An improved rapid analytical method for the arsenic speciation analysis of marine environmental samples using high-performance liquid chromatography/inductively coupled plasma mass spectrometry

Arsenic contamination in marine environments is a serious issue because some arsenicals are very toxic, increasing the health risks associated with the consumption of marine products. This study describes the development of an improved rapid method for the quantification of arsenic species, including arsenite (AsIII), arsenate (AsV), arsenocholine (AsC), arsenobetaine (AsB), dimethylarsinic acid (DMA), and monomethyl arsonic acid (MMA), in seaweed, sediment, and seawater samples using high-performance liquid chromatography/inductively coupled plasma-mass spectrometry (HPLC/ICP-MS). ICP-MS based on dynamic reaction cells was used to eliminate spectral interference. Ammonium nitrate- and phosphate-based eluents were used as the mobile phases for HPLC analysis, leading to shorter overall retention time (6 min) and improved peak separation. Arsenicals were extracted with a 1% HNO3 solution that required no clean-up process and exhibited reasonable sensitivity and peak resolution. The optimized method was verified by applying it to hijiki seaweed certified reference material (CRM, NMIJ 7405-a) and to spiked blank samples of sediment and seawater. The proposed method measured the concentration of AsV in the CRM as 9.6 ± 0.6 μg/kg dry weight (dw), which is close to the certified concentration (10.1 ± 0.5 μg/kg dw). The recovery of the six arsenicals was 87-113% for the sediment and 99-101% for the seawater. In the analysis of real samples, AsV was the most abundant arsenical in hijiki and gulfweed, whereas AsB was dominant in other seaweed species. The two inorganic arsenicals (AsIII and AsV) and AsV were the most dominant in the sediment and seawater samples, respectively.