Oxidation state specific generation of arsines from methylated arsenicals based on l-cysteine treatment in buffered media for speciation analysis by hydride generation-automated cryotrapping-gas chromatography-atomic absorption spectrometry with the multiatomizer

Tomáš Matoušek, Araceli Hernández-Zavala, Milan Svoboda, Lenka Langrová, Blakely M. Adair, Zuzana Drobná, David J. Thomas, Miroslav Stýblo, Jiří Dědina

Research output: Contribution to journalArticle

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Abstract

An automated system for hydride generation-cryotrapping-gas chromatography-atomic absorption spectrometry with the multiatomizer is described. Arsines are preconcentrated and separated in a Chromosorb filled U-tube. An automated cryotrapping unit, employing nitrogen gas formed upon heating in the detection phase for the displacement of the cooling liquid nitrogen, has been developed. The conditions for separation of arsines in a Chromosorb filled U-tube have been optimized. A complete separation of signals from arsine, methylarsine, dimethylarsine, and trimethylarsine has been achieved within a 60 s reading window. The limits of detection for methylated arsenicals tested were 4 ng l- 1. Selective hydride generation is applied for the oxidation state specific speciation analysis of inorganic and methylated arsenicals. The arsines are generated either exclusively from trivalent or from both tri- and pentavalent inorganic and methylated arsenicals depending on the presence of l-cysteine as a prereductant and/or reaction modifier. A TRIS buffer reaction medium is proposed to overcome narrow optimum concentration range observed for the l-cysteine modified reaction in HCl medium. The system provides uniform peak area sensitivity for all As species. Consequently, the calibration with a single form of As is possible. This method permits a high-throughput speciation analysis of metabolites of inorganic arsenic in relatively complex biological matrices such as cell culture systems without sample pretreatment, thus preserving the distribution of tri- and pentavalent species. © 2007 Elsevier B.V. All rights reserved.
Original languageAmerican English
Pages (from-to)396-406
Number of pages355
JournalSpectrochimica Acta - Part B Atomic Spectroscopy
DOIs
StatePublished - 1 Mar 2008
Externally publishedYes

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cryotrapping
Arsenicals
Atomic absorption spectrometry
cysteine
gas chromatography
Hydrides
Gas chromatography
Gas Chromatography
hydrides
Cysteine
manometers
Spectrum Analysis
Oxidation
oxidation
Liquid nitrogen
Metabolites
Arsenic
Cell culture
spectroscopy
Nitrogen

Cite this

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title = "Oxidation state specific generation of arsines from methylated arsenicals based on l-cysteine treatment in buffered media for speciation analysis by hydride generation-automated cryotrapping-gas chromatography-atomic absorption spectrometry with the multiatomizer",
abstract = "An automated system for hydride generation-cryotrapping-gas chromatography-atomic absorption spectrometry with the multiatomizer is described. Arsines are preconcentrated and separated in a Chromosorb filled U-tube. An automated cryotrapping unit, employing nitrogen gas formed upon heating in the detection phase for the displacement of the cooling liquid nitrogen, has been developed. The conditions for separation of arsines in a Chromosorb filled U-tube have been optimized. A complete separation of signals from arsine, methylarsine, dimethylarsine, and trimethylarsine has been achieved within a 60 s reading window. The limits of detection for methylated arsenicals tested were 4 ng l- 1. Selective hydride generation is applied for the oxidation state specific speciation analysis of inorganic and methylated arsenicals. The arsines are generated either exclusively from trivalent or from both tri- and pentavalent inorganic and methylated arsenicals depending on the presence of l-cysteine as a prereductant and/or reaction modifier. A TRIS buffer reaction medium is proposed to overcome narrow optimum concentration range observed for the l-cysteine modified reaction in HCl medium. The system provides uniform peak area sensitivity for all As species. Consequently, the calibration with a single form of As is possible. This method permits a high-throughput speciation analysis of metabolites of inorganic arsenic in relatively complex biological matrices such as cell culture systems without sample pretreatment, thus preserving the distribution of tri- and pentavalent species. {\circledC} 2007 Elsevier B.V. All rights reserved.",
author = "Tom{\'a}š Matoušek and Araceli Hern{\'a}ndez-Zavala and Milan Svoboda and Lenka Langrov{\'a} and Adair, {Blakely M.} and Zuzana Drobn{\'a} and Thomas, {David J.} and Miroslav St{\'y}blo and Jiř{\'i} Dědina",
year = "2008",
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language = "American English",
pages = "396--406",
journal = "Spectrochimica Acta - Part B Atomic Spectroscopy",
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Oxidation state specific generation of arsines from methylated arsenicals based on l-cysteine treatment in buffered media for speciation analysis by hydride generation-automated cryotrapping-gas chromatography-atomic absorption spectrometry with the multiatomizer. / Matoušek, Tomáš; Hernández-Zavala, Araceli; Svoboda, Milan; Langrová, Lenka; Adair, Blakely M.; Drobná, Zuzana; Thomas, David J.; Stýblo, Miroslav; Dědina, Jiří.

In: Spectrochimica Acta - Part B Atomic Spectroscopy, 01.03.2008, p. 396-406.

Research output: Contribution to journalArticle

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T1 - Oxidation state specific generation of arsines from methylated arsenicals based on l-cysteine treatment in buffered media for speciation analysis by hydride generation-automated cryotrapping-gas chromatography-atomic absorption spectrometry with the multiatomizer

AU - Matoušek, Tomáš

AU - Hernández-Zavala, Araceli

AU - Svoboda, Milan

AU - Langrová, Lenka

AU - Adair, Blakely M.

AU - Drobná, Zuzana

AU - Thomas, David J.

AU - Stýblo, Miroslav

AU - Dědina, Jiří

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N2 - An automated system for hydride generation-cryotrapping-gas chromatography-atomic absorption spectrometry with the multiatomizer is described. Arsines are preconcentrated and separated in a Chromosorb filled U-tube. An automated cryotrapping unit, employing nitrogen gas formed upon heating in the detection phase for the displacement of the cooling liquid nitrogen, has been developed. The conditions for separation of arsines in a Chromosorb filled U-tube have been optimized. A complete separation of signals from arsine, methylarsine, dimethylarsine, and trimethylarsine has been achieved within a 60 s reading window. The limits of detection for methylated arsenicals tested were 4 ng l- 1. Selective hydride generation is applied for the oxidation state specific speciation analysis of inorganic and methylated arsenicals. The arsines are generated either exclusively from trivalent or from both tri- and pentavalent inorganic and methylated arsenicals depending on the presence of l-cysteine as a prereductant and/or reaction modifier. A TRIS buffer reaction medium is proposed to overcome narrow optimum concentration range observed for the l-cysteine modified reaction in HCl medium. The system provides uniform peak area sensitivity for all As species. Consequently, the calibration with a single form of As is possible. This method permits a high-throughput speciation analysis of metabolites of inorganic arsenic in relatively complex biological matrices such as cell culture systems without sample pretreatment, thus preserving the distribution of tri- and pentavalent species. © 2007 Elsevier B.V. All rights reserved.

AB - An automated system for hydride generation-cryotrapping-gas chromatography-atomic absorption spectrometry with the multiatomizer is described. Arsines are preconcentrated and separated in a Chromosorb filled U-tube. An automated cryotrapping unit, employing nitrogen gas formed upon heating in the detection phase for the displacement of the cooling liquid nitrogen, has been developed. The conditions for separation of arsines in a Chromosorb filled U-tube have been optimized. A complete separation of signals from arsine, methylarsine, dimethylarsine, and trimethylarsine has been achieved within a 60 s reading window. The limits of detection for methylated arsenicals tested were 4 ng l- 1. Selective hydride generation is applied for the oxidation state specific speciation analysis of inorganic and methylated arsenicals. The arsines are generated either exclusively from trivalent or from both tri- and pentavalent inorganic and methylated arsenicals depending on the presence of l-cysteine as a prereductant and/or reaction modifier. A TRIS buffer reaction medium is proposed to overcome narrow optimum concentration range observed for the l-cysteine modified reaction in HCl medium. The system provides uniform peak area sensitivity for all As species. Consequently, the calibration with a single form of As is possible. This method permits a high-throughput speciation analysis of metabolites of inorganic arsenic in relatively complex biological matrices such as cell culture systems without sample pretreatment, thus preserving the distribution of tri- and pentavalent species. © 2007 Elsevier B.V. All rights reserved.

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