Selenite and Selenate Quantification by Hydride Generation‐Atomic Absorption Spectrometry, Ion Chromatography, and Colorimetry

Abstract

AbstractThe need for a routine, inexpensive method with nanomolar detection limits for soluble SeO2−3 and SeO2−4 is increasing as Se research on soil‐plant‐water systems intensifies and speciation of Se valence states is required. This study was undertaken to compare hydride generation‐atomic absorption spectrometry (HGAAS), colorimetry using 2,3‐diaminonaphthalene (DAN), and ion chromatography (IC) as suitable methods for analysis of SeO2−3 and SeO2−4 in soil extracts and water samples. Selenium standards in solutions of either 1.0 mM KH2PO4, CaSO4, and KNO3, or in distilled water were analyzed to determine detection limits (DL), limits of quantitation (LOQ), and practicality for routine use of the above methods. A 0.1 mM K2HPO4/KH2PO4 soil extract spiked with 2.0 or 20 µM SeO2−3 and SeO2−4 was also used to compare the precision of the three methods. The HGAAS method was the most sensitive (0.212 absorbance units/µM) and had the lowest DL for SeO23 (0.03 µmol Se/L) of the three methods employed. Detection limits for the DAN and IC methods were significantly higher (18 and 0.24 µmol Se/L, respectively). Poor reproducibility between methods was obtained for SeO2−4 content of the soil extract containing 20 µM SeO2−4, with concentrations ranging from 9.1 ± 1.2 µmol/L determined by HGAAS to 24.6 ± 0.05 µmol/L by IC. The variability and poor recovery of SeO2−4 was due to variabilty in efficiency of the HCl reduction required to reduce SeO2−4 to SeO2−3 before analysis in the HGAAS and DAN procedures. Selenium determinations in samples where low detection limits (<0.1 µM) are required are most effectively accomplished with HGAAS. Colorimetry requires greater effort and time from the analyst to obtain the low detection limits of HGAAS, but is useful in that only a visible light spectrometer is required. Ion chromatography is capable of automated determinations of Se2−3 and SeO2−4 directly in combination with other ions of interest and may be appropriate for soil solution Se analysis where Se speciation is required.