Combined exposure to lead and microplastics increased risk of glucose metabolism in mice via the Nrf2/NF-κB pathway.

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.

Controls of Mineral Solubility on Adsorption-Induced Molecular Fractionation of Dissolved Organic Matter Revealed by 21 T FT-ICR MS.

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 Al3+ 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 Degradation by Trivalent Manganese.

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 (MnO2-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 NaNO3 at 25 °C. The presence of low-molecular-weight organic acids (e.g., oxalate and citrate) substantially enhances MeHg degradation by MnO2-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 Oxidation States in Volcanic Soils across Annual Rainfall Gradients.

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.

Secondary Mineral Formation and Carbon Dynamics during FeS Oxidation in the Presence of Dissolved Organic Matter.

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 O2, 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.

Coupling Molecular-Scale Spectroscopy with Stable Isotope Analyses to Investigate the Effect of Si on the Mechanisms of Zn-Al LDH Formation on Al Oxide.

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 (Δ66Znsorbed-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-Al2O3, indicating that >Si-Zn inner-sphere complexes (">" denotes surface) likely bond to the γ-Al2O3 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.

X-ray Spectroscopic Quantification of Phosphorus Transformation in Saharan Dust during Trans-Atlantic Dust Transport.

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 Isotope Fractionation during Adsorption and Substitution with Iron (Oxyhydr)oxides.

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 (Δ114/110Cdsolid-solution) for goethite (Goe) (-0.51 ± 0.04‰), hematite (Hem) (-0.54 ± 0.10‰), and ferrihydrite (Fh) (-0.55 ± 0.03‰). Neither the initial Cd2+ 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 [CdO6] 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 Δ114/110Cdsolid-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.

Macromolecular Characterization of Compound Selectivity for Oxidation and Oxidative Alterations of Dissolved Organic Matter by Manganese Oxide.

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-MnO2) at pH 4 or 6. Polycyclic aromatic hydrocarbons, polyphenols, and carbohydrates were more reactive in reducing δ-MnO2 than highly unsaturated and phenolic (HuPh) compounds and aliphatics, but highly abundant HuPh contributed the most (∼50%) to the overall reduction of δ-MnO2. 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.

A Bioinspired Molybdenum Catalyst for Aqueous Perchlorate Reduction.

Perchlorate (ClO4-) is a pervasive, harmful, and inert anion on both Earth and Mars. Current technologies for ClO4- reduction entail either harsh conditions or multicomponent enzymatic processes. Herein, we report a heterogeneous (L)Mo-Pd/C catalyst directly prepared from Na2MoO4, a bidentate nitrogen ligand (L), and Pd/C to reduce aqueous ClO4- into Cl- with 1 atm of H2 at room temperature. A suite of instrument characterizations and probing reactions suggest that the MoVI precursor and L at the optimal 1:1 ratio are transformed in situ into oligomeric MoIV active sites at the carbon-water interface. For each Mo site, the initial turnover frequency (TOF0) for oxygen atom transfer from ClOx- substrates reached 165 h-1. The turnover number (TON) reached 3840 after a single batch reduction of 100 mM ClO4-. This study provides a water-compatible, efficient, and robust catalyst to degrade and utilize ClO4- for water purification and space exploration.

Molecular-Scale Understanding of Sulfate Exchange from Schwertmannite by Chromate Versus Arsenate.

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/OH2, with 0.59-0.71 sulfate released per Cr(VI) sorbed. While As(V) also forms BB complexes, it exchanges sulfate and >Fe-OH/OH2 equally with 0.49-0.52 sulfate released per As(V) sorbed. At high As(V) loadings, As(V) precipitates as amorphous FeAsO4, 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.

Inhibition of Oxyanions on Redox-driven Transformation of Layered Manganese Oxides.

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-MnO2, a nanoparticulate hexagonal birnessite, in the presence of phosphate or silicate at pH 6-8 and a wide range of Mn(II)/MnO2 molar ratios. Without the oxyanions, δ-MnO2 transforms into triclinic birnessite (T-bir) and 4 × 4 tunneled Mn oxide (TMO) at low Mn(II)/MnO2 ratios (0.09 and 0.13) and into δ-MnOOH and Mn3O4 with minor poorly crystallized α- and γ-MnOOH at high Mn(II)/MnO2 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-MnO2, 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.

Oxidation of Mn(III) Species by Pb(IV) Oxide as a Surrogate Oxidant in Aquatic Systems.

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 PbO2 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 PbO2 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 PbO2 with detectable production of Pb(II). The favorability of Mn(III) oxidation by PbO2 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 PbO2 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.

Process-based modeling of arsenic(III) oxidation by manganese oxides under circumneutral pH conditions.

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.

Coupled Manganese Redox Cycling and Organic Carbon Degradation on Mineral Surfaces.

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 O2 on goethite surfaces. The impacts were more pronounced at higher pH. Mn(II) oxidation produced ß-MnOOH, γ-MnOOH, and Mn3O4 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 ß-MnOOH while favoring the production of γ-MnOOH and Mn(II) adsorbed on the HA-mineral assemblage. Nonconducting γ-Al2O3 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.

Surveying Manganese Oxides as Electrode Materials for Harnessing Salinity Gradient Energy.

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 (ß-MnO2) to 1.18 ± 0.01 W/m2 (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.

Quantifying Uncertainties in Sequential Chemical Extraction of Soil Phosphorus Using XANES Spectroscopy.

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 NaHCO3 and then 0.1 M NaOH), creating new Ca-P via formation of Ca phosphates between NaOH-desorbed phosphate and exchangeable Ca2+ 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 Ca2+ regardless of the presence or absence of CaCO3, 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.

Cd(II) retention and remobilization on δ-MnO2 and Mn(III)-rich δ-MnO2 affected by Mn(II).

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-MnO2 and Mn(III)-rich δ-MnO2 (denoted as HE-MnO2). At pH 5.5, Cd(II) sorption to birnessite was inhibited by Mn(II) addition. Mn(II) addition to δ-MnO2 led to Cd(II) migration from vacant sites to edge sites, forming double-corner sharing (DCS) complexes. Mn(II) introduction to δ-MnO2 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-MnO2. Mn(II) addition to HE-MnO2 increased the CdMn distance in DES complexes. The stability of adsorbed Cd(II) on HE-MnO2 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-MnO2 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.

Metal Adsorption Controls Stability of Layered Manganese Oxides.

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-MnO2 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-MnO2 first transforms to Mn(III)-rich δ-MnO2 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-MnO2 and T-bir form and persist in the Mg2+ and Ca2+ chloride solutions. However, in the presence of surface adsorbed Cu(II), Mn(II)-bearing δ-MnO2 turns into Mn(III)-rich δ-MnO2 without forming T-bir or TMOs. The stabilizing power of the cations on the δ-MnO2 structure positively correlates with their binding strength to δ-MnO2 (Li+, Na+, and K+ < Mg2+ and Ca2+ < 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.