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The simultaneous sorption of cations and anions at the mineral-water interface can substantially alter their individual sorption characteristics; however, this phenomenon lacks a mechanistic understanding. Our study provides direct spectroscopic and modeling evidence of the molecular cosorption mechanisms of the cadmium ion (Cd 2+ ) and phosphate (P) on goethite and layered manganese (Mn) oxide of birnessite, through in situ attenuated total reflection Fourier-transform infrared (ATR-FTIR), P K -edge X-ray absorption near-edge structure (XANES) spectroscopy, and surface complexation modeling. Phosphate synergistically cosorbed with Cd on goethite predominantly through P-bridged ternary complexes (≡Fe-P-Cd) and electrostatic interactions at wide pH conditions. Likewise, P and Cd exhibited synergistic cosorption on birnessite by forming P-bridged ternary complexes (≡Mn-P-Cd) and weak competitive sorption at the layer edge sites. As pH and Cd loading increased, the surface P species transitioned from a binary complex to a ternary complex and/or Cd 3 (PO 4 ) 2 precipitate for both goethite and birnessite. Compared to that in solution at pH 8, the formation of Cd 3 (PO 4 ) 2 was inhibited by the presence of goethite and birnessite, ascribed to the specific adsorption of P and Cd, more pronounced in birnessite due to the stronger sorption of Cd at its vacant sites. The discovered cosorption mechanisms of P and Cd have important implications for understanding and predicting their mobility and availability in Cd-contaminated settings.

The cycling processes of elemental manganese (Mn), including the redox reactions of dissolved Mn(III) (dMn(III)), directly and indirectly influences the biogeochemical processes of many elements. Though increasing evidence indicates the widespread presence of dMn(III) mediates the fate of many elements, its role may be currently underestimated. There is both a lack of clear understanding of the historical research framework of dMn(III) and a systematic overview of its geochemical properties and detection methods. Therefore, the primary aim of this review is to outline the understanding of dMn(III) in multiple fields, including soil science, analytical chemistry, biochemistry, geochemistry, and water treatment, and summarize the formation pathways, species forms, and detection methods of dMn(III) in aquatic systems. This review considers how the characteristics of dMn(III), the intermediate formed in the single-electron reaction processes of Mn(II) oxidation and Mn(IV) reduction, determines its participation in environmental geochemical processes. Its widespread presence in diverse water systems and active redox properties coupling with various elements confirm its significant role in natural elemental geochemistry cycle and artificial water treatment processes. Therefore, further investigation into the role of dissolved Mn(III) in aquatic systems is warranted to unravel unexplored coupled elemental redox reaction processes mediated by dissolved Mn(III), filling in the gaps in our understanding of manganese environmental geochemistry, and providing a theoretical basis for recognizing the role of dMn(III) role in water treatment technologies., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The purpose of this study was to explore the effects of combined lead (Pb) and two types of microplastic (MP) (polyvinyl chloride [PVC] and polyethylene [PE]) exposure on glucose metabolism and investigate the role of the nuclear factor erythroid 2-related factor 2 (Nrf2)/nuclear factor-kappa B (NF-κB) signaling pathway in mediating these effects in mice. Adult C57BL/6J mice were randomly divided into four groups: control, Pb (100 mg/L), MPs (containing 10 mg/L PE and PVC), and Pb + MPs, each of which was treated with drinking water. Treatments were conducted for 6 weeks. Co-exposure to Pb + MPs exhibited increase glycosylated serum protein levels, insulin resistance, and damaged glucose tolerance compared with the control mice. Additionally, treatment with Pb + MPs caused more severe damage to hepatocytes than when exposed to them alone concomitantly, exposed to Pb + MPs exhibited improved the levels of interleukin-6, tumor necrosis factor-alpha, and malondialdehyde, but reduced superoxide dismutase, glutathione peroxidase, and catalase assay in livers. Furthermore, they increase the Kelch-like ECH-associated protein 1 (Keap1) and phosphorylated p-NF-κB protein levels but reduced the protein levels of heme oxygenase-1 and Nrf2, as well as increased Keap1 mRNA and Nrf2 mRNA. Co-exposure to Pb + MP impacts glucose metabolism via the Nrf2 /NF-κB pathway., (© 2024 Wiley Periodicals LLC.)

Mineral adsorption-induced molecular fractionation of dissolved organic matter (DOM) affects the composition of both DOM and OM adsorbed and thus stabilized by minerals. However, it remains unclear what mineral properties control the magnitude of DOM fractionation. Using a combined technique approach that leverages the molecular composition identified by ultrahigh resolution 21 T Fourier transform ion cyclotron resonance mass spectrometry and adsorption isotherms, we catalogue the compositional differences that occur at the molecular level that results in fractionation due to adsorption of Suwannee River fulvic acid on aluminum (Al) and iron (Fe) oxides and a phyllosilicate (allophane) species of contrasting properties. The minerals of high solubility (i.e., amorphous Al oxide, boehmite, and allophane) exhibited much stronger DOM fractionation capabilities than the minerals of low solubility (i.e., gibbsite and Fe oxides). Specifically, the former released Al 3+ to solution (0.05-0.35 mM) that formed complexes with OM and likely reduced the surface hydrophobicity of the mineral-OM assemblage, thus increasing the preference for adsorbing polar DOM molecules. The impacts of mineral solubility are exacerbated by the fact that interactions with DOM also enhance metal release from minerals. For sparsely soluble minerals, the mineral surface hydrophobicity, instead of solubility, appeared to be the primary control of their DOM fractionation power. Other chemical properties seemed less directly relevant than surface hydrophobicity and solubility in fractionating DOM.

Methylmercury (MeHg) is a potent neurotoxin and has great adverse health impacts on humans. Organisms and sunlight-mediated demethylation are well-known detoxification pathways of MeHg, yet whether abiotic environmental components contribute to MeHg degradation remains poorly known. Here, we report that MeHg can be degraded by trivalent manganese (Mn(III)), a naturally occurring and widespread oxidant. We found that 28 ± 4% MeHg could be degraded by Mn(III) located on synthesized Mn dioxide (MnO 2- x ) surfaces during the reaction of 0.91 μg·L -1 MeHg and 5 g·L -1 mineral at an initial pH of 6.0 for 12 h in 10 mM NaNO 3 at 25 °C. The presence of low-molecular-weight organic acids (e.g., oxalate and citrate) substantially enhances MeHg degradation by MnO 2- x via the formation of soluble Mn(III)-ligand complexes, leading to the cleavage of the carbon-Hg bond. MeHg can also be degraded by reactions with Mn(III)-pyrophosphate complexes, with apparent degradation rate constants comparable to those by biotic and photolytic degradation. Thiol ligands (cysteine and glutathione) show negligible effects on MeHg demethylation by Mn(III). This research demonstrates potential roles of Mn(III) in degrading MeHg in natural environments, which may be further explored for remediating heavily polluted soils and engineered systems containing MeHg.

Manganese (Mn) exists as Mn(II), Mn(III), or Mn(IV) in soils, and the Mn oxidation state controls the roles of Mn in numerous environmental processes. However, the variations of Mn oxidation states with climate remain unknown. We determined the Mn oxidation states in highly weathered bulk volcanic soils (primary minerals free) across two rainfall gradients covering mean annual precipitation (MAP) of 0.25-5 m in the Hawaiian Islands. With increasing MAP, the soil redox conditions generally shifted from oxic to suboxic and to anoxic despite fluctuating at each site; concurrently, the proportions of Mn(IV) and Mn(II) decreased and increased, respectively. Mn(III) was low at both low and high MAP, but accumulated substantially, up to 80% of total Mn, in soils with prevalent suboxic conditions at intermediate MAP. Mn(III) was likely hosted in Mn(III,IV) and iron(III) oxides or complexed with organic matter, and its distribution among these hosts varied with soil redox potentials and soil pH. Soil redox conditions and rainfall-driven leaching jointly controlled exchangeable Mn(II) in soils, with its concentration peaking at intermediate MAP. The Mn redox chemistry was at disequilibrium, with the oxidation states correlating with long-term average soil redox potentials better than with soil pH. The soil redox conditions likely fluctuated between oxic and anoxic conditions more frequently at intermediate than at low and high MAP, creating biogeochemical hot spots where Mn, Fe, and other redox-sensitive elements may be actively cycled.

While silicate has been known to affect metal sorption on mineral surfaces, the mechanisms remain poorly understood. We investigated the effects of silicate on Zn sorption onto Al oxide at pH 7.5 and elucidated the mechanisms using a combination of X-ray absorption fine structure (XAFS) spectroscopy, Zn stable isotope analysis, and scanning transmission electron microscopy (STEM). XAFS analysis revealed that Zn-Al layered double hydroxide (LDH) precipitates were formed in the absence of silicate or at low Si concentrations (≤0.4 mM), whereas the formation of Zn-Al LDH was inhibited at high silicate concentrations (≥0.64 mM) due to surface-induced Si oligomerization. Significant Zn isotope fractionation (Δ 66 Zn sorbed-aqueous = 0.63 ± 0.03‰) was determined at silicate concentrations ≥0.64 mM, larger than that induced by sorption of Zn on Al oxide (0.47 ± 0.03‰) but closer to that caused by Zn bonding to the surface of Si oxides (0.60-0.94‰), suggesting a presence of Zn-Si bonding environment. STEM showed that the sorbed silicates had a close spatial coupling with γ-Al 2 O 3 , indicating that >Si-Zn inner-sphere complexes (">" denotes surface) likely bond to the γ-Al 2 O 3 surface to form >Al-Si-Zn ternary inner-sphere complexes. This study not only demonstrates that dissolved silicate in the natural environment plays an important role in the fate and bioavailability of Zn but also highlights the potential of coupled spectroscopic and isotopic methods in probing complex environmental processes.

Iron (Fe) minerals constitute a major control on organic carbon (OC) storage in soils and sediments. While previous research has mainly targeted Fe (oxyhydr)oxides, the impact of Fe sulfides and their subsequent oxidation on OC dynamics remains unresolved in redox-fluctuating environments. Here, we investigated the impact of dissolved organic matter (DOM) on FeS oxidation and how FeS and its oxidation may alter the retention and nature of DOM. After the anoxic reaction of DOM with FeS, FeS preferentially removed high-molecular-weight and nitrogen-rich compounds and promoted the formation of aqueous sulfurized organic molecules, according to Fourier transform-ion cyclotron resonance-mass spectrometry (FT-ICR-MS) analysis. When exposed to O 2 , FeS oxidized to nanocrystalline lepidocrocite and additional aqueous sulfurized organic compounds were generated. The presence of DOM decreased the particle size of the resulting nano-lepidocrocite based on Mössbauer spectroscopy. Following FeS oxidation, most solid-phase OC remained associated with the newly formed lepidocrocite via a monodentate chelating mechanism (based on FTIR analysis), and FeS oxidation caused only a slight increase in the solubilization of solid-phase OC. Collectively, this work highlights the under-appreciated role of Fe sulfides and their oxidation in driving OC transformation and preservation.

Saharan dust is an important phosphorus (P) supply to remote and oligotrophic parts of the oceans and American lowland tropical rainforests. Phosphorus speciation in aeolian dust ultimately controls the release and bioavailability of P after dust deposition, but the speciation in Saharan dust and its change during the trans-Atlantic transport remains unclear. Using P K-edge X-ray absorption near edge structure (XANES) spectroscopy, we showed that with increasing dust traveling distance from the Sahara Desert to Cape Verde and to Puerto Rico, about 570 and 4000 km, respectively, the proportion of Ca-bound P (Ca-P), including both apatite and non-apatite forms, decreased from 68-73% to 50-71% and to 21-37%. The changes were accompanied by increased iron/aluminum-bound P proportion from 14-25% to 23-46% and to 44-73%, correspondingly. Laboratory simulation experiments suggest that the changes in P speciation can be ascribed to increasing degrees of particle sorting and atmospheric acidification during dust transport. The presence of relatively soluble non-apatite Ca-P in the Cape Verde dust but not in the Puerto Rico dust is consistent with the higher P water solubility of the former than the latter. Our findings provide insights into the controls of atmospheric processes on P speciation, solubility, and stability in Saharan dust.

Cadmium (Cd) isotopes have great potential for understanding Cd geochemical cycling in soil and aquatic systems. Iron (oxyhydr)oxides can sequester Cd via adsorption and isomorphous substitution, but how these interactions affect Cd isotope fractionation remains unknown. Here, we show that adsorption preferentially enriches lighter Cd isotopes on iron (oxyhydr)oxide surfaces through equilibrium fractionation, with a similar fractionation magnitude (Δ 114/110 Cd solid-solution ) for goethite (Goe) (-0.51 ± 0.04‰), hematite (Hem) (-0.54 ± 0.10‰), and ferrihydrite (Fh) (-0.55 ± 0.03‰). Neither the initial Cd 2+ concentration or ionic strength nor the pH influence the fractionation magnitude. The enrichment of the light isotope is attributed to the adsorption of highly distorted [CdO 6 ] on solids, as indicated by Cd K-edge extended X-ray absorption fine-structure analysis. In contrast, Cd incorporation into Goe by substitution for lattice Fe at a Cd/Fe molar ratio of 0.05 preferentially sequesters heavy Cd isotopes, with a Δ 114/110 Cd solid-solution of 0.22 ± 0.01‰. The fractionation probably occurs during the transformation of Fh into Goe via dissolution and reprecipitation. These results improve the understanding of the Cd isotope fractionation behavior being affected by iron (oxyhydr)oxides in Earth's critical zone and demonstrate that interactions with minerals can obscure anthropogenic and natural Cd isotope characteristics, which should be carefully considered when applying Cd isotopes as environmental tracers.

Perchlorate (ClO 4 - ) is a pervasive, harmful, and inert anion on both Earth and Mars. Current technologies for ClO 4 - reduction entail either harsh conditions or multicomponent enzymatic processes. Herein, we report a heterogeneous ( L )Mo-Pd/C catalyst directly prepared from Na 2 MoO 4 , a bidentate nitrogen ligand ( L ), and Pd/C to reduce aqueous ClO 4 - into Cl - with 1 atm of H 2 at room temperature. A suite of instrument characterizations and probing reactions suggest that the Mo VI precursor and L at the optimal 1:1 ratio are transformed in situ into oligomeric Mo IV active sites at the carbon-water interface. For each Mo site, the initial turnover frequency (TOF 0 ) for oxygen atom transfer from ClO x - substrates reached 165 h -1 . The turnover number (TON) reached 3840 after a single batch reduction of 100 mM ClO 4 - . This study provides a water-compatible, efficient, and robust catalyst to degrade and utilize ClO 4 - for water purification and space exploration.

Manganese (Mn) oxides can oxidize dissolved organic matter (DOM) and alter its chemical properties and microbial degradability, but the compound selectivity for oxidation and oxidative alterations remain to be determined. We applied ultrahigh mass spectrometry to catalog the macromolecular composition of Suwannee River fulvic acid (SRFA) before and after oxidation by a Mn oxide (δ-MnO 2 ) at pH 4 or 6. Polycyclic aromatic hydrocarbons, polyphenols, and carbohydrates were more reactive in reducing δ-MnO 2 than highly unsaturated and phenolic (HuPh) compounds and aliphatics, but highly abundant HuPh contributed the most (∼50%) to the overall reduction of δ-MnO 2 . On average, oxidized species had higher molecular weights, aromaticity, carbon unsaturation degree, nominal oxidation state of carbon, and oxygen and nitrogen contents but were lower in hydrogen content compared to unoxidized species. The oxidation decreased these molecular indices and oxygen and nitrogen contents but increased the hydrogen content, with stronger changes at the lower pH. This DOM oxidation on polar mineral surfaces was more selective but shared similar selectivity rules to adsorption. The abiotic oxidation resembles microbial oxidative degradation of organic matter, and Mn oxide-oxidizable carbon may be a useful index for detection and identification of labile organic carbon.

Schwertmannite effectively sorbs chromate (Cr(VI)), yet the sorption mechanisms remain elusive. We determined the Cr(VI) sorption mechanisms on schwertmannite at pH 3.2 and 5 using combined macroscopic sorption experiments with molecular-scale characterization and by comparing them to arsenate (As(V)) sorption. Cr(VI) adsorbs as bidentate-binuclear (BB) inner-sphere complexes through exchanging more sulfate and less >Fe-OH/OH 2 , with 0.59-0.71 sulfate released per Cr(VI) sorbed. While As(V) also forms BB complexes, it exchanges sulfate and >Fe-OH/OH 2 equally with 0.49-0.52 sulfate released per As(V) sorbed. At high As(V) loadings, As(V) precipitates as amorphous FeAsO 4 , particularly at low pH. The abovementioned differences between Cr(VI) and As(V) can be related to their different ionic radii and binding strength. Moreover, Cr(VI) and As(V) preferentially exchange sulfate inner-sphere complexes, increasing the proportion of sulfate outer-sphere complexes in schwertmannite. In turn, the concentration of sulfate outer-sphere complexes increases and then decreases with increasing Cr(VI) loading. Results suggest that an oxyanion, which would form inner-sphere complexes on a mineral surface, preferentially exchanges inner-spherically bound oxyanions than outer-spherically bound ones on the surface, even though both are exchanged. This study improves our understanding of the sorption of oxyanions on schwertmannite and their capabilities to template schwertmannite formation and stabilize its structure.

Layered manganese (Mn) oxides, such as birnessite, can reductively transform into other phases and thereby affect the environmental behavior of Mn oxides. Solution chemistry strongly influences the transformation, but the effects of oxyanions remain unknown. We determined the products and rates of Mn(II)-driven reductive transformation of δ-MnO 2 , a nanoparticulate hexagonal birnessite, in the presence of phosphate or silicate at pH 6-8 and a wide range of Mn(II)/MnO 2 molar ratios. Without the oxyanions, δ-MnO 2 transforms into triclinic birnessite (T-bir) and 4 × 4 tunneled Mn oxide (TMO) at low Mn(II)/MnO 2 ratios (0.09 and 0.13) and into δ-MnOOH and Mn 3 O 4 with minor poorly crystallized α- and γ-MnOOH at high Mn(II)/MnO 2 ratios (0.5 and 1). The presence of phosphate or silicate substantially decreases the rate and extent of the above transformation, probably due to adsorption of the oxyanions on layer edges or the formation of Mn(II,III)-oxyanion ternary complexes on vacancies of δ-MnO 2 , adversely interfering with electron transfer, Mn(III) distribution, and structural rearrangements. The oxyanions also reduce the crystallinity and particle sizes of the transformation products, ascribed to adsorption of the oxyanions on the products, preventing their further particle growth. This study enriches our understanding of the solution chemistry control on redox-driven transformation of Mn oxides.

Dissolved Mn(III) species have been recognized as a significant form of Mn in redox transition environments, but a holistic understanding of their geochemical properties still lacks the characterization of their reactivity as reductants. Through using PbO 2 as a surrogate oxidant and pyrophosphate (PP) as a model ligand, we evaluated the thermodynamic and kinetic constrains of dissolved Mn(III) oxidation under environmentally relevant pH. Without disproportionation, Mn(III) complexes could be directly oxidized by PbO 2 to produce Mn oxides. The reaction rates decreased with increasing PP:Mn(III) ratio and became negligible when the ratio was above a threshold value. Particulate manganite could also be oxidized by PbO 2 with detectable production of Pb(II). The favorability of Mn(III) oxidation by PbO 2 as a function of the PP:Mn ratio could be predicted by the stability constant of the Mn(III)-PP complex. We developed kinetic models that couple multiple pathways of Mn oxidation by PbO 2 to simulate the dynamics of Pb release, loss of dissolved Mn, as well as Mn(III) production and consumption. Beyond the context of Mn geochemistry, the interactions between Pb and various Mn species, including its trivalent forms, may also have important implications to the water quality in lead service lines within distribution systems.

Numerous experimental studies have identified a multi-step reaction mechanism to control arsenite (As(III)) oxidation by manganese (Mn) oxides. The studies highlighted the importance of edge sites and intermediate processes, e.g., surface passivation by reaction products. However, the identified reaction mechanism and controlling factors have rarely been evaluated in a quantitative context. In this study, a process-based modeling framework was developed to delineate and quantify the relative contributions and rates of the different processes affecting As(III) oxidation by Mn oxides. The model development and parameterization were constrained by experimental observations from literature studies involving environmentally relevant Mn oxides at circumneutral pH using both batch and stirred-flow reactors. Our modeling results highlight the importance of a transitional phase, solely evident in the stirred-flow experiments, where As(III) oxidation gradually shifts from fast reacting Mn(IV) to slowly reacting Mn(III) edge sites. The relative abundance of these edge sites was the most important factor controlling the oxidation rate, whereas surface passivation restricted oxidation only in the stirred-flow experiment. The Mn(III) edge sites were demonstrated to play a crucial role in the oxidation and therefore in controlling the long-term fate of As. This study provided an improved understanding of Mn oxide reactivity and the significance in the cycling of redox-sensitive metal(loid)s in the environment., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020. Published by Elsevier Ltd.)

Minerals, natural organic matter (NOM), and divalent manganese (Mn(II)) often coexist in suboxic/oxic environment. Multiple adsorption and oxidation processes occur in this ternary system, which are coupled to affect the fate of both OM and Mn therein and alter their chemical reactivity toward metals and other pollutants. However, the details about the coupling are poorly known although much has been gained for the binary systems. We determined the mutual influence of surface-catalyzed Mn(II) oxidation and humic acid (HA) adsorption and oxidation in a Fe(III) oxide (goethite)-HA-Mn(II) system at pH 5-8. The presence of Mn(II) substantially increased HA adsorption whereas HA greatly impaired the extent and rate of Mn(II) oxidation by O 2 on goethite surfaces. The impacts were more pronounced at higher pH. Mn(II) oxidation produced β-MnOOH, γ-MnOOH, and Mn 3 O 4 which in turn oxidized HA, producing small organic acids. The presence of HA markedly altered the composition of Mn(II) oxidation products by inhibiting the formation of β-MnOOH while favoring the production of γ-MnOOH and Mn(II) adsorbed on the HA-mineral assemblage. Nonconducting γ-Al 2 O 3 exhibited similar but weaker effects than semiconducting goethite in the above processes. Our results suggest that similar to Mn-oxidizing microorganisms, mineral surfaces can drive the coupling of the Mn redox cycle with NOM oxidative degradation under suboxic/oxic and circumneutral/alkaline conditions.

The potential energy contained in the controlled mixing of waters with different salt concentrations (i.e., salinity gradient energy) can theoretically provide a substantial fraction of the global electrical demand. One method for generating electricity from salinity gradients is to use electrode-based reactions in electrochemical cells. Here, we examined the relationship between the electrical power densities generated from synthetic NaCl solutions and the crystal structures and morphologies of manganese oxides, which undergo redox reactions coupled to sodium ion uptake and release. Our aim was to make progress toward developing rational frameworks for selecting electrode materials used to harvest salinity gradient energy. We synthesized 12 manganese oxides having different crystal structures and particle sizes and measured the power densities they produced in a concentration flow cell fed with 0.02 and 0.5 M NaCl solutions. Power production varied considerably among the oxides, ranging from no power produced (β-MnO 2 ) to 1.18 ± 0.01 W/m 2 (sodium manganese oxide). Power production correlated with the materials' specific capacities, suggesting that cyclic voltammetry may be a simple method to screen possible materials. The highest power densities were achieved with manganese oxides capable of intercalating sodium ions when their potentials were prepoised prior to power production.

Sequential chemical extraction has been widely used to study soil phosphorus (P) dynamics and inform nutrient management, but its efficacy for assigning P into biologically meaningful pools remains unknown. Here, we evaluated the accuracy of the modified Hedley extraction scheme using P K-edge X-ray absorption near-edge structure (XANES) spectroscopy for nine carbonate-free soil samples with diverse chemical and mineralogical properties resulting from different degrees of soil development. For most samples, the extraction markedly overestimated the pool size of calcium-bound P (Ca-P, extracted by 1 M HCl) due to (1) P redistribution during the alkaline extractions (0.5 M NaHCO 3 and then 0.1 M NaOH), creating new Ca-P via formation of Ca phosphates between NaOH-desorbed phosphate and exchangeable Ca 2+ and/or (2) dissolution of poorly crystalline Fe and Al oxides by 1 M HCl, releasing P occluded by these oxides into solution. The first mechanism may occur in soils rich in well-crystallized minerals and exchangeable Ca 2+ regardless of the presence or absence of CaCO 3 , whereas the second mechanism likely operates in soils rich in poorly crystalline Fe and Al minerals. The overestimation of Ca-P simultaneously caused underestimation of the pools extracted by the alkaline solutions. Our findings identify key edaphic parameters that remarkably influenced the extractions, which will strengthen our understanding of soil P dynamics using this widely accepted procedure.

Birnessite owing to its negative surface charge and defective structure exhibits high sorption affinities for Cd(II). However, Mn(II) can not only compete for the sorption sites with Cd(II), but also react with structural Mn(IV) in birnessite to form Mn(III), and thus, affect Cd(II) immobilization by birnessite. Herein, we investigate effects of Mn(II) on Cd(II) retention and remobilization on two birnessite δ-MnO 2 and Mn(III)-rich δ-MnO 2 (denoted as HE-MnO 2 ). At pH 5.5, Cd(II) sorption to birnessite was inhibited by Mn(II) addition. Mn(II) addition to δ-MnO 2 led to Cd(II) migration from vacant sites to edge sites, forming double-corner sharing (DCS) complexes. Mn(II) introduction to δ-MnO 2 led to less stable Cd(II) species formed on birnessite, indicating that Cd(II) was more firmly bound to vacant sites than edge sites of birnessite. Cd(II) formed double-edge sharing (DES) and DCS complexes on HE-MnO 2 . Mn(II) addition to HE-MnO 2 increased the CdMn distance in DES complexes. The stability of adsorbed Cd(II) on HE-MnO 2 was slightly elevated due to Mn(II) addition. At pH 7.5, Mn(II) had no effect on Cd(II) sorption and desorption amounts on birnessite. However, low concentration of Mn(II) added to δ-MnO 2 induced partial migration of Cd(II) from vacant sites to edge sites while high concentration of Mn(II) added to birnessite led to the formation of amorphous Cd(II)-Mn(III) coprecipitate. These findings imply that aqueous Mn(II) is an important factor in influencing Cd(II) immobilization by birnessite in the environment., (Copyright © 2019 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Hexagonal birnessite, a typical layered Mn oxide (LMO), can adsorb and oxidize Mn(II) and thereby transform to Mn(III)-rich hexagonal birnessite, triclinic birnessite, or tunneled Mn oxides (TMOs), remarkably changing the environmental behavior of Mn oxides. We have determined the effects of coexisting cations on the transformation by incubating Mn(II)-bearing δ-MnO 2 at pH 8 under anoxic conditions for 25 d (dissolved Mn < 11 μM). In the Li + , Na + , and K + chloride solutions, the Mn(II)-bearing δ-MnO 2 first transforms to Mn(III)-rich δ-MnO 2 or triclinic birnessite (T-bir) due to the Mn(II)-Mn(IV) comproportionation, most of which eventually transform to a 4 × 4 TMO. In contrast, Mn(III)-rich δ-MnO 2 and T-bir form and persist in the Mg 2+ and Ca 2+ chloride solutions. However, in the presence of surface adsorbed Cu(II), Mn(II)-bearing δ-MnO 2 turns into Mn(III)-rich δ-MnO 2 without forming T-bir or TMOs. The stabilizing power of the cations on the δ-MnO 2 structure positively correlates with their binding strength to δ-MnO 2 (Li + , Na + , and K + < Mg 2+ and Ca 2+ < Cu(II)). Since metal adsorption decreases the surface energy of minerals, our finding suggests that the surface energy largely controls the thermodynamic stability of LMOs. Our study indicates that the adsorption of divalent metal cations, particularly transition metals, can be an important cause of the high abundance of LMOs, rather than the more stable TMO phases, in the environment.

Apart from surface complexation, precipitation of minerals also plays an important role in reducing the mobility and transport of heavy metals in the environment. In this study, Cd(II) sorption species on surfaces of γ-Al 2 O 3 at pH 7.5 were characterized using multiple techniques. Results show that in addition to adsorption complexes, Cd hydroxide phases (Cd(OH) 2 precipitates and Cd x (OH) y polynuclear complexes) were formed at the initial stages of Cd(II) sorption and gradually transformed to CdCO 3 with time. In addition, Cd(II) formed CdAl layered double hydroxide (LDH) on γ-Al 2 O 3 under various conditions, independent of temperature and Cd loadings. The formation of Cd hydroxide phases and CdAl LDH could be ascribed to surface-induced precipitation because the bulk solution was undersaturated with respect to hydroxides. CdAl LDH formation on the Al-bearing mineral here is rather surprising because typically this occurs with elements of ionic radii similar to that of Al 3+ ; this formation is unknown for metals such as Cd(II) with a much larger ionic radius. The thermodynamic feasibility of CdAl LDH formation was further confirmed by laboratory synthesis of CdAl LDH and density function theory (DFT) calculations. These results suggest that Cd precipitation on Al-bearing minerals can be an important mechanism for Cd immobilization in the natural environment. Additionally, the finding of CdAl LDH formation on Al-bearing minerals and the thermodynamic stability of CdAl LDH provides new insights into the remediation of Cd-polluted soils and aquatic systems., (Copyright © 2019 The Authors. Published by Elsevier Ltd.. All rights reserved.)

In natural environments, kinetics of As(V) sequestration/release is usually coupled with dynamic Fe mineral transformation, which is further influenced by the presence of natural organic matter (NOM). Previous work mainly focused on the interactions between As(V) and Fe minerals. However, there is a lack of both mechanistic and quantitative understanding on the coupled kinetic processes in the As(V)-Fe mineral-NOM system. In this study, we investigated the effect of humic acids (HA) on the coupled kinetics of ferrihydrite transformation into hematite/goethite and sequestration of As(V) on Fe minerals. Time-resolved As(V) and HA interactions with Fe minerals during the kinetic processes were studied using aberration-corrected scanning transmission electron microscopy, chemical extractions, stirred-flow kinetic experiments, and X-ray absorption spectroscopy. Based on the experimental results, we developed a mechanistic kinetics model for As(V) fate during Fe mineral transformation. Our results demonstrated that the rates of As(V) speciation changes within Fe minerals were coupled with ferrihydrite transformation rates, and the overall reactions were slowed down by the presence of HA that sorbed on Fe minerals. Our kinetics model is able to account for variations of Fe mineral compositions, solution chemistry, and As(V) speciation, which has significant environmental implications for predicting As(V) behavior in the environment.

The Fe-Zr binary oxide adsorbents have higher arsenic adsorptive capacities than either iron oxide or zirconium oxide alone, indicating a strong synergistic effect exists between Fe and Zr oxides. However, no generally accepted in-depth explanations have been reached on the origin of this better performance. In the present study, the component phases, the active surface sites, the structure of the adsorbed As(V) surface species, and the mechanism of the synergistic effect, were investigated and elucidated using multiple advanced experimental techniques combined with quantum chemical calculations. Goethite and lepidocrocite were identified as the main Fe oxide components while amorphous zirconium hydroxide was the main Zr oxide component, respectively. A monodentate-mononuclear complex and a bidentate-binuclear complex were revealed to be dominant on the surface, respectively, when at lower and higher initial As(V) concentrations. Density functional theory calculations indicated that As(V) preferred to bind with Zr-OH rather than Fe-OH. This was verified with the As K-edge EXAFS results and XPS observations. The synergistic effect was due to a short-range ordering state, the enlarged contents of amorphous and poorly-crystalline fractions, and increased hydroxyl surface site density. These results lead to the realization that the above properties are preferred in future adsorbent preparations., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Aeolian dust is a significant source of phosphorus (P) to alpine oligotrophic lakes, but P speciation in dust and source sediments and its release kinetics to lake water remain unknown. Phosphorus K-edge XANES spectroscopy shows that calcium-bound P (Ca-P) is dominant in 10 of 12 dust samples (41-74%) deposited on snow in the central Rocky Mountains and all 42 source sediment samples (the fine fraction) (68-80%), with a lower proportion in dust probably because acidic snowmelt dissolves some Ca-P in dust before collection. Iron-bound P (Fe-P, ∼54%) dominates in the remaining two dust samples. Chemical extractions (SEDEX) on these samples provide inaccurate results because of unselective extraction of targeted species and artifacts introduced by the extractions. Dust releases increasingly more P in synthetic lake water within 6-72 h thanks to dissolution of Ca-P, but dust release of P declines afterward due to back adsorption of P onto Fe oxides present in the dust. The back sorption is stronger for the dust with a lower degree of P saturation determined by oxalate extraction. This work suggests that P speciation, poorly crystalline minerals in the dust, and lake acidification all affect the availability and fate of dust-borne P in lakes.

The structure and Mn(III) concentration of birnessite dictate its reactivity and can be changed by birnessite partial reduction, but effects of pH and reductant/birnessite ratios on the changes by reduction remain unclear. We found that the two factors strongly affect the structure of birnessite (δ-MnO 2 ) and its Mn(III) content during its reduction by fulvic acid (FA) at pH 4-8 and FA/solid mass ratios of 0.01-10 under anoxic conditions over 600 h. During the reduction, the structure of δ-MnO 2 is increasingly accumulated with both Mn(III) and Mn(II) but much more with Mn(III) at pH 8, whereas the accumulated Mn is mainly Mn(II) with little Mn(III) at pH 4 and 6. Mn(III) accumulation, either in layers or over vacancies, is stronger at higher FA/solid ratios. At FA/solid ratios ≥1 and pH 6 and 8, additional hausmannite and MnOOH phases form. The altered birnessite favorably adsorbs FA because of the structural accumulation of Mn(II, III). Like during microbially mediated oxidative precipitation of birnessite, the dynamic changes during its reduction are ascribed to the birnessite-Mn(II) redox reactions. Our work suggests low reactivity of birnessite coexisting with organic matter and severe decline of its reactivity by partial reduction in alkaline environment.

Fe(II)-rich clay minerals found in subsurface redox transition zones (RTZs) can serve as important sources of electron equivalents limiting the transport of redox-active contaminants. While most laboratory reactivity studies are based on reduced model clays, the reactivity of naturally reduced field samples remains poorly explored. Characterization of the clay size fraction of a fine-grained unit from the RTZ interface at the Hanford site, Washington, including mineralogy, crystal chemistry, and Fe(II)/(III) content, indicates that ferruginous montmorillonite is the dominant mineralogical component. Oxic and anoxic fractions differ significantly in Fe(II) natural content, but Fe TOTAL remains constant, demonstrating no Fe loss during its reduction-oxidation cyclings. At native pH of 8.6, the anoxic fraction, despite its significant Fe(II), ∼23% of Fe TOTAL , exhibits minimal reactivity with TcO 4 - and CrO 4 2- and much slower reaction kinetics than those measured in studies with biologically/chemically reduced model clays. Reduction capacity is enhanced by added/sorbed Fe(II) (if Fe(II) SORBED > 8% clay Fe(II) LABILE ); however, the kinetics of this conceptually surface-mediated reaction remain sluggish. Surface-sensitive Fe L-edge X-ray absorption spectroscopy shows that Fe(II) SORBED and the resulting reducing equivalents are not available in the outermost few nanometers of clay surfaces. Slow kinetics thus appear related to diffusion-limited access to electron equivalents retained within the clay mineral structure.

The role of microbial activities on the transformation of chromium (Cr) remediation products has generally been overlooked. This study investigated the stability of Cr(III)-Fe(III)-(oxy)hydroxides, common Cr(VI) remediation products, with a range of compositions in the presence of common microbial exudates, siderophores and small organic acids. In the presence of a representative siderophore, desferrioxamine B (DFOB), iron (Fe) was released at higher rates and to greater extents relative to Cr from all solid phases. The presence of oxalate alone caused the release of Cr, but not of Fe, from all solid phases. In the presence of both DFOB and oxalate, oxalate acted synergistically with DFOB to increase the Fe, but not the Cr, release rate. Upon reaction with DFOB or DFOB + oxalate, the remaining solids became enriched in Cr relative to Fe. Such incongruent dissolution led to solid phases with different compositions and increased solubility relative to the initial solid phases. Thus, the presence of microbial exudates can promote the release of Cr(III) from remediation products via both ligand complexation and increased solid solubility. Understanding the potential reaction kinetics and pathways of Cr(VI) remediation products in the presence of microbial activities is necessary to assess their long-term stability.

Layered manganese (Mn) oxides, such as birnessite, are versatile materials in industrial applications and common minerals mediating elemental cycling in natural environment. Many of birnessite properties are controlled by Mn(III) concentration and particle sizes. Thus, it is important to synthesize birnessite nanoparticles with controlled Mn(III) concentrations and sizes so that one can tune its properties for many applications. Birnessite was synthesized in the presence of oxyanions (phosphate, silicate, or sulfate) during reductive precipitation of KMnO 4 by HCl and characterized using multiple synchrotron X-ray techniques, electron microscopy, and diffuse reflectance UV-vis spectroscopy. Results indicate that all three anions decrease MnO 6 sheet sizes, attributed to oxyanion adsorption on edges of the sheets, inhibiting their lateral growth. As a result of decreased sizes, sheets undergo significant structural contraction. Meanwhile, Mn(III) concentration significantly increases with increasing oxyanion/Mn ratio. The increased Mn(III) concentration, along with the decreased size, enlarges both direct and indirect band gaps of birnessite. Phosphate imposes the strongest influence, followed by silicate and then by sulfate, consistent with their decreasing adsorption affinity. Reacting with 1 M KOH solution effectively removed the adsorbed oxyanions while leading to increased sheet sizes, probably due to oriented attachment-driven particle growth mechanisms. The results have important implications for developing highly performed birnessite materials, for example, small size Mn(III)-rich birnessite for photochemical and catalytic applications, as well as for understanding chemical compositional variations of naturally occurring birnessite.

Sulfate adsorption on mineral surfaces is an important environmental chemical process, but the structures and respective contribution of different adsorption complexes under various environmental conditions are unclear. By combining sulfur K-edge XANES and EXAFS spectroscopy, quantum chemical calculations, and surface complexation modeling (SCM), we have shown that sulfate forms both outer-sphere complexes and bidentate-binuclear inner-sphere complexes on ferrihydrite surfaces. The relative fractions of the complexes vary with pH, ionic strength (I), and sample hydration degree (wet versus air-dried), but their structures remained the same. The inner-sphere complex adsorption loading decreases with increasing pH while remaining unchanged with I. At both I = 0.02 and 0.1 M, the outer-sphere complex loading reaches maximum at pH ∼5 and then decreases with pH, whereas it monotonically decreases with pH at I = 0.5 M. These observations result from a combination of the ionic-strength effect, the pH dependence of anion adsorption, and the competition between inner- and outer-sphere complexation. Air-drying drastically converts the outer-sphere complexes to the inner-sphere complexes. The respective contributions to the overall adsorption loading of the two complexes were directly modeled with the extended triple layer SCM by implementing the bidentate-binuclear inner-sphere complexation identified in the present study. These findings improve our understanding of sulfate adsorption and its effects on other environmental chemical processes and have important implications for generalizing the adsorption behavior of anions forming both inner- and outer-sphere complexes on mineral surfaces.

Birnessite, a phyllomanganate and the most common type of Mn oxide, affects the fate and transport of numerous contaminants and nutrients in nature. Birnessite exhibits hexagonal (HexLayBir) or orthogonal (OrthLayBir) layer symmetry. The two types of birnessite contain contrasting content of layer vacancies and Mn(III), and accordingly have different sorption and oxidation abilities. OrthLayBir can transform to HexLayBir, but it is still vaguely understood if and how the reverse transformation occurs. Here, we show that HexLayBir (e.g., δ-MnO2 and acid birnessite) transforms to OrthLayBir after reaction with aqueous Mn(II) at low Mn(II)/Mn (in HexLayBir) molar ratios (5-24%) and pH ≥ 8. The transformation is promoted by higher pH values, as well as smaller particle size, and/or greater stacking disorder of HexLayBir. The transformation is ascribed to Mn(III) formation via the comproportionation reaction between Mn(II) adsorbed on vacant sites and the surrounding layer Mn(IV), and the subsequent migration of the Mn(III) into the vacancies with an ordered distribution in the birnessite layers. This study indicates that aqueous Mn(II) and pH are critical environmental factors controlling birnessite layer structure and reactivity in the environment.

Fe-doped cryptomelanes were synthesized by refluxing at ambient pressure, followed by characterization with multiple techniques and test in photocatalytic degradation of phenol. The introduction of Fe(III) into the structure of cryptomelane results in a decrease in particle size and the contents of Mn and K(+), and an increase in the Mn average oxidation state (AOS), specific surface area and UV-vis light absorption ability. Mn and Fe K-edge extended X-ray absorption fine structure spectroscopy analysis indicates that some Fe(III) is incorporated into the framework of cryptomelane by replacing Mn(III) while the remaining Fe(3+) is adsorbed in the tunnel cavity. These Fe-doped cryptomelanes have significantly improved the photocatalytic degradation rate of phenol, with the sample of ∼3.04 wt.% Fe doping being the most reactive and achieving a degradation rate of 36% higher than that of the un-doped one. The enhanced reactivity can be ascribed to the increase in the coherent scattering domain size of the crystals, Mn AOS and light absorption, as well as the presence of sufficient K(+) in the tunnel. The results imply that metal doping is an effective way to improve the performance of cryptomelane in pollutants removal and has the potential for modification of Mn oxide materials., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Schwertmannite, a nanocrystalline ferric oxyhydroxy-sulfate mineral, plays an important role in many environmental geochemical processes in acidic sulfate-rich environments. The sulfate coordination environment in schwertmannite, however, remains unclear, hindering our understanding of the structure, formation, and environmental behavior of the mineral. In this study, sulfur K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopic analyses in combination with infrared spectroscopy were used to determine the sulfate local atomic environment in wet and air-dried schwertmannite samples after incubation at various pHs and ionic strengths. Results indicate that sulfate exists as both inner- and outer-sphere complexes in schwertmannite. Regardless of the sample preparation conditions, the EXAFS-determined S-Fe interatomic distances are 3.22-3.26 Å, indicative of bidentate-binuclear sulfate inner-sphere complexes. XANES spectroscopy shows that the proportion of the inner-sphere complexes decreases with increasing pH for both wet and dried samples and that the dried samples contain much more inner-sphere complexes than the wet ones at any given pH. Assuming that schwertmannite is a distorted akaganéite-like structure, the sulfate inner-sphere complexation suggests that, the double chains of the edge-sharing Fe octahedra, enclosing the tunnel, must contain defects, on which reactive singly-Fe coordinated hydroxyl functional groups form for ligand exchange with sulfate. The drying effect suggests that the tunnel contains readily exchangeable H2O molecules in addition to sulfate ions.

Cryptomelane is a reactive Mn oxide and has been used in removal of heavy metal from wastewaters. Co-doped cryptomelane was synthesized by refluxing at ambient pressure and characterized by powder X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and extended X-ray absorption fine structure spectroscopy, and its performances for removal of Pb(2+) and Cr(3+) from aqueous solutions were investigated. Co doping has a negligible effect on the structure and morphology of cryptomelane but increases the specific surface area and Mn average oxidation state. Mn and Co K-edge extended X-ray absorption fine structure spectroscopy (EXAFS) analysis shows that Co barely affects the atomic coordination environments of Mn, and distances of edge- and corner-sharing Co-Me (MeCo, Mn) pairs are shorter than those of the corresponding Mn-Me pairs, implying the replacement of framework Mn(III) by Co(III). These Co-doped cryptomelanes can quickly oxidize Cr(3+) to be HCrO4(-) and remove 45%-66% of the total Cr in the reaction systems by adsorption and fixation, and they have enhanced Pb(2+) adsorption capacities. Thus these materials are promising adsorbents for heavy metal remediation. The results demonstrate the design and modification of environmental friendly Mn oxide materials and can help us understand the interaction mechanisms of transition metals with Mn oxides., (Copyright © 2015. Published by Elsevier B.V.)

Vanadium(V)-doped hexagonal turbostratic birnessites were synthesized and characterized by multiple techniques and were used to remove Pb(2+) from aqueous solutions. With increasing V content, the V(V)-doped birnessites have significantly decreased crystallinity, i.e., the thickness of crystals in the c axis decreases from 9.8 nm to ∼0.7 nm, and the amount of vacancies slightly increases from 0.063 to 0.089. The specific surface areas of these samples increase after doping while the Mn average oxidation sates are almost constant. V has a valence of +5 and tetrahedral symmetry, and exists as oxyanions, including V₆O₁₆(2-), and VO4(3-) on birnessite edge sites by forming monodentate corning-sharing complexes. Pb LIII-edge extended X-ray absorption fine structure (EXAFS) spectra analysis shows that, at low V contents (V/Mn≤0.07) Pb(2+) mainly binds with birnessite on octahedral vacancy and especially edge sites whereas at higher V contents (V/Mn>0.07) more Pb(2+) associates with V oxyanions and form vanadinite [Pb₅(VO₄)₃Cl]-like precipitates. With increasing V(V) content, the Pb(2+) binding affinity on the V-doped birnessites significantly increases, ascribing to both the formation of the vanadinite precipitates and decreased particle sizes of birnessite. These results are useful to design environmentally benign materials for treatment of metal-polluted water., (Copyright © 2015 Elsevier B.V. All rights reserved.)

The transport of nanoparticles through aqueous systems is a complex process with important environmental policy ramifications. Ferrihydrite nanoparticles commonly form aggregates, with structures that depend upon solution chemistry. The impact of aggregation state on transport and deposition is not fully understood. In this study, small-angle X-ray scattering (SAXS) and cryogenic transmission electron microscopy (cryo-TEM) were used to directly observe the aggregate structure of ferrihydrite nanoparticles and show how the aggregate structure responds to changing ionic strength. These results were correlated with complementary studies on ferrihydrite transport through saturated quartz sand columns. Within deionized water, nanoparticles form stable suspensions of low-density fractal aggregates that are resistant to collapse. The particles subsequently show limited deposition on sand grain surfaces. Within sodium nitrate solutions the aggregates collapse into denser clusters, and nanoparticle deposition increases dramatically by forming thick, localized, and mechanically unstable deposits. Such deposits limit nanoparticle transport and make transport less predictable. The action of ionic strength is distinct from simpler models of colloidal stability and transport, in that salt not only drives aggregation or attachment but also alters the behavior of preexisting aggregates by triggering their collapse.

Aggregation impacts the reactivity, colloidal stability, and transport behavior of nanomaterials, yet methods to characterize basic structural features of aggregates are limited. Here, cryo-transmission electron microscope (cryo-TEM) based tomography is utilized as a method for directly imaging fragile aggregates of nanoparticles in aqueous suspension and an approach for extracting quantitative fractal dimensions from the resulting three-dimensional structural models is introduced. The structural quantification approach is based upon the mass autocorrelation function, and is directly comparable with small-angle X-ray scattering (SAXS) models. This enables accurate characterization of aggregate structure, even in suspensions where the aggregate cluster size is highly polydisperse and traditional SAXS modeling is not reliable. This technique is applied to study real suspensions of ferrihydrite nanoparticles. By comparing tomographic measurements with SAXS-based measurements, we infer that certain suspensions contain polydisperse aggregate size distributions. In other suspensions, fractal-type structures are identified with low intrinsic fractal dimensions. The fractal dimensions are lower than would be predicted by simple models of particle aggregation, and this low dimensionality enables large, low-density aggregates to exist in stable colloidal suspension.

The structure of ferric iron (Fe(3+)) dimers in aqueous solutions has long been debated. In this work, we have determined the dimer structure in situ in aqueous solutions using extended X-ray absorption fine structure (EXAFS) spectroscopy. An Fe K-edge EXAFS analysis of 0.2 M ferric nitrate solutions at pH 1.28-1.81 identified a Fe-Fe distance at ∼3.6 Å, strongly indicating that the dimers take the μ-oxo form. The EXAFS analysis also indicates two short Fe-O bonds at ∼1.80 Å and ten long Fe-O bonds at ∼2.08 Å, consistent with the μ-oxo dimer structure. The scattering from the Fe-Fe paths interferes destructively with that from paths belonging to Fe(OH2)6(3+) monomers that coexist with the dimers, leading to a less apparent Fe shell in the EXAFS Fourier transform. This might be a reason why the characteristic Fe-Fe distance was not detected in previous EXAFS studies. The existence of μ-oxo dimers is further confirmed by Mössbauer analyses of analogous quick frozen solutions. This work also explores the electronic structure and the relative stability of the μ-oxo dimer in a comparison to the dihydroxo dimer using density function theory (DFT) calculations. The identification of such dimers in aqueous solutions has important implications for iron (bio)inorganic chemistry and geochemistry, such as understanding the formation mechanisms of Fe oxyhydroxides at molecular scale.

In this research, the effects of glyphosate (GPS) on Zn sorption/precipitation on γ-alumina were investigated using a batch technique, Zn K-edge EXAFS, and (31)P NMR spectroscopy. The EXAFS analysis revealed that, in the absence of glyphosate, Zn adsorbed on the aluminum oxide surface mainly as bidentate mononuclear surface complexes at pH 5.5, whereas Zn-Al layered double hydroxide (LDH) precipitates formed at pH 8.0. In the presence of glyphosate, the EXAFS spectra of Zn sorption samples at pH 5.5 and 8.0 were very similar, both of which demonstrated that Zn did not directly bind to the mineral surface but bonded with the carboxyl group of glyphosate. Formation of γ-alumina-GPS-Zn ternary surface complexes was further suggested by (31)P solid state NMR data which indicated the glyphosate binds to γ-alumina via a phosphonate group, bridging the mineral surface and Zn. Additionally, we showed the sequence of additional glyphosate and Zn can influence the sorption mechanism. At pH 8, Zn-Al LDH precipitates formed if Zn was added first, and no precipitates formed if glyphosate was added first or simultaneously with Zn. In contrast, at pH 5.5, only γ-alumina-GPS-Zn ternary surface complexes formed regardless of whether glyphosate or Zn was added first or both were added simultaneously.

The phases and stability of ferric iron products formed early during neutralization of acid mine drainage waters remain largely unknown. In this work, we used in situ and time-resolved quick-scanning X-ray absorption spectroscopy and X-ray diffraction to study products formed between 4 min and 1 h after ferric iron sulfate solutions were partially neutralized by addition of NaHCO(3) ([HCO(3)(-)]/[Fe(3+)] < 3). When [HCO(3)(-)]/[Fe(3+)] = 0.5 and 0.6 (initial pH ∼ 2.1 and 2.2, respectively), the only large species formed were sulfate-complexed ferrihydrite-like molecular clusters that were stable throughout the duration of the experiment. When [HCO(3)(-)]/[Fe(3+)] = 1 (initial pH ∼ 2.5), ferrihydrite-like molecular clusters formed initially, but most later converted to schwertmannite. In contrast, when [HCO(3)(-)]/[Fe(3+)] = 2 (initial pH ∼ 2.7), schwertmannite and larger ferrihydrite particles formed immediately upon neutralization. However, the ferrihydrite particles subsequently converted to schwertmannite. The schwertmannite particles formed under both conditions aggregated extensively with increasing time. This work provides new insight into the formation, stability and reactivity of some early products that may form during the neutralization of natural acid mine drainage.

Manganese (Mn) oxides are among the strongest mineral oxidants in the environment and impose significant influence on mobility and bioavailability of redox-active substances, such as arsenic, chromium, and pharmaceutical products, through oxidation processes. Oxidizing potentials of Mn oxides are determined by Mn valence states (2+, 3+, 4+). In this study, the effects of beam damage during electron energy-loss spectroscopy (EELS) in the transmission electron microscope have been investigated to determine the "safe dose" of electrons. Time series analyses determined the safe dose fluence (electrons/nm(2)) for todorokite (10(6) e/nm(2)), acid birnessite (10(5)), triclinic birnessite (10(4)), randomly stacked birnessite (10(3)), and δ-MnO(2) (<10(3)) at 200 kV. The results show that meaningful estimates of the mean Mn valence can be acquired by EELS if proper care is taken.

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.

Biologically catalyzed Mn(II) oxidation produces biogenic Mn-oxides (BioMnO(x)) and may serve as one of the major formation pathways for layered Mn-oxides in soils and sediments. The structure of Mn octahedral layers in layered Mn-oxides controls its metal sequestration properties, photochemistry, oxidizing ability, and topotactic transformation to tunneled structures. This study investigates the impacts of cations (H(+), Ni(II), Na(+), and Ca(2+)) during biotic Mn(II) oxidation on the structure of Mn octahedral layers of BioMnO(x) using solution chemistry and synchrotron X-ray techniques. Results demonstrate that Mn octahedral layer symmetry and composition are sensitive to previous cations during BioMnO(x) formation. Specifically, H(+) and Ni(II) enhance vacant site formation, whereas Na(+) and Ca(2+) favor formation of Mn(III) and its ordered distribution in Mn octahedral layers. This study emphasizes the importance of the abiotic reaction between Mn(II) and BioMnO(x) and dependence of the crystal structure of BioMnO(x) on solution chemistry.

Biogenic Mn-oxides (BioMnO(x)), produced by microorganisms, possess an extraordinary ability to sequester metals. BioMnO(x) are generally layered structures containing varying amounts of Mn(III) and vacant sites in the Mn layers. However the relationship between the varying structure of BioMnO(x) and metal sorption properties remains unclear. In this study, BioMnO(x) produced by Pseudomonas putida strain GB-1 was synthesized at either pH 6, 7, or 8 in CaCl(2) solution, and Ni(II) sorption mechanisms were determined at pH 7 and at different Ni(II) loadings, using isotherm and extended X-ray absorption fine structure (EXAFS) spectroscopic analyses. Our data demonstrate that Ni(II) sorbs at vacant sites in the interlayer of the BioMnO(x) and the maximum Ni(II) sorption capacity increases as the formation pH of BioMnO(x) decreases. This relation indicates that the quantity of BioMnO(x) vacant sites increases as formation conditions become more acidic, which is in good agreement with our companion study. Contents of the vacant sites were quantitatively estimated based on maximum Ni(II) sorption capacity. Additionally, this study reveals that imidazole groups are involved in Ni(II) binding to biomaterials, and have a higher Ni(II) sorption affinity, but a lower site density compared to carboxyl groups.

Density functional theory (DFT) calculations were used to investigate As(V) and As(III) surface complex structures and reaction energies on both Mn(III) and Mn(IV) sites in an attempt to better understand As(III) oxidation bybirnessite, a layered Mn-dioxide mineral. Edge-sharing dioctahedral Mn(III) and Mn(IV) clusters with different combinations of surface functional groups (>MnOH and >MnOH2) were employed to mimic pH variability. Results show that As(V) adsorption was more thermodynamically favorable than As(III) adsorption on both Mn(III) and Mn(IV) surface sites under simulated acidic pH conditions. Therefore, we propose that As(V) adsorption inhibits As(III) oxidation by blocking adsorption sites. Under simulated acidic pH conditions, Mn(IV) sites exhibited stronger adsorption affinity than Mn(III) sites for both As(III) and As(V). Overall, we hypothesize that Mn(III) sites are less reactive in terms of As(III) oxidation due to their lower affinity for As(III) adsorption, higher potential to be blocked by As(V) complexes, and slower electron transfer rates with adsorbed As(III). Results from this study offer an explanation regarding the experimental observations of Mn(III) accumulation on birnessite and the long residence time of As(III) adsorption complexes on manganite (r-MnOOH) during As(III) oxidation.

Optimal geometries, charge distributions, bond analysis, changes of Gibbs free energy, entropies and enthalpies of hydration, and hydrolysis reactions for mononuclear species of Zn(2+) including hydrated and hydrolysis complexes were investigated using quantum chemical calculations in the gas phase. Optimized geometrical structures showed that the stable hydrated and hydrolysis zinc species without outer-sphere water molecules were Zn(H(2)O)(6)(2+), Zn(OH)(H(2)O)(3)(+), Zn(OH)(2)(H(2)O)(2), Zn(OH)(3)(-), and Zn(OH)(4)(2-). Results of NPA (Natural Population Analysis) indicated that the charge on the Zn atom of the hydrated ions decreased but the charge on the zinc atom of the hydrolysis species increased with the increase of inner-sphere water molecules. NBO (Natural Bond Orbital) analyses demonstrated that hydrated and hydrolysis species of zinc were mainly electrostatic bonding compounds. Calculations of reaction energies indicated that inner-sphere water molecules became more unfavorable as the hydrolysis increased. Stepwise hydrolysis equilibrium constants decreased successively and the order remained unchanged when the inner-sphere dehydration occurred.