Arsenic toxicity to humans critically depends on the chemical form of the arsenic. The Expert Committee of the Food and Agriculture Organization and the World Health Organization defined a tolerable intake only for inorganic arsenic, although the toxicity of some organoarsenic compounds is known. Arsenobetaine (AsB), arsenocholine (AsC), dimethylarsinic acid (DMA), and monomethylarsonic acid (MMA) are abundant in shellfish. We present a fast and reliable method for identification of the type of organic arsenic in mussels by using liquid chromatography coupled to electrospray ionization tandem mass spectrometry on triple quadrupole with parallel determination of total arsenic by atomic absorption spectrophotometry. The method was validated by evaluating mean recoveries, repeatability, specificity, limits of quantification, and limits of detection that produced satisfactory results. The method was used to carry out the first survey of the concentrations of AsB, AsC, MMA, and DMA in seafood from southern Italy. Total As concentrations ranged from 1.38 to 12.79 mg/kg. AsB and DMA were detected in all samples (AsB: 0.72 to 10.36 mg/kg; DMA: 0.28 to 1.08 mg/kg), and concentrations of AsC and MMA ranged from 0.20 to 1.53 mg/kg. This method allowed us to rapidly and inexpensively identify arsenic types in fishery products and would be suitable for routine detection of organoarsenic compounds in molluscs.
