Critical evaluation of the ability of sequential extraction procedures to quantify discrete forms of selenium in sediments and soils.
Sequential extraction procedures (SEPs) have been widely used to characterize the mobility, bioavailibility, and potential toxicity of trace elements in soils and sediments. Although oft-criticized, these methods may perform best with redox-labile elements (As, Hg, Se) for which more discrete biogeochemical phases may arise from variations in oxidation number. We critically evaluated two published SEPs for Se for their specificity and precision by applying them to four discrete components in an inert silica matrix: soluble Se(VI) (selenate), Se(IV) (selenite) adsorbed onto goethite, elemental Se, and a metal selenide (FeSe; achavalite). These were extracted both individually and in a mixed model sediment. The more selective of the two procedures was modified to further improve its selectivity (SEP 2M). Both SEP 1 and SEP 2M quantitatively recovered soluble selenate but yielded incomplete recoveries of adsorbed selenite (64% and 81%, respectively). SEP 1 utilizes 0.1 M K2S2O8 to target "organically associated" Se, but this extractant also solubilized most of the elemental (64%) and iron selenide (91%) components of the model sediment. In SEP 2M, the Na2SO3 used in step III is effective in extracting elemental Se but also extracted 17% of the Se from the iron selenide, such that the elemental fraction would be overestimated should both forms coexist. Application of SEP 2M to eight wetland sediments further suggested that the Na2SO3 in step III extracts some organically associated Se, so a NaOH extraction was inserted beforehand to yield a further modification, SEP 2OH. Results using this five-step procedure suggested that the four-step SEP 2M could overestimate elemental Se by as much as 43% due to solubilization of organic Se. Although still imperfect in its selectivity, SEP 20H may be the most suitable procedure for routine, accurate fractionation of Se in soils and sediments. However, the strong oxidant (NaOCl) used in the final step cannot distinguish between refractory organic forms of Se and pyritic Se that might form under sulfur-reducing conditions.
Soil and Water Sciences Section, Department of Environmental Sciences, University of California, Riverside, California 92521, USA.
Michael T
MT
Wright
David R
DR
Parker
Christopher
C
Amrhein
D001682:Biological Availability; D002623:Chemistry Techniques, Analytical / Q000379:methods; D019015:Geologic Sediments / Q000737:chemistry*; D016877:Oxidants / Q000737:chemistry; D015203:Reproducibility of Results; D012643:Selenium / Q000032:analysis* / Q000493:pharmacokinetics; D012680:Sensitivity and Specificity; D012989:Soil Pollutants / Q000032:analysis* / Q000493:pharmacokinetics; D014131:Trace Elements / Q000737:chemistry
D016877:Oxidants; D012989:Soil Pollutants; D014131:Trace Elements; D012643:Selenium