Comparison of the quantitation of heavy metals in soil using handheld LIBS, XRFS, and ICP-OES

Abstract

Handheld laser-induced breakdown spectroscopy (LIBS) is an emerging analytical technique that shows the potential to replace X-ray fluorescence spectroscopy (XRFS) in the field characterization of soils containing heavy metals. This study explored the accuracy and precision of handheld LIBS for analyzing soils containing copper and zinc to support LIBS as a re-placement for XRFS technology in situ. Success was defined by handheld LIBS results that could be replicated across field analyzers and verified by inductively coupled plasma–optical emission spectrometry (ICP-OES). A total of 108 soil samples from eight military installations were pressed into 13 mm pellets and then analyzed by XRFS and LIBS. Handheld LIBS has a spot-size area 100-fold smaller than that of XRFS, and though it provided accurate measurements for NIST-certified reference materials, it was not able to measure unknown soils of varying soil texture with high particle size variability, regardless of sample size. Thus, soil sample particle size heterogeneity hindered the ability to provide accurate results and replicate quantitation results across LIBS and XRFS. Increasing the number of particles encountered by each shot through particle size reduction improved both field-analyzer correlation and the correlation between handheld LIBS and ICP-OES from weak (<15%) to strong (>80%).