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.

Cadmium Isotope Fractionation during Adsorption onto Edge Sites and Vacancies in Phyllomanganate.

Cadmium (Cd) geochemical behavior is strongly influenced by its adsorption onto natural phyllomanganates, which contain both layer edge sites and vacancies; however, Cd isotope fractionation mechanisms at these sites have not yet been addressed. In the present work, Cd isotope fractionation during adsorption onto hexagonal (containing both types of sites) and triclinic birnessite (almost only edge sites) was investigated using a combination of batch adsorption experiments, extended X-ray absorption fine structure (EXAFS) spectroscopy, surface complexation modeling, and density functional theory (DFT) calculations. Light Cd isotopes are preferentially enriched on solid surfaces, and the isotope fractionation induced by Cd2+ adsorption on edge sites (Δ114/110Cdedge-solution = -1.54 ± 0.11‰) is smaller than that on vacancies (Δ114/110Cdvacancy-solution = -0.71 ± 0.21‰), independent of surface coverage or pH. Both Cd K-edge EXAFS and DFT results indicate the formation of double corner-sharing complexes on layer edge sites and mainly triple cornering-sharing complexes on vacancies. The distortion of both complexes results in the negative isotope fractionation onto the solids, and the slightly longer first Cd-O distances and a smaller number of nearest Mn atoms around Cd at edge sites probably account for the larger fractionation magnitude compared to that of vacancies. These results provide deep insights into Cd isotope fractionation mechanisms during interactions with phyllomanganates.

Adsorption Mechanisms of Glyphosate on Ferrihydrite: Effects of Al Substitution and Aggregation State.

Ferrihydrite is one of the most reactive iron (Fe) (oxyhydr)oxides in soils, but the adsorption mechanisms of glyphosate, the most widely used herbicide, on ferrihydrite remain unknown. Here, we determined the adsorption mechanisms of glyphosate on pristine and Al-substituted ferrihydrites with aggregated and dispersed states using macroscopic adsorption experiments, zeta potential, phosphorus K-edge X-ray absorption near-edge structure spectroscopy, in situ attenuated total reflectance Fourier transform infrared spectroscopy coupled with two-dimensional correlation spectroscopy, and multivariate curve resolution analyses. Aggregation of ferrihydrite decreases the glyphosate adsorption capacity. The partial substitution of Al in ferrihydrite inhibits glyphosate adsorption on aggregated ferrihydrite due to the decrease of external specific surface area, while it promotes glyphosate adsorption on dispersed ferrihydrite, which is ascribed to the increase of surface positive charge. Glyphosate predominately forms protonated and deprotonated, depending on the sorption pH, monodentate-mononuclear complexes (MMH1/MMH0, 77-90%) on ferrihydrites, besides minor deprotonated bidentate-binuclear complexes (BBH0, 23-10%). Both Al incorporation and a low pH favor the formation of the BB complex. The adsorbed glyphosate preferentially forms the MM complex on ferrihydrite and preferentially bonds with the Al-OH sites on Al-substituted ferrihydrite. These new insights are expected to be useful in predicting the environmental fate of glyphosate in ferrihydrite-rich environments.

Simultaneous oxidation of Mn(II) and As(III) on cupric oxide (CuO) promotes As(III) removal at circumneutral pH.

Oxidation of Mn(II) or As(III) by molecular oxygen is slow at pH < 9, while they can be catalytically oxidized in the presence of oxide minerals and then removed from contaminated water. However, the reaction mechanisms on simultaneous oxidation of Mn(II) and As(III) on oxide mineral surface and their accompanied removal efficiency remain unclear. This study compared Mn(II) oxidation on four common metal oxides (γ-Al2O3, CuO, α-Fe2O3 and ZnO) and investigated the simultaneous oxidation and removal of Mn(II) and As(III) through batch experiments and spectroscopic analyses. Among the tested oxides, CuO and α-Fe2O3 possess greater catalytic activity toward Mn(II) oxidation. Oxidation and removal kinetics of Mn(II) and As(III) on CuO indicate that O2 is the terminal electron acceptor for Mn(II) and As(III) oxidation on CuO, and Mn(II) acts as an electron shuttle to promote As(III) oxidation and removal. The main oxidized product of Mn(II) on CuO is high-valent MnOx species. This newly formed Mn(III) or Mn(IV) phases promote As(III) oxidation on CuO at circumneutral pH 8 and is reduced to Mn(II), which may be then released into solution. This study provides new insights into metal oxide-catalyzed oxidation of pollutants Mn(II) and As(III) and suggests that CuO should be considered as an efficient material to remediate Mn(II) and As(III) contamination.

Facet-Dependent Photoinduced Transformation of Cadmium Sulfide (CdS) Nanoparticles.

Microbial-mediated transformation of anthropogenic Cd2+ controls its distribution, bioavailability, and potential risks. However, the processes readily form CdS nanoparticles (CdS-NPs), which exhibit dissolution behavior different from that of larger sized particles. Here, we investigated the effects of morphologies and facets of CdS-NPs on their photoinduced dissolution. Three CdS-NPs, CdS-sphere, CdS-rod, and CdS-sheet, and one nanosized biogenic CdS (Bio-CdS) were synthesized with different dominant facets of {101}, {100}, {001}, and {111} and thus distinct surface chemistry. As explored by HRTEM, EPR, and DFT calculations, photogenerated e-/h+ pairs were more likely to generate on CdS-sheet surfaces due to higher surface energies and a narrower band gap, facilitating the formation of •OH and thereby faster dissolution (kobs = 6.126-6.261 × 10-2 h-1). The wider band gaps of CdS-sphere and CdS-rod caused less formation of O2•- and •OH, leading to slower oxidative dissolutions (kobs = 0.090-0.123 and 2.174-3.038 × 10-2 h-1, respectively). Given the similar surface energy as that of CdS-sheet, the dissolution rate of Bio-CdS was close to that of CdS-rod and CdS-sheet, which was 1.6-3.5 times faster than that of larger sized CdS, posing higher environmental risks than thought. Altogether, this work revealed the facet effects on the dissolution of CdS-NPs, manifesting a deeper understanding of metal sulfides' environmental behaviors.

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.

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.

Catalytic oxidation of arsenite and reaction pathways on the surface of CuO nanoparticles at a wide range of pHs.

Recently, the wide application of CuO nanoparticles (NPs) in engineering field inevitably leads to its release into various geologic settings, which has aroused great concern about the geochemical behaviors of CuO NPs due to its high surface reactivity and impact on the fate of co-existing contaminants. However, the redox transformation of pollutants mediated by CuO NPs and the underlying mechanism still remain poorly understood. Here, we studied the interaction of CuO NPs with As(III), and explored the reaction pathways using batch experiments and multiple spectroscopic techniques. The results of in situ quick scanning X-ray absorption spectroscopy (Q-XAS) analysis verified that CuO NPs is capable of catalytically oxidize As(III) under dark conditions efficiently at a wide range of pHs. As(III) was firstly adsorbed on CuO NPs surface and then gradually oxidized to As(V) with dissolved O2 as the terminal electron acceptor. As(III) adsorption increased to the maximum at a pH close to PZC of CuO NPs (~ pH 9.2), and then sharply decreased with increasing pH, while the oxidation capacity monotonically increased with pH. X-ray photoelectron spectroscopy and electron paramagnetic resonance characterization of samples from batch experiments indicated that two pathways may be involved in As(III) catalytic oxidation: (1) direct electron transfer from As(III) to Cu(II), followed by concomitant re-oxidation of the produced Cu(I) by dissolved O2 back to Cu(II) on CuO NPs surface, and (2) As(III) oxidation by reactive oxygen species (ROS) produced from the above Cu(I) oxygenation process. These observations facilitate a better understanding of the surface catalytic property of CuO NPs and its interaction with As(III) and other elements with variable valence in geochemical environments.

Enhanced Dissolution and Transformation of ZnO Nanoparticles: The Role of Inositol Hexakisphosphate.

The toxicity, reactivity, and behavior of zinc oxide (ZnO) nanoparticles (NPs) released in the environment are highly dependent on environmental conditions. Myo-inositol hexakisphosphate (IHP), a common organic phosphate, may interact with NPs and generate new transformation products. In this study, the role of IHP in mediating the dissolution and transformation of ZnO NPs was investigated in the laboratory kinetic experiments using powder X-ray diffraction, attenuated total reflectance Fourier transform infrared spectroscopy, (31)P nuclear magnetic resonance spectroscopy, high-resolution transmission electronic microscopy, and synchrotron-based extended X-ray absorption fine structure spectroscopy. The results indicate that IHP shows a dissolution-precipitation effect, which is different from citrate and EDTA that only enhances Zn dissolution. The enhanced dissolution and transformation of ZnO NPs by IHP (<0.5 h) is found to be strikingly faster than that induced by inorganic phosphate (Pi, > 3.0 h) at pH 7.0, and the reaction rate increases with decreasing pH and increasing IHP concentration. Multitechnique analyses reveal that interaction of ZnO NPs with IHP induces rapid transformation of ZnO NPs into zinc phytate complexes initially and poorly crystalline zinc phytate-like (Zn-IHP) phase finally. Additionally, ZnO NPs preferentially react with IHP and transform to Zn-IHP when Pi and IHP concurrently coexist in a system. Overall, results from this study contribute to an improved understanding of the role of organic phosphates (e.g., IHP) in the speciation and structural transformation of ZnO NPs, which can be leveraged for remediation of ZnO-polluted water and soils.

Redox Reactions between Mn(II) and Hexagonal Birnessite Change Its Layer Symmetry.

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.

Effects of Al(3+) doping on the structure and properties of goethite and its adsorption behavior towards phosphate.

Al substitution in goethite is common in soils, and has strong influence on the structure and physicochemical properties of goethite. In this research, a series of Al-doped goethites were synthesized, and characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR) and extended X-ray absorption fine structure (EXAFS) spectroscopy. The adsorption behavior of these samples towards PO4(3-) was also investigated. Characterization results demonstrated that increasing Al content in goethite led to a reduction in crystallinity, increase in specific surface area (SSA), and morphology change from needle-like to granular. Rietveld structure refinement revealed that the lattice parameter a remained almost constant and b slightly decreased, but c was significantly reduced, and the calculated crystal density increased. EXAFS analysis demonstrated that the Fe(Al)-O distance in the structure of the doped goethites was almost the same, but the Fe-Fe(Al) distance decreased with increasing Al content. Surface analysis showed that, with increasing Al content, the content of OH groups on the mineral surface increased. The adsorption of phosphate per unit mass of Al-doped goethite increased, while adsorption per unit area decreased owing to the decrease of the relative proportion of (110) facets in the total surface area of the minerals. The results of this research facilitate better understanding of the effect of Al substitution on the structure and properties of goethite and the cycling of phosphate in the environment.

Absorption mechanisms of Cu(2+) on a biogenic bixbyite-like Mn2O3 produced by Bacillus CUA isolated from soil.

BACKGROUND: Although most reported biogenic Mn oxides are hexagonal birnessites, other types of biogenic Mn oxides also commonly occur in the environment. However, sorption characteristics and underlying mechanisms of the adsorption of heavy-metal ions on these biogenic Mn oxides are still rarely addressed. In this study, the sorption mechanisms of Cu(II) on a low valence biogenic Mn oxide, poorly crystallized bixbyite-like Mn2O3 (α-Mn2O3), were investigated. RESULTS: The maximum adsorption capacity of Cu(II) onto this biogenic Mn oxide at pH 6.00 was 796 mmol/kg (0.45 mol Cu mol(-1) Mn). The complex structure of adsorbed Cu(II) was constrained using Cu extended X-ray absorption fine structure (EXAFS) analysis, combined with structural parameters of the biogenic Mn oxide with alternately arranged regular and distorted MnO6 octahedra obtained through multiple-FEFF fitting of Mn EXAFS data. The sorbed Cu(II) was found to coordinate with the biogenic Mn oxide particle edges as inner-sphere complexes. At a relatively low Cu(2+) loading (233 mmol/kg, pH 6.00), Cu(II) adsorbed onto the biogenic Mn oxide with two types of coordinated complexes, i.e., (1) coordinated with one regular/distorted MnO6 octahedron as a monodentate-mononuclear complex and (2) with two adjacent MnO6 octahedra as a bidentate-binuclear complex. While, at a relatively high Cu(2+) loading (787 mmol/kg, pH 6.00), only one type of coordinated complex was constrained, the adsorbed Cu(II) coordinated with one regular/distorted MnO6 octahedron as a monodentate-mononuclear complex. CONCLUSIONS: This research extends further insight into the bacterial Mn(II) oxidation in the environment and serves as a good reference for understanding the interactions between metal ions and biogenic low valence Mn oxides, which are still poorly explored either theoretically or practically.

Interaction mechanisms and kinetics of ferrous ion and hexagonal birnessite in aqueous systems.

BACKGROUND: In soils and sediments, manganese oxides and oxygen usually participate in the oxidation of ferrous ions. There is limited information concerning the interaction process and mechanisms of ferrous ions and manganese oxides. The influence of air (oxygen) on reaction process and kinetics has been seldom studied. Because redox reactions usually occur in open systems, the participation of air needs to be further investigated. RESULTS: To simulate this process, hexagonal birnessite was prepared and used to oxidize ferrous ions in anoxic and aerobic aqueous systems. The influence of pH, concentration, temperature, and presence of air (oxygen) on the redox rate was studied. The redox reaction of birnessite and ferrous ions was accompanied by the release of Mn2+ and K+ ions, a significant decrease in Fe2+ concentration, and the formation of mixed lepidocrocite and goethite during the initial stage. Lepidocrocite did not completely transform into goethite under anoxic condition with pH about 5.5 within 30 days. Fe2+ exhibited much higher catalytic activity than Mn2+ during the transformation from amorphous Fe(III)-hydroxide to lepidocrocite and goethite under anoxic conditions. The release rates of Mn2+ were compared to estimate the redox rates of birnessite and Fe2+ under different conditions. CONCLUSIONS: Redox rate was found to be controlled by chemical reaction, and increased with increasing Fe2+ concentration, pH, and temperature. The formation of ferric (hydr)oxides precipitate inhibited the further reduction of birnessite. The presence of air accelerated the oxidation of Fe2+ to ferric oxides and facilitated the chemical stability of birnessite, which was not completely reduced and dissolved after 18 days. As for the oxidation of aqueous ferrous ions by oxygen in air, low and high pHs facilitated the formation of goethite and lepidocrocite, respectively. The experimental results illustrated the single and combined effects of manganese oxide and air on the transformation of Fe2+ to ferric oxides. Graphical abstract:Lepidocrocite and goethite were formed during the interaction of ferrous ion and birnessite at pH 4-7. Redox rate was controlled by the adsorption of Fe2+ on the surface of birnessite. The presence of air (oxygen) accelerated the oxidation of Fe2+ to ferric oxides and facilitated the chemical stability of birnessite.

Formation of todorokite from "c-disordered" H(+)-birnessites: the roles of average manganese oxidation state and interlayer cations.

BACKGROUND: Todorokite, a 3 × 3 tectomanganate, is one of three main manganese oxide minerals in marine nodules and can be used as an active MnO6 octahedral molecular sieve. The formation of todorokite is closely associated with the poorly crystalline phyllomanganates in nature. However, the effect of the preparative parameters on the transformation of "c-disordered" H(+)-birnessites, analogue to natural phyllomanganates, into todorokite has not yet been explored. RESULTS: Synthesis of "c-disordered" H(+)-birnessites with different average manganese oxidation states (AOS) was performed by controlling the MnO4 (-)/Mn(2+) ratio in low-concentrated NaOH or KOH media. Further transformation to todorokite, using "c-disordered" H(+)-birnessites pre-exchanged with Na(+) or K(+) or not before exchange with Mg(2+), was conducted under reflux conditions to investigate the effects of Mn AOS and interlayer cations. The results show that all of these "c-disordered" H(+)-birnessites exhibit hexagonal layer symmetry and can be transformed into todorokite to different extents. "c-disordered" H(+)-birnessite without pre-exchange treatment contains lower levels of Na/K and is preferably transformed into ramsdellite with a smaller 1 × 2 tunnel structure rather than todorokite. Na(+) pre-exchange, i.e. to form Na-H-birnessite, greatly enhances transformation into todorokite, whereas K(+) pre-exchange, i.e. to form K-H-birnessite, inhibits the transformation. This is because the interlayer K(+) of birnessite cannot be completely exchanged with Mg(2+), which restrains the formation of tunnel "walls" with 1 nm in length. When the Mn AOS values of Na-H-birnessite increase from 3.58 to 3.74, the rate and extent of the transformation sharply decrease, indicating that a key process is Mn(III) species migration from layer into interlayer to form the tunnel structure during todorokite formation. CONCLUSIONS: Structural Mn(III), together with the content and type of interlayer metal ions, plays a crucial role in the transformation of "c-disordered" H(+)-birnessites with hexagonal symmetry into todorokite. This provides further explanation for the common occurrence of todorokite in the hydrothermal ocean environment, where is usually enriched in large metal ions such as Mg, Ca, Ni, Co and etc. These results have significant implications for exploring the origin and formation process of todorokite in various geochemical settings and promoting the practical application of todorokite in many fields.Graphical abstractXRD patterns of Mg(2+)-exchanged and reflux treatment products for the synthetic "c-disordered" H(+)-birnessites.

Sulfate Local Coordination Environment in Schwertmannite.

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.

Structure and properties of Co-doped cryptomelane and its enhanced removal of Pb²âº and Cr³âº from wastewater.

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.

Mechanism of myo-inositol hexakisphosphate sorption on amorphous aluminum hydroxide: spectroscopic evidence for rapid surface precipitation.

Inositol hexakisphosphates are the most abundant organic phosphates (OPs) in most soils and sediments. Adsorption, desorption, and precipitation reactions at environmental interfaces govern the reactivity, speciation, mobility, and bioavailability of inositol hexakisphosphates in terrestrial and aquatic environments. However, surface complexation and precipitation reactions of inositol hexakisphosphates on soil minerals have not been well understood. Here we investigate the surface complexation-precipitation process and mechanism of myo-inositol hexakisphosphate (IHP, phytate) on amorphous aluminum hydroxide (AAH) using macroscopic sorption experiments and multiple spectroscopic tools. The AAH (16.01 µmol m(-2)) exhibits much higher sorption density than boehmite (0.73 µmol m(-2)) and α-Al2O3 (1.13 µmol m(-2)). Kinetics of IHP sorption and accompanying OH(-) release, as well as zeta potential measurements, indicate that IHP is initially adsorbed on AAH through inner-sphere complexation via ligand exchange, followed by AAH dissolution and ternary complex formation; last, the ternary complexes rapidly transform to surface precipitates and bulk phase analogous to aluminum phytate (Al-IHP). The pH level, reaction time, and initial IHP loading evidently affect the interaction of IHP on AAH. In situ ATR-FTIR and solid-state NMR spectra further demonstrate that IHP sorbs on AAH and transforms to surface precipitates analogous to Al-IHP, consistent with the results of XRD analysis. This study indicates that active metal oxides such as AAH strongly mediate the speciation and behavior of IHP via rapid surface complexation-precipitation reactions, thus controlling the mobility and bioavailability of inositol phosphates in the environment.

Iron (hydr)oxides-induced activation of sulfite for contaminants degradation: The critical role of structural Fe(III).

Iron-based sulfite (S(IV)) activation has emerged as a novel strategy to generate sulfate radicals (SO4•-) for contaminants degradation. However, numerous studies focused on dissolved iron-induced homogeneous activation processes while the potential of structural Fe(III) remains unclear. In this study, five iron (hydr)oxide soil minerals (FeOx) including ferrihydrite, schwertmannite, lepidocrocite, goethite and hematite, were successfully employed as sources of structural Fe(III) for S(IV) activation. Results showed that the catalytical ability of structural Fe(III) primarily depended on the crystallinity of FeOx instead of their specific surface area and particle size, with ferrihydrite and schwertmannite being the most active. Furthermore, in-situ ATR-FTIR spectroscopy and 2D-COS analysis revealed that HSO3- was initially adsorbed on FeO6 octahedrons of FeOx via monodentate inner-sphere complexation, ultimately oxidized into SO42- which was then re-adsorbed via outer-sphere complexation. During this process, strong oxidizing SO4•- and •OH were formed for pollutants degradation, confirmed by radical quenching experiments and electron spin resonance. Moreover, FeOx/S(IV) system exhibited superior applicability with respect to recycling test, real waters and twenty-six pollutants degradation. Eventually, plausible degradation pathways of three typical pollutants were proposed. This study highlights the feasibility of structural Fe(III)-containing soil minerals for S(IV) activation in wastewater treatment.

New insight into wastewater treatment by activation of sulfite with humic acid under visible light irradiation.

Sulfite (S(IV)), as an alternative to persulfate, has demonstrated its cost-effectiveness and environmentally friendly nature, garnering increasing attention in Advanced Oxidation Processes (AOPs). Dissolved organic matter (DOM) commonly occurred in diverse environments and was often regarded as an interfering factor in sulfite-based AOPs. However, less attention has been paid to the promotion of the activation of sulfite by excited DOM, which could produce various reactive intermediates. The study focused on the activation of sulfite using visible light (VL) - excited humic acid (HA) to efficiently degrade many common organic pollutants, which was better than peroxydisulfate (PDS) and peroxymonosulfate (PMS) systems. Quenching experiments and electron paramagnetic resonance (EPR) analysis revealed that the triplet states of HA (3HA*) activated sulfite through energy transfer, resulting in the production of SO4·-, O2·-, and 1O2. The most significant active species found in the degradation of roxarsone (ROX) was 1O2, which was a non-radical pathway and exhibits high selectivity for pollutant degradation. This non-radical pathway was not commonly observed in traditional sulfite-based AOPs. Additionally, the coexistence of various inorganic anions, such as NO3-, Cl-, SO42-, CO32-, and PO43-, had little effect on the degradation of ROX. Furthermore, DOM from different natural water demonstrated efficient activation of S(IV) under light conditions, opening up new possibilities for applying sulfite-based advanced oxidation to the remediation of organic pollution in diverse sites and water bodies. In summary, this research offered promising insights into the potential application of sulfite-based AOPs, facilitated by photo-excited HA, as a new strategy for efficiently degrading organic pollutants in various environmental settings.

Photocatalytic activation of sulfite by maghemite (γ-Fe2O3) for iohexol degradation and alleviation effect of HCO3- on water acidification.

Photo-catalyzing sulfite (S(IV)) for the generation of sulfate radical (SO4•-) has emerged as a novel advanced oxidation process (AOP) recently. However, both the potential of soil minerals as effective photocatalysts and the process of water acidification due to S(IV) oxidation have been overlooked. Herein, maghemite (γ-Fe2O3), a typical soil iron oxide with excellent photocatalytic reactivity like hematite and magnetic-collectible property like magnetite, was successfully used to activate S(IV) for iohexol degradation under visible light irradiation. As a result, 91.3% of iohexol was eliminated within 15 min at 0.1 g/L maghemite and 0.5 mM S(IV) under neutral conditions. The influencing factors, including initial pH, catalyst dosage, S(IV) amount, co-existing substances and water matrix, were systematically investigated. The maghemite/S(IV)/vis system exhibited superior performance in iohexol degradation at a wide pH range (3-10). It was found that the released proton via S(IV) oxidation led to severe water acidification. Interestingly, a low dose of HCO3- could evidently resist water acidification with little influence on iohexol elimination. Radical quenching experiments and electron spin resonance (ESR) analysis confirmed that SO4•-, •OH and •O2- were involved in iohexol abatement with SO4•- being the dominant reactive species. Compared with hydrogen peroxide, persulfate and peroxymonosulfate, the established maghemite/S(IV)/vis system achieved much more remarkable degradation performance. Furthermore, the reactivity of the catalyst was not obviously reduced even after 10 runs of reaction. This study expands the application of soil iron oxide mineral in S(IV) activation in water treatment and proposes an approach to regulate water acidification in S(IV)-based AOP.