Analytical and Bioanalytical Chemistry

, Volume 385, Issue 2, pp 367–376 | Cite as

Human metabolism of arsenolipids present in cod liver

  • Ernst Schmeisser
  • Walter Goessler
  • Kevin A. Francesconi
Original Paper


We report results from the first investigation of the human metabolism of arsenic-containing lipids (arsenolipids), significant arsenic constituents of some seafood products. Two male volunteers ingested canned cod liver and the arsenic metabolites in their urine were monitored by high-performance liquid chromatography inductively coupled plasma mass spectrometry over a 66-h period. Volunteer A consumed 85 g (wet mass) of cod liver containing a total of approximately 120 μg arsenic, 77% of which was present as arsenolipids, and volunteer B consumed 85 g (wet mass) of cod liver, 25% of which was present as arsenolipids, together with 20 g of cod liver oil, containing a total of about 180 μg arsenic. The structures of the arsenolipids are currently unknown, whereas the majority of the non-lipid arsenic in the cod liver was identified as arsenobetaine, which was excreted unchanged. The arsenolipids were rapidly metabolised to water-soluble compounds and excreted in the urine; peak arsenic concentrations were recorded between 7 and 15 h (volunteer A) and between 6.5 and 15 h (volunteer B), and by the end of the experiment about 90% of the ingested arsenic had been accounted for in the urine for both volunteers. The major arsenolipid metabolite was dimethylarsinate (DMA), constituting 73% (volunteer A) or 41% (volunteer B) of the total urinary arsenic, and most of the remaining arsenolipid-derived arsenic, constituting about 10% (volunteer A) and 5% (volunteer B), comprised four novel arsenic-containing fatty acids, namely oxo-dimethylarsenopropanoic acid, thio-dimethylarsenopropanoic acid, oxo-dimethylarsenobutanoic acid, and thio-dimethylarsenobutanoic acid. Unchanged arsenobetaine (15% for volunteer A and 51% for volunteer B) made up the remaining urinary arsenic together with trace quantities of other, mostly unknown, arsenicals. In a second experiment (volunteer A only), performed with pure cod liver oil, which contains only arsenolipids, DMA and the same four arsenic fatty acids were excreted in the urine. The study shows that arsenolipids in cod liver are bioavailable, and that they are quickly biotransformed to several water-soluble arsenicals, the structures of which suggest that the native arsenolipids contain a dimethylarsine oxide moiety.


Arsenolipids Biotransformation Arsenic speciation Urine metabolites 


  1. 1.
    Vahter M (2002) Toxicology 181:211–217PubMedCrossRefGoogle Scholar
  2. 2.
    National Research Council (2001) Arsenic in drinking water. National Academic, Washington, DCGoogle Scholar
  3. 3.
    Francesconi KA, Kuehnelt D (2002) In: Frankenberger WT (ed) Environmental chemistry of arsenic. Dekker, New York, pp 51–94Google Scholar
  4. 4.
    Schmeisser E, Goessler W, Kienzl N, Francesconi KA (2005) Analyst 6:948–955CrossRefGoogle Scholar
  5. 5.
    Morita M, Shibata Y (1988) Chemosphere 17:1147–1152CrossRefGoogle Scholar
  6. 6.
    Lunde G (1977) Environ Health Perspect 19:47–52PubMedCrossRefGoogle Scholar
  7. 7.
    Edmonds JS, Shibata Y, Francesconi KA, Yoshinaga J, Morita M (1991) Sci Total Environ 122:321–335CrossRefGoogle Scholar
  8. 8.
    Hanaoka K, Goessler W, Yoshida K, Fujitaka Y, Kaise T, Irgolic KJ (1999) Appl Organomet Chem 13:765–770CrossRefGoogle Scholar
  9. 9.
    Hanaoka K, Tanaka Y, Nagata Y, Yoshida K, Kaise T (2001) Appl Organomet Chem 15:299–305CrossRefGoogle Scholar
  10. 10.
    Ebisuda K, Kunito T, Fujihara J, Kubota R, Shibata Y, Tanabe S (2003) Talanta 61:779–787CrossRefGoogle Scholar
  11. 11.
    Devalla S, Feldmann J (2003) Appl Organomet Chem 17:906–912CrossRefGoogle Scholar
  12. 12.
    Brown MR, Newton D, Pickford CJ, Sherlock JC (1990) Hum Exp Toxicol 9:41–46PubMedCrossRefGoogle Scholar
  13. 13.
    Le XC, Cullen WR, Reimer KJ (1994) Clin Chem 40:617–624PubMedGoogle Scholar
  14. 14.
    Ma MS, Le XC (1998) Clin Chem 44:539–550PubMedGoogle Scholar
  15. 15.
    Francesconi KA, Tanggaard R, McKenzie CJ, Goessler W (2002) Clin Chem 48:92–101PubMedGoogle Scholar
  16. 16.
    Van Hulle M, Zhang C, Schotte B, Mees L, Vanhaecke F, Vanholder R, Zhang XR, Cornelis R (2004) J Anal At Spectrom 19:58–64CrossRefGoogle Scholar
  17. 17.
    Raml R, Goessler W, Traar P, Ochi T, Francesconi KA (2005) Chem Res Toxicol 18:1444–1450PubMedCrossRefGoogle Scholar
  18. 18.
    Schmeisser E, Rumpler A, Kollroser M, Rechberger G, Goessler W, Francesconi KA (2006) Angew Chem Int Ed Engl 45:150–154CrossRefGoogle Scholar
  19. 19.
    Merijanian A, Zingaro RA (1966) Inorg Chem 5:187–191CrossRefGoogle Scholar
  20. 20.
    McShane WJ (1982) PhD thesis, Texas A&M UniversityGoogle Scholar
  21. 21.
    Irgolic KJ, Junk T, Kos K, McShane WT, Pappalardo GC (1987) Appl Organomet Chem 1:403–412CrossRefGoogle Scholar
  22. 22.
    Francesconi KA, Edmonds JS, Stick R (1992) J Chem Soc Perkin Trans 1:1349–1357CrossRefGoogle Scholar
  23. 23.
    Schmeisser E, Raml R, Francesconi KA, Kuehnelt D, Lindberg AL, Soeroes C, Goessler W (2004) Chem Commun 16:1824–1825CrossRefGoogle Scholar
  24. 24.
    Kuehnelt D, Goessler W, Francesconi KA (2002) Rapid Commun Mass Spectrom 17:654–659CrossRefGoogle Scholar
  25. 25.
    Schmeisser E, Goessler W, Kienzl N, Francesconi K (2004) Anal Chem 76:418–423PubMedCrossRefGoogle Scholar
  26. 26.
    Sloth JJ, Larsen EH, Julshamn K (2005) Rapid Commun Mass Spectrom 19:227–235PubMedCrossRefGoogle Scholar
  27. 27.
    Hansen HR, Pickford R, Thomas-Oates J, Jaspars M, Feldmann J (2004) Angew Chem Int Ed Engl 43:337–340PubMedCrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2006

Authors and Affiliations

  • Ernst Schmeisser
    • 1
  • Walter Goessler
    • 1
  • Kevin A. Francesconi
    • 1
  1. 1.Institute of Chemistry—Analytical ChemistryKarl Franzens University GrazGrazAustria

Personalised recommendations