Analysis and speciation of selenium ions in mine environments

Abstract

 Aqueous extracts of five mine soil samples and a set of selenite (SeO₃ ^2–)–selenate (SeO₄ ^2–) solutions (0.5, 1, 5, 10 and 25 mg/l) were speciated using atomic absorption spectroscopy with hydride generation (AAS-HG) and ion chromatography (IC) to compare these methods for Se speciation. In another experiment, a SeO₃ ^2––SeO₄ ^2––SO₄ ^2– solution (25 mg/l) was reacted with CaO, MgO, MnO₂, CuO, La₂O₃, and WO₃ to evaluate the relative distribution of the Se species and SO₄ ^2– in the SORB (sorbed ions that were desorbed by NaOH), SOLN (equilibrium concentrations), CMPX (irreversibly sorbed and neutral ion pair complexes) fractions. The AAS-HG method was capable of analyzing Se as low as 0.002 mg/l, which was below the detection limit of IC. High concentration of SO₄ ^2– affected the chromatographic Se speciation either by shifting or overlapping Se peaks, in which AAS-HG was more useful. However, IC was capable of speciating aqueous SeO₃ ^2––SeO₄ ^2– directly without any sample pretreatment, whereas AAS-HG measured SeO₃ ^2–+SeO₄ ^2–, and SeO₃ ^2– in separate runs and SeO₄ ^2– was calculated from the difference, i.e., spectrophotometric speciation was an indirect method. For both Se species, AAS-HG and IC data were comparable within detection standard deviations. Ratios of different Se species at measured soil pH and pe indicated that SeO₃ ^2– or SeO₄ ^2– would be the dominant Se species; the p(SeO₄ ^2–/SeO₃ ^2–) values further suggested SeO₄ ^2– would be the major solution species. Except for CaO and MgO treatments, the %SeO₃ ^2– in the SORB fraction was ≥%SeO₄ ^2–. In the SOLN fraction %SeO₄ ^2– was ≥%SeO₃ ^2– for all oxides but CaO, whereas in the CMPX fraction this order was observed for only CaO and MnO₂. The %SeO₃ ^2– was highest in the SOLN fraction for all oxides but MgO and La₂O₃ for these two oxides SeO₃ ^2– dominated in CMPX and SORB fractions, respectively. The SOLN fraction also contained the highest %SeO₄ ^2– for all oxides but MgO which retained SeO₄ ^2– primarily in the SORB fraction. The %SeO₃ ^2– and %SeO₄ ^2– in the CMPX fraction were highest for MgO, thus, suggesting a possible formation of MgSeO₃ ⁰ and MgSeO₄ ⁰. A similar trend of SORB %SO₄ ^2– and SORB %SeO₄ ^2– was attributed to the analogous adsorption mechanisms (outer-sphere complexation). For all oxides but MgO, %SO₄ ^2– was <%SeO₄ ^2– in the SOLN fraction and ≥%SeO₄ ^2– in the CMPX fraction. Comparative ionic distributions provide an overall picture of the relative abundance of different Se species in various fractions associated with different oxides present in micro- and macrolevels in soils and geological materials.