Specific extraction of chromium(VI) using supercritical fluid extraction

In some situations, it is no longer sufficient to give a total concentration of a metal. Instead, what is required to understand the potential toxicity of a sample is the concentration of metal species or oxidation state. When developing species specific methods, the major concern is that the integrity of the species ratio is not changed. In other words, the sample preparation or the analytical method will not convert metal ions from one oxidation state to another. Normal extraction techniques and chromatography methods have shown some tendencies to change species ratios. An ideal extraction method would extract the metal efficiently while retaining the metal's oxidation state. The properties of supercritical fluids should approach the ideal of retention of oxidation states. For example, the need for speciation of chromium is obvious since Cr(III) is considered an essential element while Cr(YI) is thought to be toxic and carcinogenic. This paper presents the results of a species specific extraction of Cr(VI) using two different carbamate derivatives as the chelator. Supercritical fluid extraction (SFE) coupled with a fluorinated dithiocarbamate and a methanol modifier allows extraction of 1 ppm Cr(VI) from a solid matrix with a recovery level of 88.4 +/- 2.57% using the NIST standard sample. The optimized conditions using the HP 7680 supercritical fluid extractor were: 0.1 mi of methanol, 0.05 mi of pure water, and 0.01 g of chelate via a saturation chamber. (C) 2000 Elsevier Science B.V. All rights reserved.