With the use of laser-induced breakdown spectroscopy (LIBS), the effects of chemical speciation and matrix composition on Pb and Ba measurements have been investigated by using sand and soil matrices. A cylindrical lens was used to focus the laser pulses on the samples because it yielded higher measurement precision than a spherical lens for the experimental conditions used here. The detection limits for Pb and Ba spiked in a sand matrix were 17 and 76 ppm (w/w), respectively. In spiked soil, the detection limits were 57 and 42 ppm (w/w) for Pb and Ba, respectively. Measurement precision for five replicate measurements was typically 10% RSD or less. Two factors were found to influence emissions from Pb and Ba present in sand and soil matrices as crystalline compounds: (1) compound speciation, where Ba emission intensities varied in the order carbonate > oxide > sulfate > chloride > nitrate, and where Pb emission intensities varied in the order oxide > carbonate > chloride > sulfate > nitrate; and (2) the composition of the bulk sample matrix. Emissions from Ba(II) correlated inversely with the plasma electron density, which in turn was dependent upon the percent sand in a sand/soil mixture. The analytical results obtained here show that a field-screening instrument based on LIBS would be useful for the initial screening of soils contaminated with Pb and Ba.
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