RESUMO
Extensive research has used dimethylarsinic acid (DMA) in urine as a marker of arsenic methylation. The premise is that humans methylate inorganic arsenicals to monomethylarsonic acid (MMA) and DMA and excrete these arsenic species into the urine. However, DMA in urine not only comes from the methylation of inorganic arsenic but also could be a result of metabolism of other arsenic species, such as arsenosugars and arsenolipids. Most environmental health and epidemiological studies of arsenic methylation might have overlooked confounding factors that contribute to DMA in urine. Here we critically evaluate reported studies that used methylation indexes, concentration ratios of methylated arsenicals, or the percentage of DMA in urine as markers of arsenic methylation efficiency. Dietary intake of arsenosugars potentially confounds the calculation and interpretation of the arsenic methylation efficiencies. Many studies have not considered incidental dietary intake of arsenosugars, arsenolipids, and other organic arsenic species. Future studies should consider the dietary intake of diverse arsenic species and their potential effect on the urinary concentrations of DMA.
RESUMO
Food and water are the main sources of human exposure to arsenic. It is important to determine arsenic species in food because the toxicities of arsenic vary greatly with its chemical speciation. Extensive research has focused on high concentrations of arsenic species in marine organisms. The concentrations of arsenic species in freshwater fish are much lower, and their determination presents analytical challenges. In this review, we summarize the current state of knowledge on arsenic speciation in freshwater fish and discuss challenges and research needs. Fish samples are typically homogenized, and arsenic species are extracted using water/methanol with the assistance of sonication and enzyme treatment. Arsenic species in the extracts are commonly separated using high-performance liquid chromatography (HPLC) and detected using inductively coupled plasma mass spectrometry (ICPMS). Electrospray ionization tandem mass spectrometry, used in combination with HPLC and ICPMS, provides complementary information for the identification and characterization of arsenic species. The methods and perspectives discussed in this review, covering sample preparation, chromatography separation, and mass spectrometry detection, are directed to arsenic speciation in freshwater fish and applicable to studies of other food items. Despite progress made in arsenic speciation analysis, a large fraction of the total arsenic in freshwater fish remains unidentified. It is challenging to identify and quantify arsenic species present in complex sample matrices at very low concentrations. Further research is needed to improve the extraction efficiency, chromatographic resolution, detection sensitivity, and characterization capability.
