Skip to main content
SpringerLink
Log in

Speciation analysis of arsenic in seafood and seaweed: Part II—single laboratory validation of method

  • Research Paper
  • Published:
Analytical and Bioanalytical Chemistry Aims and scope Submit manuscript

Abstract

Single laboratory validation of a method for arsenic speciation analysis in seafood and seaweed is presented. The method is based on stepwise extraction of water-soluble and non-polar arsenic with hot water and a mixture of dichloromethane and methanol, respectively. While the water-soluble arsenicals were speciated by anion and cation exchange liquid chromatography inductively coupled plasma mass spectrometry (LC-ICP-MS), the non-polar arsenicals were collectively determined by ICP-MS after digestion in acid. The performance characteristics and broad application of the method were evaluated by analyzing eight commercial samples (cod, haddock, mackerel, crab, shrimp, geoduck clam, oyster, and kombu) and four reference materials (fish protein (DORM-4), lobster hepatopancreas (TORT-3), mussel tissue (SRM 2976), and hijiki seaweed (CRM 7405-a)) representing finfish, crustaceans, molluscs, and seaweed. Matrices spiked at three levels in duplicates were also analyzed. The stepwise extraction provided 76–106% extraction of the total arsenic from the test materials. The method demonstrated satisfactory repeatability for analysis of replicate extracts prepared over several days. The accuracy of the method was evaluated by analyzing reference materials certified for both total arsenic and a few arsenicals; the experimental results were 90–105% of the certified values. Comparison between the total water-soluble arsenic and the sum of the concentrations of the chromatographed species gave 80–92% mass balance. While spike recoveries of most arsenicals were in the acceptance range set by CODEX, a few species spiked into cod, haddock, and shrimp were poorly recovered due to transformation to other forms. After thorough investigations, strategies were devised to improve the recoveries of these species by averting their transformations. Limits of quantification (LOQ) for the extraction and quantification of 16 arsenicals using the current method were in the range 6–16 ng g−1 arsenic.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3

Similar content being viewed by others

References

  1. Larsen R, Eilertsen K-E, Elvevoll EO. Health benefits of marine foods and ingredients. Biotechnol Adv. 2011;29:508–18.

    Article  CAS  PubMed  Google Scholar 

  2. Molin M, Ulven SM, Meltzer HM, Alexander J. Arsenic in the human food chain, biotransformation and toxicology—review focusing on seafood arsenic. J Trace Elem Med Biol. 2015;31:249–59.

    Article  CAS  PubMed  Google Scholar 

  3. Francesconi KA. Arsenic species in seafood: origin and human health implication. Pure Appl Chem. 2010;82:373–81.

    Article  CAS  Google Scholar 

  4. Taylor V, Goodale B, Raab A, Schwerdtle T, Reimer K, Conklin S, et al. Human exposure to organic arsenic species from seafood. Sci Total Environ. 2017;580:266–82.

    Article  CAS  PubMed  Google Scholar 

  5. Kaise T, Watanabe S, Itoh K. The acute toxicity of arsenobetaine. Chemosphere. 1985;14:1327–32.

    Article  CAS  Google Scholar 

  6. Feldmann J, Krupp EM. Critical review or scientific opinion paper: arsenosugars—a class of benign arsenic species or justification for developing partly speciated arsenic fractionation in foodstuffs? Anal Bioanal Chem. 2011;399:1735–41.

    Article  CAS  PubMed  Google Scholar 

  7. World Health Organization, International Agency for Research on Cancer (IARC Monographs 100), A review of human carcinogens. C. Metals, arsenic, dusts and fibres, 2012, Lyon, France.

  8. Francesconi KA, Tanggaard R, McKenzie CJ, Goessler W. Arsenic metabolites in human urine after ingestion of an arsenosugar. Clin Chem. 2002;48:92–101.

    CAS  PubMed  Google Scholar 

  9. Hulle M, Zhang C, Schotte B, Mees L, Vanhaecke F, Vanholder R, et al. Identification of some arsenic species in human urine and blood after ingestion of Chinese seaweed Laminaria. J Anal At Spectrom. 2004;19:58–64.

    Article  CAS  Google Scholar 

  10. Andrewes P, Demarini DM, Funasaka K, Wallace K, Lai VWM, Sun H, et al. Do arsenosugars pose a risk to human health? The comparative toxicities of a trivalent and pentavalent arsenosugar. Environ Sci Technol. 2004;38:4140–8.

    Article  CAS  PubMed  Google Scholar 

  11. Schmeisser E, Goessler W, Francesconi KA. Human metabolism of arsenolipids present in cod liver. Anal Bioanal Chem. 2006;385:367–76.

    Article  CAS  PubMed  Google Scholar 

  12. Meyer S, Matissek M, Muller SM, Taleshi MS, Ebert F, Francesconi KA, et al. In vitro toxicological characterization of three arsenic-containing hydrocarbons. Metallomics. 2014;6:1023–33.

    Article  CAS  PubMed  Google Scholar 

  13. Sele V, Sloth JJ, Lundebye A-K, Larsen EH, Berntssen MHG, Amlund H. Arsenolipids in marine oils and fats: a review of occurrence, chemistry and future research needs. Food Chem. 2012;133:618–30.

    Article  CAS  Google Scholar 

  14. Francesconi KA, Kuehnelt D. Determination of arsenic species: a critical review of methods and applications, 2000–2003. Analyst. 2004;129:373–95.

    Article  CAS  PubMed  Google Scholar 

  15. Maher WA, Ellwood MJ, Krikowa F, Raber G, Foster S. Measurement of arsenic species in environmental, biological fluids and food samples by HPLC-ICPMS and HPLC-HG-AFS. J Anal At Spectrom. 2015;30:2129–83.

    Article  CAS  Google Scholar 

  16. Larsen EH, Engman J, Sloth JJ, Hansen M, Jorhem L. Determination of inorganic arsenic in white fish using microwave-assisted alkaline alcoholic sample dissolution and HPLC-ICP-MS. Anal Bioanal Chem. 2005;381:339–46.

    Article  CAS  PubMed  Google Scholar 

  17. Pétursdóttir ÁH, Gunnlaugsdóttir H, Krupp EM, Feldmann J. Inorganic arsenic in seafood: does the extraction method matter? Food Chem. 2014;150:353–9.

    Article  CAS  PubMed  Google Scholar 

  18. Wahlen R, McSheehy S, Scriver C, Mester Z. Arsenic speciation in marine certified reference materials part 2. The quantification of water-soluble arsenic species by high-performance liquid chromatography-inductively coupled plasma mass spectrometry. J Anal At Spectrom. 2004;19:876–82.

    Article  CAS  Google Scholar 

  19. Ackley KL, B’Hymer C, Sutton KL, Caruso JA. Speciation of arsenic in fish tissue using microwave-assisted extraction followed by HPLC-ICP-MS. J Anal At Spectrom. 1999;14:845–50.

    Article  CAS  Google Scholar 

  20. Kuehnelt D, Irgolic KJ, Goessler W. Comparison of three methods for extraction of arsenic compounds from NRCC standard reference material DORM-2 and the brown alga Hijiki fuziforme. Appl Organomet Chem. 2001;15:445–56.

    Article  CAS  Google Scholar 

  21. Reyes LH, Mar JLG, Rahman GMM, Seybert B, Fahrenholz T, Kingston HM. Simultaneous determination of arsenic and selenium species in fish tissues using microwave-assisted enzymatic extraction and ion chromatography–inductively coupled plasma mass spectrometry. Talanta. 2009;78:983–90.

    Article  CAS  PubMed  Google Scholar 

  22. Leufroy A, Noël L, Dufailly V, Beauchemin D, Guérin T. Determination of seven arsenic species in seafood by ion exchange chromatography coupled to inductively coupled plasma-mass spectrometry following microwave assisted extraction: method validation and occurrence data. Talanta. 2011;83:770–9.

    Article  CAS  PubMed  Google Scholar 

  23. Zmozinski AV, Llorente-Mirandes T, López-Sánchez JF, da Silva MM. Establishment of a method for determination of arsenic species in seafood by LC-ICP-MS. Food Chem. 2015;173:1073–82.

    Article  CAS  PubMed  Google Scholar 

  24. Wolle MM, Conklin SD. Speciation analysis of arsenic in seafood and seaweed: part I—evaluation and optimization of methods. Anal Bioanal Chem. https://doi.org/10.1007/s00216-018-0906-0

  25. US FDA Office of Foods and Veterinary Medicine, Guidelines for validation of chemical methods for the FDA Foods and Veterinary Medicine Program, 2nd ed., April 2015 (https://www.fda.gov/downloads/ScienceResearch/FieldScience/UCM273418.pdf).

  26. US FDA Elemental Analysis Manual for Food and Related Products, Section 4.7. Inductively Coupled Plasma-Mass Spectrometric Determination of Arsenic, Cadmium, Chromium, Lead, Mercury, and Other Elements in Food Using Microwave Assisted Digestion, Version 1.1, March 2015 (https://www.fda.gov/Food/FoodScienceResearch/LaboratoryMethods/ucm2006954.htm).

  27. US FDA Elemental Analysis Manual for Food and Related Products, Section 3.2. Terminology, September 2015 (https://www.fda.gov/Food/FoodScienceResearch/LaboratoryMethods/ucm2006954.htm).

  28. Sloth JJ, Larsen EH, Julshamn K. Selective arsenic speciation analysis of human urine reference materials using gradient elution ion-exchange HPLC-ICP-MS. J Anal At Spectrom. 2004;19:973–8.

    Article  CAS  Google Scholar 

  29. Codex Alimentarius Commission, Procedural Manual, 24th ed., 2015, Rome, Italy.

  30. US FDA Elemental Analysis Manual for Food and Related Products, Section 4.10. High Performance Liquid Chromatography-Inductively Coupled Plasma-Mass Spectrometric Determination of Four Arsenic Species in Fruit Juice, Version 1.0, July 2013 (https://www.fda.gov/Food/FoodScienceResearch/LaboratoryMethods/ucm2006954.htm).

  31. US FDA Elemental Analysis Manual for Food and Related Products, Section 4.11. Arsenic Speciation in Rice and Rice Products Using High Performance Liquid Chromatography-Inductively Coupled Plasma-Mass Spectrometric Determination, Version Draft 1.1, November 2012 (https://www.fda.gov/Food/FoodScienceResearch/LaboratoryMethods/ucm2006954.htm).

  32. Rey NA, Howarth OW, Pereira-Maia EC. Equilibrium characterization of the as(III)–cysteine and the as(III)–glutathione systems in aqueous solution. J Inorg Biochem. 2004;98:1151–9.

    Article  CAS  PubMed  Google Scholar 

  33. Jiang G, Gong Z, Li X-F, Cullen WR, Le XC. Interaction of trivalent arsenicals with metallothioneins. Chem Res Toxicol. 2003;16:873–80.

    Article  CAS  PubMed  Google Scholar 

  34. Lu M, Wang H, Li X-F, Lu X, Cullen WR, Arnold LL, et al. Evidence of hemoglobin binding to arsenic as a basis for the accumulation of arsenic in rat blood. Chem Res Toxicol. 2004;17:1733–42.

    Article  CAS  PubMed  Google Scholar 

  35. Wang Z, Zhang H, Li X-F, Le XC. Study of interactions between arsenicals and thioredoxins (human and E. coli) using mass spectrometry. Rapid Commun Mass Spectrom. 2007;21:3658–66.

    Article  CAS  PubMed  Google Scholar 

  36. Winther JR, Thorpe C. Quantification of thiols and disulfides. Biochim Biophys Acta. 1840;2014:838–46.

    Google Scholar 

  37. Llorente-Mirandes T, Calderón J, López-Sánchez JF, Centrich F, Rubio R. A fully validated method for the determination of arsenic species in rice and infant cereal products. Pure Appl Chem. 2012;84:225–38.

    Article  CAS  Google Scholar 

  38. Ruttens A, Blanpain AC, De Temmerman L, Waegeneers N. Arsenic speciation in food in Belgium, part 1: fish, molluscs and crustaceans. J Geochem Explor. 2012;121:55–61.

    Article  CAS  Google Scholar 

  39. Cao X, Hao C, Wang G, Yang H, Chen D, Wang X. Sequential extraction combined with HPLC–ICP-MS for As speciation in dry seafood products. Food Chem. 2009;113:720–6.

    Article  CAS  Google Scholar 

  40. Amayo KO, Raab A, Krupp EM, Marschall T, Horsfall M Jr, Feldmann J. Arsenolipids show different profiles in muscle tissues of four commercial fish species. J Trace Elem Med Biol. 2014;28:131–7.

    Article  CAS  PubMed  Google Scholar 

  41. Glabonjat RA, Raber G, Jensen KB, Ehgartner J, Francesconi KA. Quantification of arsenolipids in the certified reference material NMIJ 7405-a (Hijiki) using HPLC/mass spectrometry after chemical derivatization. Anal Chem. 2014;86:10282–7.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  42. Argese E, Bettiol C, Rigo C, Bertini S, Colomban S, Ghetti PF. Distribution of arsenic compounds in Mytilus galloprovincialis of the Venice lagoon (Italy). Sci Total Environ. 2005;348:267–77.

    Article  CAS  PubMed  Google Scholar 

Download references

Acknowledgements

The authors thank Oak Ridge Institute for Science and Education (ORISE) for financial support. Sarah Stadig (Center for Food Safety and Applied Nutrition, FDA) is acknowledged for barcoding the seafood samples, and Dr. Kevin Kubachka (Forensic Chemistry Center, FDA) for kindly providing standards of arsenosugars.

Author information

Authors and Affiliations

  1. Division of Bioanalytical Chemistry, Office of Regulatory Science, Center for Food Safety and Applied Nutrition, US Food and Drug Administration, 5001 Campus Drive, College Park, MD, 20740, USA

    Mesay Mulugeta Wolle & Sean D. Conklin

Authors
  1. Mesay Mulugeta Wolle
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Sean D. Conklin
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Sean D. Conklin.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Additional information

Published in the topical collection Food Safety Analysis with guest editor Steven J. Lehotay.

Mesay Mulugeta Wolle is an Oak Ridge Institute for Science and Education (ORISE) post-doctoral fellow.

Electronic supplementary material

ESM 1

(PDF 138 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Wolle, M.M., Conklin, S.D. Speciation analysis of arsenic in seafood and seaweed: Part II—single laboratory validation of method. Anal Bioanal Chem 410, 5689–5702 (2018). https://doi.org/10.1007/s00216-018-0910-4

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00216-018-0910-4

Keywords

Search

Navigation