Speciation analysis of arsenic in biological matrices by automated hydride generation-cryotrapping-atomic absorption spectrometry with multiple microflame quartz tube atomizer (multiatomizer)

Araceli Hernández-Zavala, Tomás Matoussek, Zuzana Drobná, David S. Paul, Felecia Walton, Blakely M. Adair, Jiří Dědina, David J. Thomas, Miroslav Stýblo

Research output: Contribution to journalArticle

78 Citations (Scopus)

Abstract

Analyses of arsenic (As) species in tissues and body fluids of individuals chronically exposed to inorganic arsenic (iAs) provide essential information about the exposure level and pattern of iAs metabolism. We have previously described an oxidation state-specific analysis of As species in biological matrices by hydride-generation atomic absorption spectrometry (HG-AAS), using cryotrapping (CT) for preconcentration and separation of arsines. To improve performance and detection limits of the method, HG and CT steps are automated and a conventional flame-in-tube atomizer replaced with a recently developed multiple microflame quartz tube atomizer (multiatomizer). In this system, arsines from AsIII-species are generated in a mixture of Tris-HCl (pH 6) and sodium borohydride. For generation of arsines from both AsIII- and AsV-species, samples are pretreated with l-cysteine. Under these conditions, dimethylthioarsinic acid, a newly described metabolite of iAs, does not interfere significantly with detection and quantification of methylated trivalent arsenicals. Analytical performance of the automated HG-CT-AAS was characterized by analyses of cultured cells and mouse tissues that contained mono- and dimethylated metabolites of iAs. The capacity to detect methylated AsIII- and AsV-species was verified, using an in vitro methylation system containing recombinant rat arsenic (+3 oxidation state) methyltransferase and cultured rat hepatocytes treated with iAs. Compared with the previous HG-CT-AAS design, detection limits for iAs and its metabolites have improved significantly with the current system, ranging from 8 to 20 pg. Recoveries of As were between 78 and 117%. The precision of the method was better than 5% for all biological matrices examined. Thus, the automated HG-CT-AAS system provides an effective and sensitive tool for analysis of all major human metabolites of iAs in complex biological matrices. © The Royal Society of Chemistry 2008.
Original languageAmerican English
Pages (from-to)342-351
Number of pages306
JournalJournal of Analytical Atomic Spectrometry
DOIs
StatePublished - 4 Mar 2008
Externally publishedYes

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Atomizers
Atomic absorption spectrometry
Quartz
Arsenic
Hydrides
Metabolites
Tissue
Arsenicals
Methylation
Body fluids
Metabolism
Cysteine
Rats
Cells
Recovery
Oxidation

Cite this

Hernández-Zavala, Araceli ; Matoussek, Tomás ; Drobná, Zuzana ; Paul, David S. ; Walton, Felecia ; Adair, Blakely M. ; Dědina, Jiří ; Thomas, David J. ; Stýblo, Miroslav. / Speciation analysis of arsenic in biological matrices by automated hydride generation-cryotrapping-atomic absorption spectrometry with multiple microflame quartz tube atomizer (multiatomizer). In: Journal of Analytical Atomic Spectrometry. 2008 ; pp. 342-351.
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abstract = "Analyses of arsenic (As) species in tissues and body fluids of individuals chronically exposed to inorganic arsenic (iAs) provide essential information about the exposure level and pattern of iAs metabolism. We have previously described an oxidation state-specific analysis of As species in biological matrices by hydride-generation atomic absorption spectrometry (HG-AAS), using cryotrapping (CT) for preconcentration and separation of arsines. To improve performance and detection limits of the method, HG and CT steps are automated and a conventional flame-in-tube atomizer replaced with a recently developed multiple microflame quartz tube atomizer (multiatomizer). In this system, arsines from AsIII-species are generated in a mixture of Tris-HCl (pH 6) and sodium borohydride. For generation of arsines from both AsIII- and AsV-species, samples are pretreated with l-cysteine. Under these conditions, dimethylthioarsinic acid, a newly described metabolite of iAs, does not interfere significantly with detection and quantification of methylated trivalent arsenicals. Analytical performance of the automated HG-CT-AAS was characterized by analyses of cultured cells and mouse tissues that contained mono- and dimethylated metabolites of iAs. The capacity to detect methylated AsIII- and AsV-species was verified, using an in vitro methylation system containing recombinant rat arsenic (+3 oxidation state) methyltransferase and cultured rat hepatocytes treated with iAs. Compared with the previous HG-CT-AAS design, detection limits for iAs and its metabolites have improved significantly with the current system, ranging from 8 to 20 pg. Recoveries of As were between 78 and 117{\%}. The precision of the method was better than 5{\%} for all biological matrices examined. Thus, the automated HG-CT-AAS system provides an effective and sensitive tool for analysis of all major human metabolites of iAs in complex biological matrices. {\circledC} The Royal Society of Chemistry 2008.",
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Speciation analysis of arsenic in biological matrices by automated hydride generation-cryotrapping-atomic absorption spectrometry with multiple microflame quartz tube atomizer (multiatomizer). / Hernández-Zavala, Araceli; Matoussek, Tomás; Drobná, Zuzana; Paul, David S.; Walton, Felecia; Adair, Blakely M.; Dědina, Jiří; Thomas, David J.; Stýblo, Miroslav.

In: Journal of Analytical Atomic Spectrometry, 04.03.2008, p. 342-351.

Research output: Contribution to journalArticle

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T1 - Speciation analysis of arsenic in biological matrices by automated hydride generation-cryotrapping-atomic absorption spectrometry with multiple microflame quartz tube atomizer (multiatomizer)

AU - Hernández-Zavala, Araceli

AU - Matoussek, Tomás

AU - Drobná, Zuzana

AU - Paul, David S.

AU - Walton, Felecia

AU - Adair, Blakely M.

AU - Dědina, Jiří

AU - Thomas, David J.

AU - Stýblo, Miroslav

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N2 - Analyses of arsenic (As) species in tissues and body fluids of individuals chronically exposed to inorganic arsenic (iAs) provide essential information about the exposure level and pattern of iAs metabolism. We have previously described an oxidation state-specific analysis of As species in biological matrices by hydride-generation atomic absorption spectrometry (HG-AAS), using cryotrapping (CT) for preconcentration and separation of arsines. To improve performance and detection limits of the method, HG and CT steps are automated and a conventional flame-in-tube atomizer replaced with a recently developed multiple microflame quartz tube atomizer (multiatomizer). In this system, arsines from AsIII-species are generated in a mixture of Tris-HCl (pH 6) and sodium borohydride. For generation of arsines from both AsIII- and AsV-species, samples are pretreated with l-cysteine. Under these conditions, dimethylthioarsinic acid, a newly described metabolite of iAs, does not interfere significantly with detection and quantification of methylated trivalent arsenicals. Analytical performance of the automated HG-CT-AAS was characterized by analyses of cultured cells and mouse tissues that contained mono- and dimethylated metabolites of iAs. The capacity to detect methylated AsIII- and AsV-species was verified, using an in vitro methylation system containing recombinant rat arsenic (+3 oxidation state) methyltransferase and cultured rat hepatocytes treated with iAs. Compared with the previous HG-CT-AAS design, detection limits for iAs and its metabolites have improved significantly with the current system, ranging from 8 to 20 pg. Recoveries of As were between 78 and 117%. The precision of the method was better than 5% for all biological matrices examined. Thus, the automated HG-CT-AAS system provides an effective and sensitive tool for analysis of all major human metabolites of iAs in complex biological matrices. © The Royal Society of Chemistry 2008.

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