Toxicology Letters 168 (2007) 310–318 Evaluation of the three most commonly used analytical methods for determination of inorganic arsenic and its metabolites in urine Anna-Lena Lindberg a , Walter Goessler b , Margaretha Grand´ er a , Barbro Nermell a , Marie Vahter a,∗ a Institute of Environmental Medicine, Division of Metals and Health, Karolinska Institutet, Box 210, SE-171 77, Stockholm, Sweden b Institute of Chemistry, Analytical Chemistry, Karl-Franzens-University, Universitaetsplatz 1, 8010 Graz, Austria Available online 16 November 2006 Abstract This work compares the three most common analytical methods for determination of inorganic arsenic and its metabolites in urine: high performance liquid chromatography coupled to either inductively coupled plasma mass spectrometry or atomic fluorescence spectrometry via hydride generation (high performance liquid chromatography-hydride generation-inductively coupled plasma mass spectrometry (HPLC-HG-ICPMS) and HPLC-HG-atomic fluorescence spectrometry (AFS), respectively) and atomic absorption spectrometry coupled to HG (HG-atomic absorption spectrometry (AAS)). This was done with the focus to find alternatives to ICPMS, the investment and running costs of which are rather high. Between-laboratory comparison of HPLC-HG-ICPMS and HPLC-HG-AFS showed good agreement for inorganic arsenic, methylarsonate (MA) and dimethylarsinate (DMA) (R 2 = 0.91, R 2 = 0.92 and R 2 = 0.90, respectively, N = 86). Within-laboratory comparisons of HPLC-HG-AFS, HPLC-HG-ICPMS and HG-AAS showed good agreement for all arsenic species and the sum of inorganic arsenic and its metabolites in urine (HPLC-HG-ICPMS versus HPLC-HG-AFS: R 2 = 0.95; HG-AAS versus HPLC-HG-AFS: R 2 = 0.95 and HPLC-HG-ICPMS versus HG-AAS: R 2 = 0.97; N = 89). HPLC-HG-AFS was found to be a simple, but high quality alternative to HPLC-HG-ICPMS for the speciation and quantification of inorganic arsenic and its metabolites in urine at arsenic concentrations above 10 gL -1 . Because of its considerably lower costs compared to HPLC-HG-ICPMS, it may be a good alternative in laboratories where the high cost of ICPMS is not justified in relation to the intended use of the instrument. © 2006 Elsevier Ireland Ltd. All rights reserved. Keywords: Arsenic; Atomic fluorescence spectrometry; Inductively coupled plasma mass spectrometry; Atomic absorption spectrometry; Urine samples 1. Introduction Inorganic arsenic is a potent human carcinogen and several epidemiological studies have shown associations between arsenic exposure and different forms of can- ∗ Corresponding author. Tel.: +46 8 728 75 40; fax: +46 8 33 69 81. E-mail address: Marie.Vahter@ki.se (M. Vahter). cer (IARC, 2004). Arsenic exposure may also cause skin lesions, vascular diseases, liver- and neuro-toxicity and diabetes mellitus (WHO, 2001). In many parts of the world arsenic is naturally occurring in mineral-rich bedrock from which it may leach to the ground water. Exposure to elevated concentrations of inorganic arsenic via drinking water is a major problem, affecting mil- lions of people, in many countries all over the world (WHO, 2001). Rural areas in Bangladesh, West Bengal in India, Inner Mongolia and several countries in South 0378-4274/$ – see front matter © 2006 Elsevier Ireland Ltd. All rights reserved. doi:10.1016/j.toxlet.2006.10.028