Analytical and Bioanalytical Chemistry

, Volume 388, Issue 4, pp 837–847 | Cite as

Determination of total mercury and methylmercury in biological samples by photochemical vapor generation

  • Mariana A. Vieira
  • Anderson S. Ribeiro
  • Adilson J. Curtius
  • Ralph E. Sturgeon
Original Paper

Abstract

Cold vapor atomic absorption spectrometry (CV-AAS) based on photochemical reduction by exposure to UV radiation is described for the determination of methylmercury and total mercury in biological samples. Two approaches were investigated: (a) tissues were digested in either formic acid or tetramethylammonium hydroxide (TMAH), and total mercury was determined following reduction of both species by exposure of the solution to UV irradiation; (b) tissues were solubilized in TMAH, diluted to a final concentration of 0.125% m/v TMAH by addition of 10% v/v acetic acid and CH3Hg+ was selectively quantitated, or the initial digests were diluted to 0.125% m/v TMAH by addition of deionized water, adjusted to pH 0.3 by addition of HCl and CH3Hg+ was selectively quantitated. For each case, the optimum conditions for photochemical vapor generation (photo-CVG) were investigated. The photochemical reduction efficiency was estimated to be ∼95% by comparing the response with traditional SnCl2 chemical reduction. The method was validated by analysis of several biological Certified Reference Materials, DORM-1, DORM-2, DOLT-2 and DOLT-3, using calibration against aqueous solutions of Hg2+; results showed good agreement with the certified values for total and methylmercury in all cases. Limits of detection of 6 ng/g for total mercury using formic acid, 8 ng/g for total mercury and 10 ng/g for methylmercury using TMAH were obtained. The proposed methodology is sensitive, simple and inexpensive, and promotes “green” chemistry. The potential for application to other sample types and analytes is evident.

Keywords

Mercury Methylmercury Speciation Photochemical reduction Vapor generation Formic acid Tetramethylammonium hydroxide 

Notes

Acknowledgement

M. A. Vieira and A.J. Curtius are grateful to the Conselho Nacional de Pesquisas e Desenvolvimento Tecnológico (CNPq) for a research scholarship.

References

  1. 1.
    Leermakers M, Baeyens W, Quevauviller P, Horvat M (2005) Trends Anal Chem 24:383–393CrossRefGoogle Scholar
  2. 2.
    Welz B, Sperling M (1999) Atomic absorption spectrometry. Wiley-VCH, WeinheimGoogle Scholar
  3. 3.
    Ribeiro AS, Vieira MA, Curtius AJ (2004) J Braz Chem Soc 15:825–831Google Scholar
  4. 4.
    Sturman BT (1985) Appl Spectrosc 39:48–56CrossRefADSGoogle Scholar
  5. 5.
    Welz B, Schubert-Jacobs M, Schlemmer G (1988) Fresenius Z Anal Chem 331:324–329CrossRefGoogle Scholar
  6. 6.
    Cai Y (2000) Trends Anal Chem 19:62–66CrossRefGoogle Scholar
  7. 7.
    Gámiz-Gracia L, Luque de Castro MD (1999) J Anal Atom Spectrom 14:1615–1617CrossRefGoogle Scholar
  8. 8.
    Yan X, Ni Z, Guo Q (1993) Anal Chim Acta 272:105–114CrossRefGoogle Scholar
  9. 9.
    Flores EMM, Welz B, Curtius AJ (2001) Spectrochim Acta B 56:1605–1614CrossRefGoogle Scholar
  10. 10.
    Akagi H, Sakagami Y (1972) J Hyg Chem (Jpn) 18:358Google Scholar
  11. 11.
    Akagi H, Takabatake E (1973) Chemosphere 3:131–133CrossRefGoogle Scholar
  12. 12.
    Akagi H, Fujita Y, Takabatake E (1976) Chem Lett 49:1–4CrossRefGoogle Scholar
  13. 13.
    Canario J, Vale C (2004) Environ Sci Technol 38:3901–3907PubMedCrossRefGoogle Scholar
  14. 14.
    Siciliano SD, O’Driscoll NJ, Tordon R, Hill J, Beauchamp S, Lead DRS (2005) Environ Sci Technol 39:1071–1077PubMedCrossRefGoogle Scholar
  15. 15.
    Golimowski J, Golimowska K (1996) Anal Chim Acta 325:111–133CrossRefGoogle Scholar
  16. 16.
    Capelo-Martínez JL, Xímenes-Embún P, Madrid Y, Cámara C (2004) Trends Anal Chem 23:331–340CrossRefGoogle Scholar
  17. 17.
    Guo X, Sturgeon RE, Mester Z, Gardner GJ (2003) Anal Chem 75:2092–2099PubMedCrossRefGoogle Scholar
  18. 18.
    Guo X, Sturgeon RE, Mester Z, Gardner GJ (2003) Environ Sci Technol 37:5645–5650PubMedCrossRefGoogle Scholar
  19. 19.
    Guo X, Sturgeon RE, Mester Z, Gardner GJ (2005) J Anal Atom Spectrom 20:702–708CrossRefGoogle Scholar
  20. 20.
    McSheehy S, Guo X-M, Sturgeon RE, Mester Z (2005) J Anal Atom Spectrom 20:709–716CrossRefGoogle Scholar
  21. 21.
    Guo X, Sturgeon RE, Mester Z, Gardner GJ (2004) Appl Organomet Chem 18:205–211CrossRefGoogle Scholar
  22. 22.
    Guo X, Sturgeon RE, Mester Z, Gardner GJ (2004) Anal Chem 76:2401–2405PubMedCrossRefGoogle Scholar
  23. 23.
    García M, Figueroa R, Lavilla I, Bendicho C (2006) J Anal Atom Spectrom 21:582–587CrossRefGoogle Scholar
  24. 24.
    Wang Q, Liang J, Qiu J, Huang B (2004) J Anal Atom Spectrom 19:715–716CrossRefGoogle Scholar
  25. 25.
    Figueroa R, García M, Lavilla I, Bendicho C (2005) Spectrochim Acta B 60:1556–1563CrossRefGoogle Scholar
  26. 26.
    Sun YC, Chang YC, Su CK (2006) Anal Chem 78:2640–2645PubMedCrossRefGoogle Scholar
  27. 27.
    Wang X, Penkonen SO, Ray AK (2004) Electrochim Acta 49:1435–1444Google Scholar
  28. 28.
    Khalil LB, Rophael MW, Mourad WE (2002) Appl Catal B36:125–130CrossRefGoogle Scholar
  29. 29.
    Zheng C, Li Y, He Y, Ma Q, Hou X (2005) J Anal Atom Spectrom 20:746–750CrossRefGoogle Scholar
  30. 30.
    Li Y, Zheng C, Ma Q, Wu L, Hu C, Hou X (2006) J Anal Atom Spectrom 21:82–85CrossRefGoogle Scholar
  31. 31.
    Bendl RF, Madden JT, Regan AL, Fitzgerald N (2006) Talanta 68:1366–1370CrossRefGoogle Scholar
  32. 32.
    Tao G, Willie SN, Sturgeon RE (1998) Analyst 123:1215–1218PubMedCrossRefGoogle Scholar
  33. 33.
    Nóbrega JA, Santos MC, De Sousa RA, Cadore S, Barnes RM, Tatro M (2006) Spectrochim Acta B 61:465–495CrossRefGoogle Scholar
  34. 34.
    Torres DP, Vieira MA, Ribeiro AS, Curtius AJ (2005) J Anal Atom Spectrom 20:289–294CrossRefGoogle Scholar
  35. 35.
    Scriver C, Kan M, Willie S, Soo C, Birnboim H (2005) Anal Bional Chem 381:1460–1466CrossRefGoogle Scholar
  36. 36.
    Kan M, Willie SN, Scriver C, Sturgeon RE (2006) Talanta 68:1259–1263CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2007

Authors and Affiliations

  • Mariana A. Vieira
    • 1
  • Anderson S. Ribeiro
    • 1
  • Adilson J. Curtius
    • 1
  • Ralph E. Sturgeon
    • 2
  1. 1.Departamento de QuímicaUniversidade Federal de Santa CatarinaFlorianópolisBrazil
  2. 2.Institute for National Measurement StandardsNational Research Council CanadaOttawaCanada

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