Characterization of laser induced breakdown plasmas used for measurements of arsenic, antimony and selenium hydrides

Studies have been performed to characterize laser induced breakdown spectroscopy (LIBS) plasmas formed in Ar/H2 gas mixtures that are used for hydride generation (HG) LIBS measurements of arsenic (As), antimony (Sb) and selenium (Se) hydrides. The plasma electron density and plasma excitation temperature have been determined through hydrogen, argon and arsenic emission measurements. The electron density ranges from 4.5 × 1017 to 8.3 × 1015 cm−3 over time delays of 0.2 to 15 μs. The plasma temperatures range from 8800 to 7700 K for Ar and from 8800 to 6500 K for As in the HG LIBS plasmas. Evaluation of the plasma properties leads to the conclusion that partial local thermodynamic equilibrium conditions are present in the HG LIBS plasmas. Comparison measurements in LIBS plasmas formed in Ar gas only indicate that the temperatures are similar in both plasmas. However it is also observed that the electron density is higher in the Ar only plasmas and that the emission intensities of Ar are higher and decay more slowly in the Ar only plasmas. These differences are attributed to the presence of H2 which has a higher thermal conductivity and provides additional dissociation, excitation and ionization processes in the HG LIBS plasma environment. Based on the observed results, it is anticipated that changes to the HG conditions that change the amount of H2 in the plasma will have a significant effect on analyte emission in the HG LIBS plasmas that is independent of changes in the HG efficiency. The HG LIBS plasmas have been evaluated for measurements of elements hydrides using a constant set of HG LIBS plasma conditions. Linear responses are observed and limits of detection of 0.7, 0.2 and 0.6 mg/L are reported for As, Sb and Se, respectively.