Arsenic chemistry with sulfide, pyrite, zero-valent iron, and magnetite.

摘要

The aim of this thesis is to study the immobilization reactions of arsenic in water. Since compounds containing iron or sulfide are common in most natural and engineered systems, the research focused on the redox reactions and adsorption of arsenic with sulfide, pyrite, zero-valent iron (ZVI), and magnetite which were studied through wet chemistry methods and spectroscopic techniques. The kinetic and thermodynamic information of the reactions of As(V) with S(-II), As(V)/As(III) with pyrite and surface-oxidized pyrite, As(V) with ZVI and acid-treated ZVI, As(III) with magnetite was used to identify mechanisms. The necessity to maintain strictly anoxic conditions was emphasized for the study of arsenic redox chemistry with sulfides and ZVI.;The major findings of this research can be stated as follows. First, dissolved sulfide reduced As(V) to lower valences to form a yellow precipitate at acidic pH. The reaction involved the formation of thioarsenic intermediate species. Dissolved O2, granular activated carbon (GAC) and dissolved Fe(II) inhibited the removal of As(V) by sulfide. Elemental sulfur catalyzed the reduction of As(V) by sulfide, which implied the possible benefit of using sulfur-loaded GAC for arsenic removal. Possible reaction mechanisms were discussed. Second, As(III) adsorbed on pristine pyrite over a broader pH range than on surface-oxidized pyrite, while As(V) adsorbed over a narrower pH range with pristine pyrite. As(V) was completely reduced to As(III) on pristine pyrite at acidic pH but not at higher pH. The reduction was first-order with respect to As(V). As(V) was not reduced on surface-oxidized pyrite at pH = 4--11. The different behaviors of As(V) and As(III) on pristine and surface oxidized pyrite determines the toxicity and mobility of arsenic under oxic/anoxic environments. Third, commercial ZVI reduced As(V) to As(III) at low pH (9) but not at higher pH. Acid-treated ZVI reduced As(V) to As(0), indicated by wet chemical analyses and by XANES/EXAFS, which could result in reduced mobility and toxicity of arsenic. Fourth, magnetite is a good adsorbent for both As(V) and As(III). As(V) was not reduced by stoichiometric magnetite even under a strictly anoxic condition. Addition of dissolved Fe(II) to magnetite did not reduce As(V) either. Under oxic conditions, the homogeneous oxidation of As(III) by dissolved oxygen was negligible. As(III) was rapidly oxidized in the presence of magnetite. The extent of the oxidation was promoted with addition of As(V). The effect is more significant at low As(III) concentrations. The effect could be important at field sites where total arsenic concentrations are low.;This research is contributes to the understanding of the behavior of arsenic in sulfidic natural systems and in sites treated with GAC, ZVI-based permeable reactive barriers or injected with nano-ZVI particles. The optimum conditions and kinetic data for arsenic removal are applicable in field situations and engineered systems.