Speciation of chromium via laser-induced breakdown spectroscopy of ion exchange polymer membranes

A new method for the speciation of ng/mL concentrations of Cr(III) and Cr(VI) solutions with analysis by laser-induced breakdown spectroscopy (LIBS) is reported. Speciation is achieved by pre-concentration of the chromium onto commercially available cation exchange polymer membranes. Chromium(III) is removed directly by cation exchange; chromium(VI) in the filtrate is reduced to Cr(111) and concentrated onto a second cation exchange membrane, affording independent measurement of both species. Large volumes of waters containing Cr(111) and Cr(VI) can be concentrated onto the membranes and directly analyzed by laser-induced breakdown spectroscopy. The estimated limit of detection corresponds to 500 ng of Cr on the membrane: if a solution volume of 1 L is used, then the detection limit corresponds to a solution concentration of 0.5 ng/mL. Excellent separation of the chromium species is attained. Results show that overall method efficiencies range from 94-116% and are independent of the matrix. The influence of pH has been measured, and although Cr(VI) converts to Cr(III) in acidic solutions, the total Cr recoveries are not appreciably influenced by pH over the range of natural waters (4 to 9). In addition, speciation was performed in the presence of a number of different cations and showed that the method is robust in many different and complex matrices.