Validated determination of total arsenic species of toxicological interest (arsenite, arsenate and their metabolites) by atomic absorption spectrometry after separation from dietary arsenic by liquid extraction: toxicological applications

Abstract

A validated method for the selective extraction of total As species of toxicological interest (arsenite, arsenate and mono- and dimethylated arsenic species) from urine, followed by atomic absorption spectrometric determination, is described. The mechanisms involved in extraction were studied and the extraction method was optimized. The urine sample was acidified with concentrated HCl and KI and sodium hypophosphite were added. Under these conditions, As species were reduced to their corresponding iodide arsines, extracted with toluene and back-extracted with 1 mmol l^–1 NaOH solution. Only inorganic arsenic and its metabolites in humans (monomethylarsonic and dimethylarsinic acid) were extracted. Arsenobetaine of dietary origin was not extracted. This method can detect if any As increase in urine originates from inorganic As intoxication or only from dietary non-toxic As species such as arsenobetaine.

References

1. L. D. Fitzgerald, in Arsenic, Industrial, Biomedical and Environmental Perspectives, ed. Lederer, W. H., and Fensterheim, R. J., Van Nostrand, New York, 1983, pp. 3–8.
2. J. T. Hindmarsh and R. F. McCurdy, Crit. Rev. Clin. Lab. Sci., 1986, 23, 315.
3. R. S. Braman, Top. Environ. Health, 1983, 6, 141.
4. Clinical Toxicology, ed. Polson, C. J., and Tattersal, R. N., Pitman, London, 1969, pp. 181–184.
5. A. Franzblau and R. Lilis, Arch. Environ. Health, 1989, 44, 385.
6. M. A. Lovell and J. G. Farmer, Hum. Toxicol., 1985, 4, 203.
7. W. Takahashi, K. Pfenninger and L. Wong, Arch. Environ. Health, 1983, 38, 209.
8. R. C. Hopenhayn, M. L. Biggs, A. Fuchs, R. Bergolio, E. E. Telo and A. H. Smith, Epidemiology, 1996, 7, 117.
9. W. Morton, G. Starr, J. Pohl and S. Stoner, Cancer, 1976, 37, 2523.
10. J. G. Farmer and L. R. Johnson, Br. Med. J., 1990, 47, 342.
11. M. Buratti, G. Calzaferri, G. Caravelli, A. Colombi, M. Maroni and V. Foa, Int. J. Environ. Anal. Chem., 1984, 17, 25.
12. N. Yamato, Bull. Environ. Contamin. Toxicol., 1988, 40, 633.
13. M. W. Arbouine and H. K. Wilson, J. Trace Elem. Electrolytes Health Dis., 1992, 6, 153.
14. Food Contamination from Environmental Sources, ed. Nriagu, J. O., and Simmons M. S., Wiley, New York, 1990, pp. 121–139.
15. W. Goessler, W. Maher, K. J. Irgolic, D. Kuehnelt, C. Schlagenhaufen and T. Kaise, Fresenius' J. Anal. Chem., 1997, 359, 434.
16. D. Beauchemin, M. E. Bednas, S. S. Berman, M. W. McLaren, K. W. M. Siu and R. E. Sturgeon, Anal. Chem., 1988, 60, 2209.
17. M. Mingsheng and X. C. Le, Clin. Chem., 1998, 44, 539.
18. D. Heitkemper, J. Creed, J. Caruso and F. L. Fricke, J. Anal. At. Spectrom., 1989, 4, 279.
19. Y. Shibata and M. Morita, Anal. Sci., 1989, 5, 107.
20. P. Bavazzano, A. Perico, K. Rosendahl and P. Apostoli, J. Anal. At. Spectrom., 1996, 11, 521.
21. M. Morita, T. Uehiro and K. Fuwa, Anal. Chem., 1981, 53, 1806.
22. R. Rubio, A. Padro, J. Alberti and G. Rauret, Microchim. Acta, 1992, 109, 39.
23. R. Rubio, A. Padro and G. Rauret, Fresenius' J. Anal. Chem., 1995, 351, 331.
24. X. Zhang, R. Cornelis, J. De Kimpe and L. Mees, Anal. Chim. Acta, 1996, 319, 177.
25. A. Lebouil, S. Notelet, A. Calleux, A. Tutcant and P. Allain, Toxicorama, 1997, 9, 171.
26. G. Charlot, Les Réactions Chimiques en Solution Aqueuse et Caractérisation des Ions, Masson, Paris, 7th edn., 1983, pp. 272–276.
27. P. Pascal, Nouveau Traité de Chimie Minérale, Masson, Paris, 1958, vol. 9, pp. 474–494.
28. V. P. Shah, K. K. Midha, S. Dighe, I. J. McGilveray, J. P. Skelly, A. Yacobi, T. Layloff, C. T. Viswamanda, C. E. Cook, R. D. McDowall, K. A. Pittman and S. Spector, J. Pharm. Sci., 1992, 81, 309.