Brandon J. Lafferty

Arsenite Oxidation by a Poorly Crystalline Manganese-Oxide 1. Stirred-Flow Experiments

Manganese-oxides (Mn-oxides) are quite reactive, with respect to arsenite (As(III)) oxidation. However, studies regarding the pathways of As(III) oxidation, over a range of time scales, by poorly crystalline Mn-oxides, are lacking. In stirred-flow experiments, As(III) oxidation by δ-MnO₂ (a poorly crystalline form of hexagonal birnessite) is initially rapid but slows appreciably after several hours of reaction. Mn(II) is the only reduced product of δ-MnO₂ formed by As(III) oxidation during the initial, most rapid phase of the reaction. There seems to be evidence that the formation of Mn(III) observed in previous studies is a result of conproportionation of Mn(II) sorbed onto Mn(IV) reaction sites rather than from direct reduction of Mn(IV) by As(III).The only evidence of arsenic (As) sorption during As(III) oxidation by δ-MnO₂ is during the first 10 h of reaction, and As sorption is greater when As(V) and Mn(II) occur simultaneously in solution. Our findings indicate that As(III) oxidation by poorly crystalline δ-MnO₂ involves several simultaneous reactions and reinforces the importance of studying reaction mechanisms over time.

Arsenite oxidation by a poorly crystalline manganese-oxide. 2. Results from X-ray absorption spectroscopy and X-ray diffraction.

Arsenite (As(III)) oxidation by manganese oxides (Mn-oxides) serves to detoxify and, under many conditions, immobilize arsenic (As) by forming arsenate (As(V)). As(III) oxidation by Mn(IV)-oxides can be quite complex, involving many simultaneous forward reactions and subsequent back reactions. During As(III) oxidation by Mn-oxides, a reduction in oxidation rate is often observed, which is attributed to Mn-oxide surface passivation. X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) data show that Mn(II) sorption on a poorly crystalline hexagonal birnessite (δ-MnO₂) is important in passivation early during reaction with As(III). Also, it appears that Mn(III) in the δ-MnO₂ structure is formed by conproportionation of sorbed Mn(II) and Mn(IV) in the mineral structure. The content of Mn(III) within the δ-MnO₂ structure appears to increase as the reaction proceeds. Binding of As(V) to δ-MnO₂ also changes as Mn(III) becomes more prominent in the δ-MnO ₂ structure. The data presented indicate that As(III) oxidation and As(V) sorption by poorly crystalline δ-MnO₂ is greatly affected by Mn oxidation state in the δ-MnO₂ structure.

Arsenite Oxidation by a Poorly-Crystalline Manganese Oxide. 3. Arsenic and Manganese Desorption

Arsenic (As) mobility in the environment is greatly affected by its oxidation state and the degree to which it is sorbed on metal oxide surfaces. Manganese oxides (Mn oxides) have the ability to decrease overall As mobility both by oxidizing toxic arsenite (As(III)) to less toxic arsenate (As(V)), and by sorbing As. However, the effect of competing ions on the mobility of As sorbed on Mn-oxide surfaces is not well understood. In this study, desorption of As(V) and As(III) from a poorly crystalline phyllomanganate (δ-MnO(2)) by two environmentally significant ions is investigated using a stirred-flow technique and X-ray absorption spectroscopy (XAS). As(III) is not observed in solution after desorption under any conditions used in this study, agreeing with previous studies showing As sorbed on Mn-oxides exists only as As(V). However, some As(V) is desorbed from the δ-MnO(2) surface under all conditions studied, while neither desorptive used in this study completely removes As(V) from the δ-MnO(2) surface.

An ATR-FTIR spectroscopic approach for measuring rapid kinetics at the mineral/water interface

This study presents a methodology for studying rapid kinetic reactions for IR active compounds. In soils, sediments, and groundwater systems a rapid initial chemical reaction can comprise a substantial portion of the total reaction process at the mineral/water interface. Rapid-scan attenuated total reflectance (ATR) Fourier transform infrared (FTIR) spectroscopy is presented here as a new method for collecting rapid in situ kinetic data. As an example of its application, the initial oxidation of arsenite (As III) via Mn-oxides is examined. Using a rapid-scan technique, IR spectra were collected with a time resolution of up to 2.55 s (24 scans, 8 cm(-1) resolution). Through observation and analysis of IR bands corresponding to arsenate (AsV), rapid chemically-controlled As III oxidation is observed (initial pH 6-9) with 50% of the reaction occurring within the first one min. The oxidation of As III is followed by rapid binding of AsV to HMO, at least in part, through surface bound Mn II. The experimental data indicate that rapid-scan FTIR is an effective technique for acquisition of kinetic data, providing molecular scale information for rapid reactions at the solid/liquid interface.

Evaluating environmental influences on AsIII oxidation kinetics by a poorly crystalline Mn-oxide.

The oxidation of arsenite (As(III)) via Mn-oxides is an important process for natural arsenic (As) cycling and for developing in situ strategies for remediation of As-contaminated waters. In this study, the influence of goethite (alpha-FeOOH), phosphate, and bacteria/biopolymer coatings on the initial As(III) oxidation kinetics by a hydrous Mn-oxide (delta-MnO(2)) is examined via both batch experiments and rapid scan ATR-spectroscopy. Under natural conditions the presence of various mineral surfaces, bacteria, organic matter, and ions in solution can block Mn-oxide reaction sites, alter reaction rates, and thus inhibit As(III) oxidation. Previous studies of As-Mn systems demonstrate rapid oxidation of As(III), catalyzed by Mn-oxides, producing less toxic and mobile arsenate (As(V)). Subsequent to oxidation, reaction products from reductive dissolution of delta-MnO(2) by As(III), bind to and passivate the mineral surface. This study demonstrates enhanced passivation through interaction with phosphate and bacteria. Increased As oxidation with high concentrations of goethite is observed, attributed to As(V) sorption to alpha-FeOOH and diminished surface passivation of delta-MnO(2). Specific competition between phosphate and As(V) for delta-MnO(2) was confirmed through diminished As sorption and decreased As(V) production when oxidation occurred in the presence of phosphate. Kinetic experiments reveal that the extent of initial As(III) oxidation in the presence of low phosphate and alpha-FeOOH concentration is reduced; however, initial reaction rates are generally not affected. Reaction rates are reduced when bacterial adhesion and high phosphate concentrations strongly passivate delta-MnO(2) and reduce As(III) interactions with the mineral surface. The data presented in this study highlight the importance of considering natural heterogeneity when investigating reaction mechanisms and initial reaction kinetics.

Additive and Competitive Effects of Bacteria and Mn Oxides on Arsenite Oxidation Kinetics

Arsenic (As) is a redox-active metalloid whose toxicity and mobility in soil depend on oxidation state. Arsenite [As(III)] can be oxidized to arsenate [As(V)] by both minerals and microbes in soil however, the interaction between these abiotic and biotic processes is not well understood. In this study, the time dependency of As(III) oxidation by two heterotrophic soil bacteria (Agrobacterium tumefaciens and Pseudomonas fluorescens) and a poorly crystalline manganese (Mn) oxide mineral (δ-MnO(2)) was determined using batch experiments. The apparent rate of As(V) appearance in solution was greater for the combined batch experiments in which bacteria and δ-MnO(2) were oxidizing As(III) at the same time than for either component alone. The additive effect of the mixed cell- δ-MnO(2) system was consistent for short (<1 h) and long (24 h) term coincubation indicating that mineral surface inhibition by cells has little effect the As(III) oxidation rate. Surface interactions between cells and the mineral surface were indicated by sorption and pH-induced desorption results. Total sorption of As on the mineral was lower with bacteria present (16.1 ± 0.8% As sorbed) and higher with δ-MnO(2) alone (23.4 ± 1%) and As was more easily desorbed from the cell-δ-MnO(2) system than from δ-MnO(2) alone. Therefore, the presence of bacteria inhibited As sorption and decreased the stability of sorbed As on δ-MnO(2) even though As(III) was oxidized fastest in a mixed cell-δ-MnO(2) system. The additive effect of biotic (As-oxidizing bacteria) and abiotic (δ-MnO(2) mineral) oxidation processes in a system containing both oxidants suggests that mineral-only results may underestimate the oxidative capacity of natural systems with biotic and abiotic As(III) oxidation pathways.

Arsenite modifies structure of soil microbial communities and arsenite oxidization potential.

The influence of arsenite [As(III)] on natural microbial communities and the capacity of exposed communities to oxidize As(III) has not been well explored. In this study, we conducted soil column experiments with a natural microbial community exposed to different carbon conditions and a continuous flow of As(III). We measured the oxidation rates of As(III) to As(V), and the composition of the bacterial community was monitored by 454 pyrosequencing of 16S rRNA genes. The diversity of As(III)-oxidizing bacteria was examined with the aox gene, which encodes the enzyme involved in As(III) oxidation. Arsenite oxidation was high in the live soil regardless of the carbon source and below detection in sterilized soil. In columns amended with 200 μmol kg(-1) of As (III), As(V) concentrations reached 158 μmol kg(-1) in the column effluent, while As(III) decreased to unmeasurable levels. Although the number of bacterial taxa decreased by as much as twofold in treatments amended with As(III), some As(III)-oxidizing bacterial groups increased up to 20-fold. Collectively, the data show the large effect of As(III) on bacterial diversity, and the capacity of natural communities from a soil with low initial As contamination to oxidize large inputs of As(III).