An ultra sensitive method for arsenic (As) speciation analysis based on selective hydride generation (HG) with preconcentration by cryotrapping (CT) and inductively coupled plasma- mass spectrometry (ICP-MS) detection is presented. Determination of valence of the As species is performed by selective HG without prereduction (trivalent species only) or with L-cysteine prereduction (sum of tri- and pentavalent species). Methylated species are resolved on the basis of thermal desorption of formed methyl substituted arsines after collection at -196°C. Limits of detection of 3.4, 0.04, 0.14 and 0.10 pg mL-1 (ppt) were achieved for inorganic As, mono-, di- and trimethylated species, respectively, from a 500 μL sample. Speciation analysis of river water (NRC SLRS-4 and SLRS-5) and sea water (NRC CASS-4, CASS-5 and NASS-5) reference materials certified to contain 0.4 to 1.3 ng mL-1 total As was performed. The concentrations of methylated As species in tens of pg mL-1 range obtained by HG-CT-ICP-MS systems in three laboratories were in excellent agreement and compared well with results of HG-CT-atomic absorption spectrometry and anion exchange liquid chromatography- ICP-MS; sums of detected species agreed well with the certified total As content. HG-CT-ICP-MS method was successfully used for analysis of microsamples of exfoliated bladder epithelial cells isolated from human urine. Here, samples of lysates of 25 to 550 thousand cells contained typically tens pg up to ng of iAs species and from single to hundreds pg of methylated species, well within detection power of the presented method. A significant portion of As in the cells was found in the form of the highly toxic trivalent species.

Institute of Analytical Chemistry of the ASCR v v i Veveří 97 602 00 Brno Czech Republic

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Rehman K, Naranmandura H. Metallomics. 2012;4:881–892. PubMed

Francesconi KA, Kuehnelt D. Analyst. 2004;129:373–395. PubMed

Gong ZL, Lu XF, Ma MS, Watt C, Le XC. Talanta. 2002;58:77–96. PubMed

Ammann AA. Am J Anal Chem. 2011;2:27–45.

Komorowicz I, Baralkiewicz D. Talanta. 2011;84:247–261. PubMed

Raab A, Meharg AA, Jaspars M, Genney DR, Feldmann J. J Anal At Spectrom. 2004;19:183–190.

Šlejkovec Z, Falnoga I, Goessler W, van Elteren JT, Raml R, Podgornik H, Èernelè P. Anal Chim Acta. 2008;607:83–91. PubMed

Currier J, Saunders JR, Ding L, Bodnar WM, Cable P, Matoušek T, Creed JT, Stýblo M. J Anal At Spectrom. 2013;2013 doi: 10.1039/C3JA30380B. Accepted Manuscript. PubMed DOI PMC

Stefanka Z, Koellensperger G, Stingeder G, Hann S. J Anal At Spectrom. 2006;21:86–89.

Kumar AR, Riyazuddin P. Int J Environ An Ch. 2007;87:469–500.

Ellwood MJ, Maher WA. J Anal At Spectrom. 2002;17:197–203.

Tseng CM, Amouroux D, Brindle ID, Donard OFX. J Environ Monitor. 2000;2:603–612. PubMed

Wuerfel O, Thomas F, Schulte MS, Hensel R, Diaz-Bone RA. Appl Organomet Chem. 2012;26:94–101.

Diaz-Bone RA, Hitzke M. J Anal At Spectrom. 2008;23:861–870.

Regmi R, Milne BF, Feldmann J. Anal Bioanal Chem. 2007;388:775–782. PubMed

Douillet C, Currier J, Saunders J, Bodnar WM, Matoušek T, Stýblo M. Toxicol App Pharm. 2013;267:11–15. PubMed PMC

Matoušek T, Hernández-Zavala A, Svoboda M, Langerová L, Adair BM, Drobná Z, Thomas DJ, Stýblo M, Dědina J. Spectrochim Acta B. 2008;63:396–406. PubMed PMC

Hernández-Zavala A, Matoušek T, Drobna Z, Paul DS, Walton FS, Adair BM, Dědina J, Thomas DJ, Stýblo M. J Anal At Spectrom. 2007;23:342–351. PubMed PMC

Ding L, Saunders RJ, Drobná Z, Walton FS, Xun P, Thomas DJ, Stýblo M. Toxicol App Pharm. 2012;264:121–130. PubMed PMC

Hernández-Zavala A, Valenzuela OL, Matoušek T, Drobná Z, Dědina J, Garcia-Vargas GG, Thomas DJ, Del Razo LM, Stýblo M. Environ Health Persp. 2008;116:1656–1660. PubMed PMC

Moraes DP, Svoboda M, Matoušek T, Flores EMM, Dědina J. J Anal At Spectrom. 2012;27:1734–1742.

Currier JM, Svoboda M, de Moraes DP, Matoušek T, Dědina J, Stýblo M. Chem Res Toxicol. 2011;24:478–480. PubMed PMC

Currier JM, Svoboda M, Matoušek T, Dědina J, Stýblo M. Metallomics. 2011;3:1347–1354. PubMed PMC

Taurková P, Svoboda M, Musil S, Matoušek T. J Anal At Spectrom. 2011;26:220–223.

Musil S, Matoušek T. Spectrochim Acta B. 2008;63:685–691. PubMed PMC

Massart DL, Vandeginste BG, Buydens LM, De Jong S, Lewi PJ, Smeyers J. Handbook of Chemometrics, Verbeke. 1999. p. 198.

Tseng CM, Amouroux D, Brindle ID, Donard OFX. J Environ Monitor. 2000;2:603–612. PubMed

Hsiung TM, Wang JM. J Anal At Spectrom. 2004;19:923–928.

Nakazato T, Tao H, Taniguchi T, Isshiki K. Talanta. 2002;58:121–132. PubMed

Gong ZL, Lu XF, Cullen WR, Le XC. J Anal At Spectrom. 2001;16:1409–1413.

Hippler J, Zdrenka R, Reichel RAD, Weber DG, Rozynek P, Johnen G, Dopp E, Hirner AV. J Anal At Spectrom. 2011;26:2396–2403.

Schmeisser E, Goessler W, Kienzl N, Francesconi KA. Anal Chem. 2004;76:418–423. PubMed

Ulivo AD’, Dědina J, Mester Z, Sturgeon RE, Wang Q, Welz B. Pure Appl Chem. 2011;83:1283–1340.

Ulivo AD’, Meija J, Mester Z, Pagliano E, Sturgeon R. Anal Bioanal Chem. 2012;66:740–747. PubMed

Sturgeon RE, Francesconi KA. Environ Chem. 2009;6:294–297.

Fate of arsenicals in mice carrying the human AS3MT gene exposed to environmentally relevant levels of arsenite in drinking water

A mass spectrometric study of hydride generated arsenic species identified by direct analysis in real time (DART) following cryotrapping

Direct Speciation Analysis of Arsenic in Whole Blood and Blood Plasma at Low Exposure Levels by Hydride Generation-Cryotrapping-Inductively Coupled Plasma Mass Spectrometry

Speciation analysis of arsenic by selective hydride generation-cryotrapping-atomic fluorescence spectrometry with flame-in-gas-shield atomizer: achieving extremely low detection limits with inexpensive instrumentation