Selective determination of Cr(VI) and non-chromatographic speciation analysis of inorganic chromium by chemical vapor generation-inductively coupled plasma mass spectrometry

A novel and sensitive method for the selective determination of Cr(VI) and non-chromatographic speciation of Cr (VI) and Cr(III) was developed based on chemical vapor generation (CVG) in KBH4-acid system for sample introduction into an inductively coupled plasma mass spectrometer (ICP-MS) for detection. The CVG of Cr(VI), rather than Cr(III), was found to be remarkably enhanced in the presence of sodium diethylaminodithioformate (DDTC). After the oxidation of Cr(III) to Cr(VI) by KMnO4, the quantitation of Cr(III) could be obtained based on the difference between the concentration of total chromium and that of Cr(VI). Parameters affecting the CVG reaction and determination of Cr(VI) were evaluated in detail, including the concentrations of DDTC, hydrochloric acid and KBH4, the sample flow rate, as well as the length of reaction and transferring tubing. Under optimal conditions, the CVG efficiency and the limit of detection (LOD) of Cr(VI) were found to be 28% and 0.2 ng mL(-1), respectively. The relative standard deviations for seven replicate measurements of 20 ng mL(-1) of Cr(VI) was 1.8%. Furthermore, with excess DDTC (100 mu g mL(-1)) added to the test solutions, possible interferences from Cu2+ (up to 400 ng mL(-1)) could be eliminated. The proposed method was thus successfully applied to the determination of Cr(VI) in three real water samples and one certified reference water sample, as well as two simulated water samples of Cr(VI) and Cr(III), all with satisfactory results. The possible reasons were discussed for the varied degrees of enhancement between Cr(III) and Cr(VI).