title: Oxidation of H2S by iron oxides in unsaturated conditions.
abstract: Previous studies have demonstrated that gas-phase H2S can immobilize certain redox-sensitive contaminants (e.g., Cr, U, Tc) in vadose zone environments. A key issue for effective and efficient delivery of H2S in these environments is the reactivity of the gas with indigenous iron oxides. To elucidate the factors that control the transport of H2S in the vadose zone, laboratory column experiments were conducted to identify reaction mechanisms and measure rates of H2S oxidation by iron oxide-coated sands using several carrier gas compositions (N2, air, and O2) and flow rates. Most experiments were conducted using ferrihydrite-coated sand. Additional studies were conducted with goethite- and hematite-coated sand and a natural sediment. Selective extractions were conducted at the end of each column experiment to determine the mass balance of the reaction products. XPS was used to confirm the presence of the reaction products. For column experiments in which ferrihydrite-coated sand was the substrate and N2 was the carrier gas, the major H2S oxidation products were FeS and elemental sulfur (mostly S8(0), represented as S(0) for simplicity) at ratios that were consistent with the stoichiometry of the postulated reactions. When air or O2 were used as the carrier gas, S(0) became the dominant reaction product along with FeS2 and smaller amounts of FeS, sulfate, and thiosulfate. A mathematical model of reactive transport was used to test the hypothesis that S(0) forming on the iron oxide surfaces reduces access of H2S to the reactive surface. Several conceptual models were assessed in the context of the postulated reactions with the final model based on a linear surface poisoning model and fitted reaction rates. These results indicate that carrier gas selection is a critical consideration with significant tradeoffs for remediation objectives.
authors.affiliation: Pacific Northwest National Laboratory, P.O. Box 999, Mail Stop K6-81, Richland, Washington 99352, USA. kirk.cantrell@pnl.gov
authors.forename: Kirk J
authors.initials: KJ
authors.lastname: Cantrell
authors.forename: Steven B
authors.initials: SB
authors.lastname: Yabusaki
authors.forename: Mark H
authors.initials: MH
authors.lastname: Engelhard
authors.forename: Alexandre V
authors.initials: AV
authors.lastname: Mitroshkov
authors.forename: Edward C
authors.initials: EC
authors.lastname: Thornton
mesh_terms: D002840:Chromates / Q000737:chemistry*; D005290:Ferric Compounds / Q000737:chemistry; D005293:Ferritins / Q000737:chemistry*; D006256:Hazardous Waste / Q000517:prevention & control*; D006862:Hydrogen Sulfide / Q000737:chemistry*; D058085:Iron Compounds / Q000737:chemistry; D008903:Minerals; D008956:Models, Chemical; D010084:Oxidation-Reduction; D012037:Refuse Disposal / Q000379:methods*
chemical_list: D002840:Chromates; D005290:Ferric Compounds; D006256:Hazardous Waste; D058085:Iron Compounds; D008903:Minerals; C094886:goethite; C000499:ferric oxide; C092844:ferric oxyhydroxide; D005293:Ferritins; D006862:Hydrogen Sulfide