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


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.

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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.

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Correspondence to Sean D. Conklin.

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The authors declare that they have no conflict of interest.

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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.

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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).

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  • Arsenic
  • Seafood
  • Seaweed
  • Speciation
  • Validation