A comprehensive analysis of water-soluble arsenicals in Icelandic macroalgae.

Environmental context: Seaweeds are known to accumulate high levels of arsenic, and cellular concentrations may reach several orders of magnitude higher than that of the surrounding environment. Arsenic may be methylated by seaweed cells and further metabolised to water-soluble arsenic-containing sugars through unknown pathways. Whether these compounds are the result of a detoxification process or are produced with a biological purpose remains to be seen. Rationale: Seaweeds are known to accumulate high levels of arsenic, which may be subsequently metabolised to small, methylated compounds or become incorporated into large biological molecules such as arsenosugars. The mechanism of arsenosugars production in macroalgae is still largely unknown. Method: This study reports the arsenic speciation of 13 brown, red and green macroalgae collected in May 2021 and February 2022. Water-soluble arsenic speciation was measured using high-performance liquid chromatography–inductively coupled plasma–mass spectrometry (HPLC-ICP-MS) after extraction with a 3% (v/v) hydrogen peroxide solution. Results: Arsenosugars were found to account for the majority of the extracted arsenic in all seaweed samples (>50%), with only small amounts of dimethylarsinate and monomethylarsonate present. Levels of toxic iAs were also low (<LOQ–1.1 mg kg⁻¹). Sulfur-containing arsenosugars were the dominant arsenicals in brown macroalgae, whereas the phosphate ribose was most abundant in red and green. Discussion: The majority of seaweed species appear to have the ability to synthesise all four arsenosugar derivatives; however, it is unclear why some are produced in higher abundances. The production of arsenosugars may be an efficient way of excluding arsenic from the cytosol, or may serve as useful components in the cell wall matrix, as extremely high levels can be tolerated by the seaweed with no ill effects. AsSug-gly and AsSug-PO₄ were detected in every sample analysed, which might suggest that AsSug-gly is the starting point for AsSug-PO₄, which could be formed by AsSug-gly binding to phosphate-containing lipids in the cell membrane. Further studies should use both imaging and speciation techniques to investigate the formation of arsenosugars. Environmental context. Seaweeds are known to accumulate high levels of arsenic, and cellular concentrations may reach several orders of magnitude higher than that of the surrounding environment. Arsenic may be methylated by seaweed cells and further metabolised to water-soluble arsenic-containing sugars through unknown pathways. Whether these compounds are the result of a detoxification process or are produced with a biological purpose remains to be seen. (Image credit: Rebecca Sim.) [ABSTRACT FROM AUTHOR]