Comparison of atomic absorption and fluorescence spectroscopic methods for the routine determination of urinary arsenic

  • Jean-François HeilierEmail author
  • Jean-Pierre Buchet
  • Vincent Haufroid
  • Dominique Lison
Original Article


Objective: Interpretation of urinary arsenic measurements is sometimes difficult because of the absorption of seafood that contains trimethylated arsenic forms (arsenobetaine and arsenocholine). The objective of this study was to develop a rapid and robust technique for the measurement of the sum of inorganic arsenic metabolites. Methods: Measurement of arsenic was performed in urine after hydride generation in acid medium. Using atomic fluorescence spectrometry (AFS) as the detection system, we developed a rapid (one determination in less than 2min) technique using 50 μl urine without pre-treatment. Standardisation was done externally with a mixed standard solution containing inorganic trivalent arsenic (As i III ), inorganic pentavalent arsenic (As i V ), monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) (15/15/12.5/57.5) Results: Samples distributed in the frame of an international comparison programme were used to assess accuracy of the AFS procedure, which gives a linear response up to 50 μg/l and proves more precise [coefficient of variation (CV)< 4% at 5 μg/l] and sensitive than the atomic absorption spectroscopy (AAS) technique using a quartz cell. An additional adaptation that allows the detection of non-directly reducible arsenic forms has also been validated for samples with high arsenic concentrations. Conclusions: The present study demonstrates the superiority of AFS over atomic absorption spectrometry (AAS) in arsenic determination and the interest of online mineralisation prior AFS detection for the determination of arsenic concentration in urine.


Arsenic Atomic fluorescence spectroscopy Atomic absorption spectroscopy Human urine 



This work was supported by the Office for Scientific, Technical and Cultural affairs from the Prime Minister of Belgium. The authors are grateful to B. Stockman for his assistance with the experiments.


  1. Albert R, Horwitz WA (1997) Heuristic derivation of the Horwitz curve. Anal Chem 69:789–790CrossRefGoogle Scholar
  2. Amarasiriwardena CJ, Lupoli N, Potula V, Korrick S, Hu H (1998) Determination of the total arsenic concentration in human urine by inductively coupled plasma mass spectrometry: a comparison of the accuracy of three analytical methods. Analyst 123:441–445CrossRefGoogle Scholar
  3. Aposhian HV, Gurzau ES, Le XC, et al (2000) Occurrence of monomethylarsonous acid in urine of humans exposed to inorganic arsenic. Chem Res Toxicol 13:693–697CrossRefPubMedGoogle Scholar
  4. Broekaert J (2002) Analytical atomic spectrometry with flames and plasmas. Wiley, New YorkGoogle Scholar
  5. Buchet JP, Lauwerys RR, Roels H (1980) Comparison of several methods for the determination of arsenic compounds in water and in urine. Their application for the study of arsenic metabolism and for the monitoring of workers exposed to arsenic. Int Arch Occup Environ Health 46:11–29CrossRefGoogle Scholar
  6. Buchet JP, Lauwerys RR, Roels H (1981) Comparison of the urinary excretion of arsenic metabolites after a single oral dose of sodium arsenite, monomethylarsonate, or dimethylarsinate in man. Int Arch Occup Environ Health 48:71–79CrossRefGoogle Scholar
  7. Buchet JP, Lison D, Ruggeri M, Foa V, Elia G (1996a) Assessment of exposure to inorganic arsenic, a human carcinogen, due to the consumption of seafood. Arch Toxicol 70:773–778CrossRefGoogle Scholar
  8. Buchet JP, Pauwels J, Lauwerys RR (1996b) Assessment of exposure to inorganic arsenic following ingestion of marine organisms by volunteers. Environ Res 66:44–51Google Scholar
  9. Col M, Col C, Soran A, Sayli BS, Ozturk S (1999) Arsenic-related Bowen’s disease, palmar keratosis, and skin cancer. Environ Health Perspect 107:687–689Google Scholar
  10. van Elteren JT, Slejkovec Z (1997) Ion-exchange separation of eight arsenic compounds by high-performance liquid chromatography-UV decomposition-hydride generation-atomic fluorescence spectrometry and stability tests for food treatment procedures. J Chromatogr A. 789:339–348CrossRefGoogle Scholar
  11. Enterline PE, Day R, Marsh GM (1995) Cancers related to exposure to arsenic at a copper smelter. Occup Environ Med 52:28–32Google Scholar
  12. Feldmann J, Lai VW, Cullen WR, Ma M, Lu X, Le XC (1999) Sample preparation and storage can change arsenic speciation in human urine. Clin Chem 45:1988–1997PubMedGoogle Scholar
  13. Francesconi KA, Kuehnelt D (2004) Determination of arsenic species: a critical review of methods and applications, 2000–2003. Analyst 129:373–395PubMedGoogle Scholar
  14. Gomez-Ariza JL, Sanchez-Rodas D, Beltran R, Corns W, Stockwel P (1998) Evaluation of atomic fluorescence spectrometry as a sensitive detection technique for arsenic speciation. Appl Organometal Chem 12:439–447CrossRefGoogle Scholar
  15. Heinrich-Ramm R, Mindt-Prufert S, Szadkowski D (2001) Arsenic species excretion in a group of persons in northern Germany—contribution to the evaluation of reference values. Int J Hyg Environ Health 203:475–477Google Scholar
  16. Henry RJ (1965) Clinical chemistry: principles and technics. Harper and Row, New YorkGoogle Scholar
  17. Inczedy J, Lengyel T, Ure AM (1998) Compendium of analytical nomenclature (definitive rules 1997), IUPAC chemical nomenclature series, 3rd edn. Blackwell, OxfordGoogle Scholar
  18. Lauwerys R, Hoet P (2001) Biological monitoring of exposure to inorganic and organometallic substances. In: Lauwerys R, Hoet P (eds) Industrial chemical exposure: guidelines for biological monitoring. Lewis, Boca Raton, pp 5–100Google Scholar
  19. Le XC, Cullen WR, Reimer KJ (1994) Human urinary arsenic excretion after one-time ingestion of seaweed, crab, and shrimp. Clin Chem 40:617–624Google Scholar
  20. Nickson R, McArthur J, Burgess W, Ahmed KM, Ravenscroft P, Rahman M (1998) Arsenic poisoning of Bangladesh groundwater. Nature 395:338CrossRefPubMedGoogle Scholar
  21. Norin H, Vahter M (1981) A rapid method for the selective analysis of total urinary metabolites of inorganic arsenic. Scand J Work Environ Health 7:38–44Google Scholar
  22. Petrick JS, Ayala-Fierro F, Cullen WR, Carter DE, Vasken AH (2000) Monomethylarsonous acid (MMA(III)) is more toxic than arsenite in Chang human hepatocytes. Toxicol Appl Pharmacol 163:203–207CrossRefPubMedGoogle Scholar
  23. Smith AH, Lingas EO, Rahman MM (2000) Contamination of drinking-water by arsenic in Bangladesh: a public health emergency. Bull World Health Organ 78:1093–1103PubMedGoogle Scholar

Copyright information

© Springer-Verlag 2005

Authors and Affiliations

  • Jean-François Heilier
    • 1
    Email author
  • Jean-Pierre Buchet
    • 1
  • Vincent Haufroid
    • 1
  • Dominique Lison
    • 1
  1. 1.Industrial Toxicology and Occupational Medicine Unit, Faculty of MedicineUniversité catholique de LouvainBrusselsBelgium

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