title: Coupled production and transport of selenium vapor in unsaturated soil: evaluation by experiments and numerical simulation.
abstract: Volatilization of selenium (Se) from soil to the atmosphere involves several sequential chemical reactions that form volatile Se species, followed by transport of the gaseous Se through the soil. This paper describes a numerical model that simulates the chemical and physical processes governing the production and transport of Se vapor in unsaturated soil. The model couples the four Se species involved in the production of Se vapor through chemical reactions, and allows each to migrate through the soil by advection, liquid or vapor diffusion depending on its affinity for the dissolved or vapor phase. The coupled transformations and transport of the four Se species, i.e., selenate, selenite, elemental and organic Se, and Se vapor, were calculated based on the Crank-Nicolson finite difference method. The model was used to analyze fluxes of Se vapor measured from a soil amended with inorganic Se in the form of selenate and covered with unamended clean soil of various thicknesses. Evolution of Se vapor from the soil was very fast, with measurable amounts of Se detected within 24 h. The peak of Se volatilization, detected at the 6th day, reached 3.31 Se microgram/day for the uncovered soil, but was reduced to near the detection limit (0.05 microgram/day) in the presence of a 8- or 16-cm clean soil cover. With two reaction rate coefficients fitted to the data, the model described Se volatilization very well. The estimated rate coefficient of Se methylation was unexpectedly high, with a value of 0.167/day. The net volatilization of Se, however, was severely inhibited by the fast demethylation, i.e., the reverse reaction which converted volatile Se species back into nonvolatile forms. As a result, Se vapor only penetrated a few centimeters in the soil. The demethylation rate coefficient, assessed by independent transport experiments using dimethyl selenide, was estimated as 186.8/day, corresponding to a half-life of only 5.3 min for Se vapor. Results of this study indicated that rapid demethylation of Se vapor during its diffusive transport through a soil is probably an important limiting factor in the volatilization of Se under natural conditions.
authors.affiliation: Department of Environmental Sciences, College of Natural and Agricultural Sciences, University of California, Riverside, CA 92521-0424, USA.
authors.forename: L
authors.initials: L
authors.lastname: Guo
authors.forename: W A
authors.initials: WA
authors.lastname: Jury
authors.forename: W T
authors.initials: WT
authors.lastname: Frankenberger
mesh_terms: D003198:Computer Simulation; D015203:Reproducibility of Results; D012643:Selenium / Q000737:chemistry*; D014835:Volatilization
chemical_list: D012643:Selenium