylated PCBs to PCB sulfate metabolites. The sensitive and selective analysis of PCB sulfate monoesters by gas chromatography-mass spectrome...
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| Format: | Article |
| Language: | English |
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BMC
2009-03-01
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| Series: | Chemistry Central Journal |
| Online Access: | http://journal.chemistrycentral.com/content/3/1/5 |
| _version_ | 1818765556619149312 |
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| author | Robertson Larry W Li Xueshu Lehmler Hans-Joachim |
| author_facet | Robertson Larry W Li Xueshu Lehmler Hans-Joachim |
| author_sort | Robertson Larry W |
| collection | DOAJ |
| description | <p>Abstract</p> <p>Background</p> <p>Polychlorinated biphenyls are persistent organic pollutants that can be metabolized via hydroxylated PCBs to PCB sulfate metabolites. The sensitive and selective analysis of PCB sulfate monoesters by gas chromatography-mass spectrometry (GC-MS) requires their derivatization, for example, as PCB 2,2,2-trichloroethyl (TCE) sulfate monoesters. To aid in the identification of unknown PCB sulfate metabolites isolated from biological samples, the electron impact MS fragmentation pathways of selected PCB TCE sulfate diesters were analyzed and compared to the fragmentation pathways of the corresponding methoxylated PCBs.</p> <p>Results</p> <p>The most abundant and characteristic fragment ions of PCB TCE sulfate diesters were formed by releasing CHCCl<sub>3</sub>, SO<sub>3</sub>, HCl<sub>2 </sub>and/or CCl<sub>3 </sub>from the TCE sulfate moiety and Cl<sub>2</sub>, HCl, ethyne and chloroethyne from an intermediate phenylcyclopentadienyl cation. The fragmentation pattern depended on the degree of chlorination and the position of the TCE sulfate moiety (i.e., <it>ortho </it>vs. <it>meta/para </it>to the second phenyl ring), but were independent of the chlorine substitution pattern. These fragmentation pathways are similar to the fragmentation pathways of structurally related methoxylated PCBs.</p> <p>Conclusion</p> <p>Knowledge of the fragmentation patterns of PCB TCE sulfate diesters will greatly aid in determining the position of sulfate moiety (<it>ortho </it>vs. <it>meta/para</it>) of unknown PCB sulfate metabolites isolated from environmental or laboratory samples.</p> |
| first_indexed | 2024-12-18T08:19:58Z |
| format | Article |
| id | doaj.art-5283ebd8c89c4c36889ea4a210f783eb |
| institution | Directory Open Access Journal |
| issn | 1752-153X |
| language | English |
| last_indexed | 2024-12-18T08:19:58Z |
| publishDate | 2009-03-01 |
| publisher | BMC |
| record_format | Article |
| series | Chemistry Central Journal |
| spelling | doaj.art-5283ebd8c89c4c36889ea4a210f783eb2022-12-21T21:14:46ZengBMCChemistry Central Journal1752-153X2009-03-0131510.1186/1752-153X-3-5Electron ionization mass spectral fragmentation study of sulfation derivatives of polychlorinated biphenylsRobertson Larry WLi XueshuLehmler Hans-Joachim<p>Abstract</p> <p>Background</p> <p>Polychlorinated biphenyls are persistent organic pollutants that can be metabolized via hydroxylated PCBs to PCB sulfate metabolites. The sensitive and selective analysis of PCB sulfate monoesters by gas chromatography-mass spectrometry (GC-MS) requires their derivatization, for example, as PCB 2,2,2-trichloroethyl (TCE) sulfate monoesters. To aid in the identification of unknown PCB sulfate metabolites isolated from biological samples, the electron impact MS fragmentation pathways of selected PCB TCE sulfate diesters were analyzed and compared to the fragmentation pathways of the corresponding methoxylated PCBs.</p> <p>Results</p> <p>The most abundant and characteristic fragment ions of PCB TCE sulfate diesters were formed by releasing CHCCl<sub>3</sub>, SO<sub>3</sub>, HCl<sub>2 </sub>and/or CCl<sub>3 </sub>from the TCE sulfate moiety and Cl<sub>2</sub>, HCl, ethyne and chloroethyne from an intermediate phenylcyclopentadienyl cation. The fragmentation pattern depended on the degree of chlorination and the position of the TCE sulfate moiety (i.e., <it>ortho </it>vs. <it>meta/para </it>to the second phenyl ring), but were independent of the chlorine substitution pattern. These fragmentation pathways are similar to the fragmentation pathways of structurally related methoxylated PCBs.</p> <p>Conclusion</p> <p>Knowledge of the fragmentation patterns of PCB TCE sulfate diesters will greatly aid in determining the position of sulfate moiety (<it>ortho </it>vs. <it>meta/para</it>) of unknown PCB sulfate metabolites isolated from environmental or laboratory samples.</p>http://journal.chemistrycentral.com/content/3/1/5 |
| spellingShingle | Robertson Larry W Li Xueshu Lehmler Hans-Joachim Electron ionization mass spectral fragmentation study of sulfation derivatives of polychlorinated biphenyls Chemistry Central Journal |
| title | Electron ionization mass spectral fragmentation study of sulfation derivatives of polychlorinated biphenyls |
| title_full | Electron ionization mass spectral fragmentation study of sulfation derivatives of polychlorinated biphenyls |
| title_fullStr | Electron ionization mass spectral fragmentation study of sulfation derivatives of polychlorinated biphenyls |
| title_full_unstemmed | Electron ionization mass spectral fragmentation study of sulfation derivatives of polychlorinated biphenyls |
| title_short | Electron ionization mass spectral fragmentation study of sulfation derivatives of polychlorinated biphenyls |
| title_sort | electron ionization mass spectral fragmentation study of sulfation derivatives of polychlorinated biphenyls |
| url | http://journal.chemistrycentral.com/content/3/1/5 |
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