Quantitation and speciation of inorganic arsenic in a biological sample by capillary ion chromatography combined with inductively coupled plasma mass spectrometry

The toxicity and biological activity of arsenic depend on its chemical form. In particular, inorganic arsenics are more toxic than organic ones. Apart from the determination of total arsenics, their accurate speciation is important for toxicity assessment. To separate arsenic species using a cation or an anion separation column, at least 0.5–1.0 mL of sample is required because conventional ion chromatography columns use a sample loop of 100–200 μL. It is thus difficult to analyze samples with small volumes, such as clinical and biological samples. In this study, a method for separating arsenic species using a 5-μL sample loop combined with a capillary ion exchange column has been developed for analyzing small volume of samples. The separated arsenics were determined by inductively coupled plasma mass spectrometry. By oxidizing As(III) to As(V) prior to analysis, the total inorganic arsenics, As(III) and As(V), could be well separated from the organic ones. Linear calibration curves (0.5–50 μg/kg) were obtained for total inorganic arsenics dissolved in water. Sub-picogram-level detection limit was obtained. The analytical capability of this method was successfully validated for certified reference materials, namely water and human urine, with total inorganic arsenic recovery efficiencies of 100% and 121%, respectively. Our method requires less than ~ 10 μL of sample and will be very useful to analyze valuable samples available in limited amounts.