A review on the transformation of birnessite in the environment: Implication for the stabilization of heavy metals.

Birnessite is ubiquitous in the natural environment where heavy metals are retained and easily transformed. The surface properties and structure of birnessite change with the changes in external environmental conditions, which also affects the fate of heavy metals. Clarifying the effect and mechanism of the birnessite phase transition process on heavy metals is the key to taking effective measures to prevent and control heavy metal pollution. Therefore, the four transformation pathways of birnessite are summarized first in this review. Second, the relationship between transformation pathways and environmental conditions is proposed. These relevant environmental conditions include abiotic (e.g., co-existing ions, pH, oxygen pressure, temperature, electric field, light, aging, pressure) and biotic factors (e.g., microorganisms, biomolecules). The phase transformation is achieved by the key intermediate of Mn(III) through interlayer-condensation, folding, neutralization-disproportionation, and dissolution-recrystallization mechanisms. The AOS (average oxidation state) of Mn and interlayer spacing are closely correlated with the phase transformation of birnessite. Last but not least, the mechanisms of heavy metals immobilization in the transformation process of birnessite are summed up. They involve isomorphous substitution, redox, complexation, hydration/dehydration, etc. The transformation of birnessite and its implication on heavy metals will be helpful for understanding and predicting the behavior of heavy metals and the crucial phase of manganese oxides/hydroxides in natural and engineered environments.

Oxidation and Nanoparticle Formation during Ce(III) Sorption onto Minerals.

The sorption of Ce(III) on three abundant environmental minerals (goethite, anatase, and birnessite) was investigated. Batch sorption experiments using a radioactive 139Ce tracer were performed to investigate the key features of the sorption process. Differences in sorption kinetics and changes in oxidation states were found in the case of the sorption of Ce(III) on birnessite compared to that on other minerals. Speciation of cerium onto all of the studied minerals was investigated using spectral and microscopic methods: high-resolution transmission electron microscopy (HRTEM), electron energy loss spectroscopy (EELS), and X-ray absorption spectroscopy (XAS) in conjunction with theoretical calculations. It was found that during the sorption process onto birnessite, Ce(III) was oxidized to Ce(IV), while the Ce(III) on goethite and anatase surfaces remained unchanged. Oxidation of Ce(III) by sorption on birnessite was also accompanied by the formation of CeO2 nanoparticles on the mineral surface, which depended on the initial cerium concentration and pH value.

Unraveling the Mechanisms of Fe Oxidation and Mn Reduction on Mn Indicators of Reduction in Soil (IRIS) Films.

Indicators of reduction in soil (IRIS) devices are low-cost soil redox sensors coated with Fe or Mn oxides, which can be reductively dissolved from the device under suitable redox conditions. Removal of the metal oxide coating from the surface, leaving behind the white film, can be quantified and used as an indicator of reducing conditions in soils. Manganese IRIS, coated with birnessite, can also oxidize Fe(II), resulting in a color change from brown to orange that complicates the interpretation of coating removal. Here, we studied field-deployed Mn IRIS films where Fe oxidation was present to unravel the mechanisms of Mn oxidation of Fe(II) and the resulting minerals on the IRIS film surface. We observed reductions in the Mn average oxidation state when Fe precipitation was evident. Fe precipitation was primarily ferrihydrite (30-90%), but lepidocrocite and goethite were also detected, notably when the Mn average oxidation state decreased. The decrease in the average oxidation state of Mn was due to the adsorption of Mn(II) to the oxidized Fe and the precipitation of rhodochrosite (MnCO3) on the film. The results were variable on small spatial scales (<1 mm), highlighting the suitability of IRIS in studying heterogeneous redox reactions in soil. Mn IRIS also provides a tool to bridge lab and field studies of the interactions between Mn oxides and reduced constituents.

Significance of MnO2 Type and Solution Parameters in Manganese Removal from Water Solution.

A very low concentration of manganese (Mn) in water is a critical issue for municipal and industrial water supply systems. Mn removal technology is based on the use of manganese oxides (MnOx), especially manganese dioxide (MnO2) polymorphs, under different conditions of pH and ionic strength (water salinity). The statistical significance of the impact of polymorph type (akhtenskite ε-MnO2, birnessite δ-MnO2, cryptomelane α-MnO2 and pyrolusite ß-MnO2), pH (2-9) and ionic strength (1-50 mmol/L) of solution on the adsorption level of Mn was investigated. The analysis of variance and the non-parametric Kruskal-Wallis H test were applied. Before and after Mn adsorption, the tested polymorphs were characterized using X-ray diffraction, scanning electron microscope techniques and gas porosimetry analysis. Here we demonstrated the significant differences in adsorption level between MnO2 polymorphs' type and pH; however, the statistical analysis proves that the type of MnO2 has a four times stronger influence. There was no statistical significance for the ionic strength parameter. We showed that the high adsorption of Mn on the poorly crystalline polymorphs leads to the blockage of micropores in akhtenskite and, contrary, causes the development of the surface structure of birnessite. At the same time, no changes in the surfaces of cryptomelane and pyrolusite, the highly crystalline polymorphs, were found due to the very small loading by the adsorbate.

Biological Oxidation of Manganese Mediated by the Fungus Neoroussoella solani MnF107.

Manganese oxides are highly reactive minerals and influence the geochemical cycling of carbon, nutrients, and numerous metals in natural environments. Natural Mn oxides are believed to be dominantly formed by biotic processes. A marine Mn-oxidizing fungus Neoroussoella solani MnF107 was isolated and characterized in this study. SEM observations show that the Mn oxides are formed on the fungal hyphal surfaces and parts of the hypha are enveloped by Mn oxides. TEM observations show that the Mn oxides have a filamentous morphology and are formed in a matrix of EPS enveloping the fungal cell wall. Mineral phase analysis of the fungal Mn oxides by XRD indicates that it is poorly crystalline. Chemical oxidation state analysis of the fungal Mn oxides confirms that it is predominantly composed of Mn(IV), indicating that Mn(II) has been oxidized to Mn (IV) by the fungus.

High-efficiency electrochemical removal of Cd(II) from wastewater using birnessite-biochar composites: Performance and mechanism.

Birnessite has been widely used for electrochemical removal of heavy metals due to its high pseudocapacitance. Incorporation of carbon-based materials into birnessite can enhance its conductivity and stability, and synergistically improve the electrochemical adsorption capacity due to the double-layer capacitor reaction derived from carbon-based materials. In this study, biochar was successfully incorporated with birnessite at various ratios to synthesize composites (BC-Mn) for effective electrochemical removal of cadmium (Cd(II)) from water. The effects of cell voltage, initial pH, and recycling performance of BC-Mn were evaluated. As a result, the electrosorption capacity of BC-Mn for Cd(II) exhibited gradual increases with increasing birnessite content and reached equilibrium at a Mn content of 20% (BC-Mn20). The Cd(II) adsorption capacity of BC-Mn20 rose at higher cell voltage, and reached the maximum at 1.2 V. At pH 3.0-6.0, the electrosorption capacity initially rose until pH 5.0 and then approached equilibrium with a further increase in pH value. The Cd(II) electrochemical adsorption capacity of BC-Mn20 in the solution could reach 104.5 mg g-1 at pH 5.0 for 8 h at 1.2 V. Moreover, BC-Mn20 exhibited excellent reusability with a stability of 95.4% (99.7 mg g-1) after five cycles of reuse. Due to its superior heavy metal adsorption capacity and reusability, BC-Mn20 may have a promising prospect in the remediation of heavy metal polluted water.

Photoelectric conversion on Earth's surface via widespread Fe- and Mn-mineral coatings.

Sunlight drives photosynthesis and associated biological processes, and also influences inorganic processes that shape Earth's climate and geochemistry. Bacterial solar-to-chemical energy conversion on this planet evolved to use an intricate intracellular process of phototrophy. However, a natural nonbiological counterpart to phototrophy has yet to be recognized. In this work, we reveal the inherent "phototrophic-like" behavior of vast expanses of natural rock/soil surfaces from deserts, red soils, and karst environments, all of which can drive photon-to-electron conversions. Using scanning electron microscopy, transmission electron microscopy, micro-Raman spectroscopy, and X-ray absorption spectroscopy, Fe and Mn (oxyhydr)oxide-rich coatings were found in rock varnishes, as were Fe (oxyhydr)oxides on red soil surfaces and minute amounts of Mn oxides on karst rock surfaces. By directly fabricating a photoelectric detection device on the thin section of a rock varnish sample, we have recorded an in situ photocurrent micromapping of the coatings, which behave as highly sensitive and stable photoelectric systems. Additional measurements of red soil and powder separated from the outermost surface of karst rocks yielded photocurrents that are also sensitive to irradiation. The prominent solar-responsive capability of the phototrophic-like rocks/soils is ascribed to the semiconducting Fe- and Mn (oxyhydr)oxide-mineral coatings. The native semiconducting Fe/Mn-rich coatings may play a role similar, in part, to photosynthetic systems and thus provide a distinctive driving force for redox (bio)geochemistry on Earth's surfaces.

Hierarchical K-Birnessite-MnO2 Carbon Framework for High-Energy-Density and Durable Aqueous Zinc-Ion Battery.

MnO2 -based material is one of the most promising cathode candidates of aqueous zinc-ion batteries (ZIBs), but its commercialization is hindered by the sluggish reaction kinetics and poor structural stability. Herein, a hierarchical framework consisting of core-shell structured carbon nanotubes@K-birnessite-MnO2 enwrapped by graphene/carbon black bicomponent networks (CNT@KMO@GC) via a simple method for ZIBs is designed and developed. The hierarchical framework characterized with favorable K+ preintercalation, δ-phase, and vertically aligned nanoflake arrays of KMO and 3D electrically conductive network shows the enhanced electronic/ionic conductivity and improved wettability with electrolyte, resulting in the fast charge/mass transport and stable structural stability of CNT@KMO@GC. When used as cathode in ZIBs, CNT@KMO@GC exhibits exciting electrochemical performance with remarkable capacity (405.5 mAh g-1 at 0.30 A g-1 ), high rate performance (166.6 mAh g-1 up to 10.0 A g-1 ), and impressive cycling stability (almost no capacity decay after 2000 cycles and 77.3% retention after 10 000 cycles at 10.0 A g-1 ). The energy storage mechanism of CNT@KMO@GC is clarified as H+ /Zn2+ coinsertion/extraction via electrochemical analysis and ex situ characterization. This study offers an innovative paradigm for the advance of ZIBs.

Antimonate Controls Manganese(II)-Induced Transformation of Birnessite at a Circumneutral pH.

Manganese (Mn) oxides, such as birnessite (δ-MnO2), are ubiquitous mineral phases in soils and sediments that can interact strongly with antimony (Sb). The reaction between birnessite and aqueous Mn(II) can induce the formation of secondary Mn oxides. Here, we studied to what extent different loadings of antimonate (herein termed Sb(V)) sorbed to birnessite determine the products formed during Mn(II)-induced transformation (at pH 7.5) and corresponding changes in Sb behavior. In the presence of 10 mM Mn(II)aq, low Sb(V)aq (10 µmol L-1) triggered the transformation of birnessite to a feitknechtite (ß-Mn(III)OOH) intermediary phase within 1 day, which further transformed into manganite (γ-Mn(III)OOH) over 30 days. Medium and high concentrations of Sb(V)aq (200 and 600 µmol L-1, respectively) led to the formation of manganite, hausmannite (Mn(II)Mn(III)2O4), and groutite (αMn(III)OOH). The reaction of Mn(II) with birnessite enhanced Sb(V)aq removal compared to Mn(II)-free treatments. Antimony K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy revealed that heterovalent substitution of Sb(V) for Mn(III) occurred within the secondary Mn oxides, which formed via the Mn(II)-induced transformation of Sb(V)-sorbed birnessite. Overall, Sb(V) strongly influenced the products of the Mn(II)-induced transformation of birnessite, which in turn attenuated Sb mobility via incorporation of Sb(V) within the secondary Mn oxide phases.

A High-Energy and Long-Life Aqueous Zn/Birnessite Battery via Reversible Water and Zn2+ Coinsertion.

Aqueous rechargeable Zn/birnessite batteries have recently attracted extensive attention for energy storage system because of their low cost and high safety. However, the reaction mechanism of the birnessite cathode in aqueous electrolytes and the cathode structure degradation mechanics still remain elusive and controversial. In this work, it is found that solvation water molecules coordinated to Zn2+ are coinserted into birnessite lattice structure contributing to Zn2+ diffusion. However, the birnessite will suffer from hydroxylation and Mn dissolution with too much solvated water coinsertion. Through engineering Zn2+ primary solvation sheath with strong-field ligand in aqueous electrolyte, highly reversible [Zn(H2 O)2 ]2+ complex intercalation/extraction into/from birnessite cathode is obtained. Cathode-electrolyte interface suppressing the Mn dissolution also forms. The Zn metal anode also shows high reversibility without formation of "death-zinc" and detrimental dendrite. A full cell coupled with birnessite cathode and Zn metal anode delivers a discharge capacity of 270 mAh g-1 , a high energy density of 280 Wh kg-1 (based on total mass of cathode and anode active materials), and capacity retention of 90% over 5000 cycles.

Layered Ca0.28 MnO2 ·0.5H2 O as a High Performance Cathode for Aqueous Zinc-Ion Battery.

Aqueous zinc-ion batteries are promising candidates for grid-scale energy storage because of their intrinsic safety, low cost, and high energy intensity. However, lack of suitable cathode materials with both excellent rate performance and cycling stability hinders further practical application of aqueous zinc-ion batteries. Here, a nanoflake-self-assembled nanorod structure of Ca0.28 MnO2 ·0.5H2 O as Zn-insertion cathode material is designed. The Ca0.28 MnO2 ·0.5H2 O exhibits a reversible capacity of 298 mAh g-1 at 175 mA g-1 and long-term cycling stability over 5000 cycles with no obvious capacity fading, which indicates that the per-insertion of Ca ions and water can significantly improve reversible insertion/extraction stability of Zn2+ in Mn-based layered type material. Further, its charge storage mechanism, especially hydrogen ions, is elucidated. A comprehensive study suggests that the intercalation of hydrogen ions in the first discharge plat is controled by both pH value and type of anion of electrolyte. Further, it can stabilize the Ca0.28 MnO2 ·0.5H2 O cathode and facilitate the following insertion of Zn2+ in 1 m ZnSO4 /0.1 m MnSO4 electrolyte. This work can enlighten and promote the development of high-performance rechargeable aqueous zinc-ion batteries.

Thermodynamics of manganese oxides: Sodium, potassium, and calcium birnessite and cryptomelane.

Manganese oxides with layer and tunnel structures occur widely in nature and inspire technological applications. Having variable compositions, these structures often are found as small particles (nanophases). This study explores, using experimental thermochemistry, the role of composition, oxidation state, structure, and surface energy in the their thermodynamic stability. The measured surface energies of cryptomelane, sodium birnessite, potassium birnessite and calcium birnessite are all significantly lower than those of binary manganese oxides (Mn3O4, Mn2O3, and MnO2), consistent with added stabilization of the layer and tunnel structures at the nanoscale. Surface energies generally decrease with decreasing average manganese oxidation state. A stabilizing enthalpy contribution arises from increasing counter-cation content. The formation of cryptomelane from birnessite in contact with aqueous solution is favored by the removal of ions from the layered phase. At large surface area, surface-energy differences make cryptomelane formation thermodynamically less favorable than birnessite formation. In contrast, at small to moderate surface areas, bulk thermodynamics and the energetics of the aqueous phase drive cryptomelane formation from birnessite, perhaps aided by oxidation-state differences. Transformation among birnessite phases of increasing surface area favors compositions with lower surface energy. These quantitative thermodynamic findings explain and support qualitative observations of phase-transformation patterns gathered from natural and synthetic manganese oxides.

Redox properties of birnessite from a defect perspective.

Birnessite, a layered-structure MnO2, is an earth-abundant functional material with potential for various energy and environmental applications, such as water oxidation. An important feature of birnessite is the existence of Mn(III) within the MnO2 layers, accompanied by interlayer charge-neutralizing cations. Using first-principles calculations, we reveal the nature of Mn(III) in birnessite with the concept of the small polaron, a special kind of point defect. Further taking into account the effect of the spatial distribution of Mn(III), we propose a theoretical model to explain the structure-performance dependence of birnessite as an oxygen evolution catalyst. We find an internal potential step which leads to the easy switching of the oxidation state between Mn(III) and Mn(IV) that is critical for enhancing the catalytic activity of birnessite. Finally, we conduct a series of comparative experiments which support our model.

Sustainable and Environmentally Friendly Na and Mg Aqueous Hybrid Batteries Using Na and K Birnessites.

Sodium and magnesium batteries with intercalation electrodes are currently alternatives of great interest to lithium in stationary applications, such as distribution networks or renewable energies. Hydrated laminar oxides such as birnessites are an attractive cathode material for these batteries. Sodium and potassium birnessite samples have been synthesized by thermal and hydrothermal oxidation methods. Hybrid electrochemical cells have been built using potassium birnessite in aqueous sodium electrolyte, when starting in discharge and with a capacity slightly higher than 70 mA h g-1. Hydrothermal synthesis generally shows slightly poorer electrochemical behavior than their thermal counterparts in both sodium and potassium batteries. The study on hybrid electrolytes has resulted in the successful galvanostatic cycling of both sodium birnessite and potassium birnessite in aqueous magnesium electrolyte, with maximum capacities of 85 and 50 mA h g-1, respectively.

Oxidation of diclofenac by birnessite: Identification of products and proposed transformation pathway.

Diclofenac (DCF), a widely used non-steroidal anti-inflammatory, reacted readily with birnessite under mild conditions, and the pseudo first order kinetic constants achieved 8.84 × 10-2 hr-1. Five products of DCF including an iminoquinone product (2,5-iminoquinone-diclofenac) and four dimer products were observed and identified by tandem mass spectrometry during the reaction. Meanwhile, 2,5-iminoquinone-diclofenac was identified to be the major product, accounting for 83.09% of the transformed DCF. According to the results of spectroscopic Mn(III) trapping experiments and X-ray Photoelectron Spectroscopy, Mn(IV) contained in birnessite solid was consumed and mainly converted into Mn(III) during reaction process, which proved that the removal of DCF by birnessite was through oxidation. Based on the identified products of DCF and the changes of Mn valence state in birnessite solid, a tentative transformation pathway of DCF was proposed.

Reduction behaviors of permanganate by microbial cells and concomitant accumulation of divalent cations of Mg2+, Zn2+, and Co2.

Permanganate treatment is widely used for disinfection of bacteria in surface-contaminated water. In this paper, the fate of the dissolved permanganate in aqueous solution after contact with cells of Pseudomonas fluorescens was studied. Concomitant accumulation of divalent cations of Mg2+, Zn2+, and Co2+ during precipitation of Mn oxides was also studied. The time course of the Mn concentration in solution showed an abrupt decrease after contact of Mn(VII) with microbial cells, followed by an increase after ~24 hr. XRD analysis of the precipitated Mn oxides, called biomass Mn oxides, showed the formation of low-crystalline birnessite. Visible spectroscopy and X-ray absorption near edge structure (XANES) analyses indicated that dissolved Mn(VII) was reduced to form biomass Mn oxides involving Mn(IV) and Mn(III), followed by reduction to soluble Mn(II). The numbers of electron transferred from microbial cells to permanganate and to biomass Mn oxides for 24 hr after the contact indicated that the numbers of electron transfer from microbial cell was approximately 50 times higher to dissolved permanganate than to the biomass Mn oxides in present experimental conditions. The 24 hr accumulation of divalent cations during formation of biomass Mn oxides was in the order of Co2+ > Zn2+ > Mg2+. XANES analysis of Co showed that oxidation of Co2+ to Co3+ resulted in higher accumulation of Co than Zn and Mg. Thus, treatment of surface water by KMnO4 solution is effective not only for disinfection of microorganisms, but also for the elimination of metal cations from surface water.

Coordination geometry of Zn2+ on hexagonal turbostratic birnessites with different Mn average oxidation states and its stability under acid dissolution.

Hexagonal turbostratic birnessite, with the characteristics of high contents of vacancies, varying amounts of structural and adsorbed Mn3+, and small particle size, undergoes strong adsorption reactions with trace metal (TM) contaminants. While the interactions of TM, i.e., Zn2+, with birnessite are well understood, the effect of birnessite structural characteristics on the coordination and stability of Zn2+ on the mineral surfaces under proton attack is as yet unclear. In the present study, the effects of a series of synthesized hexagonal turbostratic birnessites with different Mn average oxide states (AOSs) on the coordination geometry of adsorbed Zn2+ and its stability under acidic conditions were investigated. With decreasing Mn AOS, birnessite exhibits smaller particle sizes and thus larger specific surface area, higher amounts of layer Mn3+ and thus longer distances for the first MnO and MnMn shells, but a low quantity of available vacancies and thus low adsorption capacity for Zn2+. Zn K-edge EXAFS spectroscopy demonstrates that birnessite with low Mn AOS has smaller adsorption capacity but more tetrahedral Zn (IVZn) complexes on vacancies than octahedral (VIZn) complexes, and Zn2+ is more unstable under acidic conditions than that adsorbed on birnessite with high Mn AOS. High Zn2+ loading favors the formation of VIZn complexes over IVZn complexes, and the release of Zn2+ is faster than at low loading. These results will deepen our understanding of the interaction mechanisms of various TMs with natural birnessites, and the stability and thus the potential toxicity of heavy metal pollutants sequestered by engineered nano-sized metal oxide materials.

Photoelectrochemical performance of birnessite films and photoelectrocatalytic activity toward oxidation of phenol.

Birnessite films on fluorine-doped tin oxide (FTO) coated glass were prepared by cathodic reduction of aqueous KMnO4. The deposited birnessite films were characterized with X-ray diffraction, Raman spectroscopy, scanning electron microscopy and atomic force microscopy. The photoelectrochemical activity of birnessite films was investigated and a remarkable photocurrent in response to visible light was observed in the presence of phenol, resulting from localized manganese d-d transitions. Based on this result, the photoelectrocatalytic oxidation of phenol was investigated. Compared with phenol degradation by the electrochemical oxidation process or photocatalysis separately, a synergetic photoelectrocatalytic degradation effect was observed in the presence of the birnessite film coated FTO electrode. Photoelectrocatalytic degradation ratios were influenced by film thickness and initial phenol concentrations. Phenol degradation with the thinnest birnessite film and initial phenol concentration of 10mg/L showed the highest efficiency of 91.4% after 8hr. Meanwhile, the kinetics of phenol removal was fit well by the pseudofirst-order kinetic model.

Removal of ammonium ion from water by Na-rich birnessite: Performance and mechanisms.

Na-rich birnessite (NRB) was synthesized by a simple synthesis method and used as a high-efficiency adsorbent for the removal of ammonium ion (NH4+) from aqueous solution. In order to demonstrate the adsorption performance of the synthesized material, the effects of contact time, pH, initial ammonium ion concentration, and temperature were investigated. Adsorption kinetics showed that the adsorption behavior followed the pseudo second-order kinetic model. The equilibrium adsorption data were fitted to Langmuir and Freundlich adsorption models and the model parameters were evaluated. The monolayer adsorption capacity of the adsorbent, as obtained from the Langmuir isotherm, was 22.61mg NH4+-N/g at 283K. Thermodynamic analyses showed that the adsorption was spontaneous and that it was also a physisorption process. Our data revealed that the higher NH4+ adsorption capacity could be primarily attributed to the water absorption process and electrostatic interaction. Particularly, the high surface hydroxyl-content of NRB enables strong interactions with ammonium ion. The results obtained in this study illustrate that the NRB is expected to be an effective and economically viable adsorbent for ammonium ion removal from aqueous system.

Oxidation of arsenite to arsenate on birnessite in the presence of light.

The effect of simulated solar radiation on the oxidation of arsenite [As(III)] to arsenate [As(V)] on the layered manganese oxide, birnessite, was investigated. Experiments were conducted where birnessite suspensions, under both anoxic and oxic conditions, were irradiated with simulated solar radiation in the presence of As(III) at pH 5, 7, and 9. X-ray absorption spectroscopy (XAS) was used to determine the nature of the adsorbed product on the surface of the birnessite. The oxidation of As(III) in the presence of birnessite under simulated solar light irradiation occurred at a rate that was faster than in the absence of light at pH 5. At pH 7 and 9, As(V) production was significantly less than at pH 5 and the amount of As(V) production for a given reaction time was the same under dark and light conditions. The first order rate constant (kobs) for As(III) oxidation in the presence of light and in the dark at pH 5 were determined to be 0.07 and 0.04 h-1, respectively. The As(V) product was released into solution along with Mn(II), with the latter product resulting from the reduction of Mn(IV) and/or Mn(III) during the As(III) oxidation process. Post-reaction XAS analysis of As(III) exposed birnessite showed that arsenic was present on the surface as As(V). Experimental results also showed no evidence that reactive oxygen species played a role in the As(III) oxidation process.