Current knowledge indicates that total urinary arsenic is not a suitable biomarker of exposure to toxic, i.e., inorganic, arsenic (iAs), whereas measurement of iAs and its methylated metabolites in urine using speciation analysis provides much more reliable estimates of exposure. The relative proportions of urinary iAs, monomethylarsonate (MA), and dimethylarsinate (DMA) can be used as a measure of methylation capacity, provided that there are no confounding factors such as consumption of food rich in DMA or containing As compounds metabolized to DMA.We analyzed by gradient elution anion-exchange HPLC-ICP-MS (high-performance liquid chromatography-inductively coupled plasma-mass spectrometry) urine samples from 153 residents in Latium (central Italy) chronically exposed to iAs via water and food. Excluding 26 subjects that excreted high concentrations of arsenobetaine (AB) (≥50 μg As/L) due to seafood consumption, iAs and related metabolites summed up about 75 % of total urinary As as measured by ICP-MS. AB and other organoarsenic compounds were detected at low concentrations in all urine samples. Considering all subjects, the sum of iAs and metabolites ranged 2–72 μg/L and relative proportions were iAs 14 %, MA 13 %, and DMA 72 % (median values), with a wide individual variability.In addition to the above arsenocompounds, the analytical method used in this study enabled the detection of dimethylthioarsinic acid (DMTA), which was found to be present in 33 % of the samples at concentrations ranging mostly from trace amounts to ~6 μg As/L. We found that part of the certified DMA content of human urine reference material SRM 2669 was present as DMTA. Four unknown arsenicals were also detected as minor species in a small proportion of samples.
Conference
International IUPAC Symposium on Trace Elements in Food (TEF-4), International Symposium on Trace Elements in Food, TEF, Trace Elements in Food, 4th, Aberdeen, UK, 2011-06-19–2011-06-22
References
1 10.1016/S1470-2045(09)70134-2, K. Straif, L. Benbrahim-Tallaa, R. Baan, Y. Grosse, B. Secretan, F. El Ghissassi, V. Bouvard, N. Guha, C. Freeman, L. Galichet, V. Cogliano, the Working Group WHO/IARC. Lancet Oncol.10, 453 (2009).Search in Google Scholar
2 European Food Safety Authority. Panel on Contaminants in the Food Chain (CONTAM). EFSA J.7, 1351 (2009).10.2903/j.efsa.2009.1351Search in Google Scholar
3 WHO/FAO. In Safety Evaluation of Certain Contaminants in Food, prepared by the Seventy-second meeting of the Joint FAO/WHO Expert Committee on Food Additives (JECFA), pp. 153–316, World Health Organization, Geneva, and Food and Agriculture Organization, Rome (2011).Search in Google Scholar
4 10.1289/ehp.00108393, U. K. Chowdhury, B. K. Biswas, T. R. Chowdhury, G. Samanta, B. K. Mandal, G. C. Basu, C. R. Chanda, D. Lodh, K. C. Saha, S. K. Mukherjee, S. Roy, S. Kabir, Q. Quamruzzaman, D. Chakraborti. Environ. Health Perspect.108, 393 (2000).Search in Google Scholar
5 G. Concha, B. Nermell, M. Vahter. J. Health Popul. Nutr.24, 317 (2006).Search in Google Scholar
6 10.1016/S0300-483X(02)00285-8, M. Vahter. Toxicology181-182, 211 (2002).Search in Google Scholar
7 10.1289/ehp.96104620, C. Hopenhayn-Rich, M. L. Biggs, A. H. Smith, D. A. Kalman, L. E. Moore. Environ. Health Perspect.104, 620 (1996).Search in Google Scholar PubMed PubMed Central
8 10.1289/ehp.9734, K. Schläwicke-Engström, K. Broberg, G. Concha, B. Nermell, M. Warholm, M. Vahter. Environ. Health Perspect.115, 599 (2007).Search in Google Scholar PubMed PubMed Central
9 10.1016/j.envres.2007.08.011, A. L. Lindberg, E. C. Ekstrom, B. Nermell, M. Rahman, B. Lonnerdal, L. A. Persson, M. Vahter. Environ. Res.106, 110 (2008).Search in Google Scholar PubMed
10 P. Heitland, H. D. Koster. J. Anal. Toxicol.32, 308 (2008).10.1093/jat/32.4.308Search in Google Scholar
11 10.1038/jes.2008.32, K. L. Caldwell, R. L. Jones, C. P. Verdon, J. M. Jarrett, S. P. Caudill, J. D. Osterloh. J. Exposure Sci. Environ. Epidemiol.19, 59 (2009).Search in Google Scholar PubMed
12 V. Foà, A. Colombi, M. Maroni, M. Buratti, G. Calzaferri. Sci. Total Environ.34, 241 (1984).10.1016/0048-9697(84)90066-4Search in Google Scholar
13 10.1289/ehp.5838, U. Ranft, P. Miskovic, B. Pesch, P. Jakubis, E. Fabianova, T. Keegan, A. Hergemoller, M. Jakubis, M. J. Nieuwenhuijsen, EXPASCAN Study Group. Environ. Health Perspect.111, 889 (2003).Search in Google Scholar PubMed PubMed Central
14 M. Wilhelm, B. Pesch, R. Wittsiepe, P. Jakubis, P. Miskovic, T. Keegan, M. J. Nieuwenhuijsen, U. Ranft. J. Exposure Sci. Environ. Epidemiol.15, 89 (2005).10.1038/sj.jea.7500350Search in Google Scholar
15 10.1289/ehp.99107663, R. L. Calderon, E. Hudgens, X. C. Le, D. Schreinemachers, D. J. Thomas. Environ. Health Perspect.107, 663 (1999).Search in Google Scholar PubMed PubMed Central
16 10.1039/b513206a, A. L. Lindberg, W. Goessler, E. Gurzau, K. Koppova, P. Rudnai, R. Kumar, T. Fletcher, G. Leonardi, K. Slotov, E. Gheorghiu, M. Vahter. J. Environ. Monit.8, 203 (2006).Search in Google Scholar PubMed
17 M. Vahter, L. Li, B. Nermell, A. Rahman, S. El Arifeen, M. Rahman, L.A. Persson, E. C. Ekstrom. J. Health Popul. Nutr.24, 236 (2006).Search in Google Scholar
18 10.1039/c0em00482k, C. Cascio, A. Raab, R. O. Jenkins, J. Feldmann, A. A. Meharg, P. I. Haris. J. Environ. Monit.13, 257 (2011).Search in Google Scholar PubMed
19 10.1016/j.envres.2010.10.009, A. Navas-Acien, K. A. Francesconi, E. K. Silbergeld, E. Guallar. Environ. Res.111, 110 (2011).Search in Google Scholar PubMed PubMed Central
20 10.1007/s10040-007-0169-x, R. Vivona, E. Preziosi, B. Madé, G. Giuliano. Hydrogeol. J.15, 1183 (2007).Search in Google Scholar
21 10.1007/s10040-008-0401-3, M. Angelone, C. Cremisini, V. Piscopo, M. Proposito, F. Spaziani. Hydrogeol. J.17, 901 (2009).Search in Google Scholar
22 10.1080/02772240903036121, L. Achene, E. Ferretti, L. Lucentini, P. Pettine, E. Veschetti, M. Ottaviani. Toxicol. Environ. Chem.92, 509 (2010).Search in Google Scholar
23 10.1021/jf102084p, F. Cubadda, S. Ciardullo, M. D’Amato, A. Raggi, F. Aureli, M. Carcea. J. Agric. Food Chem.58, 10176 (2010).Search in Google Scholar PubMed
24 10.1039/b402994a, J. J. Sloth, E. H. Larsen, K. Julshamn. J. Anal. At. Spectrom.19, 973 (2004).Search in Google Scholar
25 10.1016/j.envres.2007.08.005, B. Nermell, A. L. Lindberg, M. Rahman, M. Berglund, L. A. Persson, S. El Arifeen, M. Vahter. Environ. Res.106, 212 (2008).Search in Google Scholar PubMed
26 10.1016/j.taap.2006.12.014, R. Raml, A. Rumpler, W. Goessler, M. Vahter, L. Li, T. Ochi, K. A. Francesconi. Toxicol. Appl. Pharmacol.222, 374 (2007).Search in Google Scholar PubMed
27 10.1039/b713145c, S. D. Conklin, M. W. Fricke, P. A. Creed, J. T. Creed. J. Anal. At. Spectrom.23, 711 (2008).Search in Google Scholar
28 10.1039/c0ja00125b, M. D’Amato, F. Aureli, S. Ciardullo, A. Raggi, F. Cubadda. J. Anal. At. Spectrom.26, 207 (2011).Search in Google Scholar
29 10.1016/j.taap.2008.02.001, A. L. Lindberg, M. Rahman, L. A. Persson, M. Vahter. Toxicol. Appl. Pharmacol.230, 9 (2008).Search in Google Scholar PubMed
30 10.1289/ehp.10026, A. L. Lindberg, R. Kumar, W. Goessler, R. Thirumaran, E. Gurzau, K. Koppova, P. Rudnai, G. Leonardi, T. Fletcher, M. Vahter. Environ. Health Perspect.115, 1081 (2007).Search in Google Scholar PubMed PubMed Central
31 10.1016/j.taap.2008.12.019, B. Fängström, J. Hamadani, B. Nermell, M. Grandér, B. Palm, M. Vahter. Toxicol. Appl. Pharmacol.239, 208 (2009).Search in Google Scholar PubMed
32 10.1039/b921588c, C. Newcombe, A. Raab, P. N. Williams, C. Deacon, P. I. Haris, A. A. Meharg, J. Feldmann. J. Environ. Monit.12, 832 (2010).Search in Google Scholar PubMed
33 10.1021/es048150n, A. H. Ackerman, P. A. Creed, A. N. Parks, M. W. Fricke, C. A. Schwegel, J. T. Creed, D. T. Heitkemper, N. P. Vela. Environ. Sci. Technol.39, 5241 (2005).Search in Google Scholar PubMed
34 10.1351/PAC-CON-09-06-08, R. A. Diaz-Bone, T. Van de Wiele. Pure Appl. Chem.82, 409 (2010).Search in Google Scholar
35 A. Navas-Acien, J. G. Umans, B. V. Howard, W. Goessler, K. A. Francesconi, C. M. Crainiceanu, E. K. Silbergeld, E. Guallar. Environ. Health Perspect.117, 1428 (2009).10.1289/ehp.0800509Search in Google Scholar
36 SIVR. Terza Lista dei Valori di Riferimento per Elementi, Composti Organici e loro Metaboliti, con integrazioni sul sito web <http://www.valoridiriferimento.it>, p. 12, Società Italiana Valori di Riferimento, Pavia (2011).Search in Google Scholar
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