Speciation of arsenic using capillary gas chromatography with atomic emission detection

A gas chromatography method with atomic emission detection (GC-AED) for the determination of dimethylarsinic acid (DMA), monomethylarsonic acid (MMA) and inorganic arsenic was optimized. The analytes were derivatized in the sample solutions with methyl thioglycolate (TGM) and the products were extracted into cyclohexane before an aliquot of this organic phase was directly injected into the chromatograph. The procedure was applied to the analysis of seawaters, wines, beers and infant foods, the last requiring an additional enzymatic reaction prior to analyte derivatization. Detection limits in seawaters and beverages were 0.05, 0.15 and 0.8 ng mL−1 for DMA, MMA and inorganic arsenic, respectively. In infant foods the detection limits were 1, 10 and 25 ng g−1 for DMA, MMA and inorganic arsenic, respectively. Inorganic arsenic was detected in some of the seawater samples and three of the wines analyzed at concentration levels in the range 1–40 ng mL−1, and DMA in several of the infant foods in the range 20–80 ng g−1. The method was validated by analyzing a certified reference material and by recovery studies. All the samples were also analyzed by hydride generation and atomic fluorescence spectrometry (HG-AFS), which provided data for the total arsenic content.