Iron Vacancy Accelerates Fe(II)-Induced Anoxic As(III) Oxidation Coupled to Iron Reduction.

Chemical oxidation of As(III) by iron (Fe) oxyhydroxides has been proposed to occur under anoxic conditions and may play an important role in stabilization and detoxification of As in subsurface environments. However, this reaction remains controversial due to lack of direct evidence and poorly understood mechanisms. In this study, we show that As(III) oxidation can be facilitated by Fe oxyhydroxides (i.e., goethite) under anoxic conditions coupled with the reduction of structural Fe(III). An excellent electron balance between As(V) production and Fe(III) reduction is obtained. The formation of an active metastable Fe(III) phase at the defective surface of goethite due to atom exchange is responsible for the oxidation of As(III). Furthermore, the presence of defects (i.e., Fe vacancies) in goethite can noticeably enhance the electron transfer (ET) and atom exchange between the surface-bound Fe(II) and the structural Fe(III) resulting in a two time increase in As(III) oxidation. Atom exchange-induced regeneration of active goethite sites is likely to facilitate As(III) coordination and ET with structural Fe(III) based on electrochemical analysis and theoretical calculations showing that this reaction pathway is thermodynamically and kinetically favorable. Our findings highlight the synergetic effects of defects in the Fe crystal structure and Fe(II)-induced catalytic processes on anoxic As(III) oxidation, shedding a new light on As risk management in soils and subsurface environments.

Incorporation of Cu into Goethite Stimulates Oxygen Activation by Surface-Bound Fe(II) for Enhanced As(III) Oxidative Transformation.

The dark production of reactive oxygen species (ROS) coupled to biogeochemical cycling of iron (Fe) plays a pivotal role in controlling arsenic transformation and detoxification. However, the effect of secondary atom incorporation into Fe(III) oxyhydroxides on this process is poorly understood. Here, we show that the presence of oxygen vacancy (OV) as a result of Cu incorporation in goethite substantially enhances the As(III) oxidation by Fe(II) under oxic conditions. Electrochemical and density functional theory (DFT) evidence reveals that the electron transfer (ET) rate constant is enhanced from 0.023 to 0.197 s-1, improving the electron efficiency of the surface-bound Fe(II) on OV defective surfaces. The cascade charge transfer from the surface-bound Fe(II) to O2 mediated by Fe(III) oxyhydroxides leads to the O-O bond of O2 stretching to 1.46-1.48 Šequivalent to that of superoxide (•O2-), and •O2- is the predominant ROS responsible for As(III) oxidation. Our findings highlight the significant role of atom incorporation in changing the ET process on Fe(III) oxyhydroxides for ROS production. Thus, such an effect must be considered when evaluating Fe mineral reactivity toward changing their surface chemistry, such as those noted here for Cu incorporation, which likely determines the fates of arsenic and other redox sensitive pollutants in the environments with oscillating redox conditions.

Degradation and fate of 2,4-dinitroanisole (DNAN) and its intermediates treated with Mg/Cu bimetal: Surface examination with XAS, DFT, and LDI-MS.

A novel Mg-based bimetal reagent (Mg/Cu) was used as an enhanced reductive system to degrade insensitive munition 2,4-dinitroanisole (DNAN), a contaminant found in energetic-laden waste. Degradation of DNAN was significantly impacted by dissolved oxygen and studied in anoxic and oxic bimetal systems (i.e., purging with N2, air, or O2 gas). Degradation occurred through sequential nitroreduction: first one nitro group was reduced (ortho or para) to form short-lived intermediates 2-amino-4-nitroanisole or 4-amino-2-nitroanisole (2-ANAN or 4-ANAN), and then subsequent reduction of the other nitro group formed 2,4-diaminoanisole (DAAN). The nitro-amino intermediates demonstrated regioselective reduction in the ortho position to 2-ANAN; Regioselectivity was also impacted by the anoxic/oxic environment. Under O2-purging DNAN degradation rate was slightly enhanced, but most notably O2 significantly accelerated DAAN generation. DAAN also further degraded only in the oxygenated Mg/Cu system. Adsorption of DNAN byproducts to the reagent occurred regardless of anoxic/oxic condition, resulting in a partition of carbon mass between the adsorbed phase (27%-35%) and dissolved phase (59%-72%). Additional surface techniques were applied to investigate contaminant interaction with Cu. Density functional theory (DFT) calculations identified preferential adsorption structures for DNAN on Cu with binding through two O atoms of one or both nitro groups. X-ray absorption spectroscopy (XAS) measurements determined the oxidation state of catalytic metal Cu and formation of a Cu-O-N bond during treatment. Laser desorption ionization mass spectrometry (LDI-MS) measurements also identified intermediate 2-ANAN adsorbed to the bimetal surface.

Competitive adsorption of nitrate, phosphate, and sulfate on amine-modified wheat straw: In-situ infrared spectroscopic and density functional theory study.

Amine-modified wheat straw (AMWS) has already been reported as a promising adsorbent for nitrate (NO3) removal due to its cost-effectiveness and high efficiency. However, the NO3 removal mechanism has not been well understood, especially in the presence of co-existing ions. Here, the effect of co-existing anions on NO3 removal by AMWS was investigated and the underlying mechanisms were revealed using a combination of in-situ infrared (IR) spectroscopy and computational modeling. The in-situ IR results indicated that NO3, sulfate (SO4), and phosphate (PO4) are all adsorbed as outer-sphere complexes on AMWS. The two-dimensional-correlation spectroscopy analysis implied the adsorption sequence of SO4 > PO4 > NO3. The adsorption energies obtained from density functional theory calculation range from -0.24 to 0.51 eV (-23.2 to 49.2 kJ/mol), confirming that these anions adsorb on AMWS as outer-sphere complexes. For the first time, this study provides direct spectroscopic evidence of the outer-sphere adsorption of NO3 on AMWS, as well as identifies the adsorption sequence, confirmed by computational modeling. The competitive mechanism of NO3, SO4, and PO4 revealed in this study is helpful to understand and predict the applications of AMWS.

Mechanistic Study of Pb(II) Removal by TiO2 and Effect of PO4.

As a commercial adsorbent, TiO2 shows a high adsorption capacity for lead (Pb(II)). However, the molecular structure of Pb(II) adsorption on TiO2 is still unknown. Meanwhile, as a widely used corrosion inhibitor, phosphate (PO4) is usually added into drinking water, and its influential mechanism on Pb(II) removal by TiO2 remains unknown. Here, the mechanisms of Pb(II) adsorption on TiO2 and the effect of PO4 were systematically investigated using a combination of spectroscopic analyses and surface complexation modeling. The adsorption structure of Pb(II) on TiO2 was revealed as a tridentate mononuclear configuration by the extended X-ray absorption fine structure (EXAFS) analysis. In the presence of 0.1-5 mg/L PO4, Pb(II) was removed mainly by adsorption on TiO2 rather than precipitation. Ternary complexation between Pb(II) and PO4 on TiO2 surfaces was found based on EXAFS and in situ Fourier transform infrared characterizations. These complexation structures were used to build a surface complexation model to accurately simulate and predict Pb(II) removal under different conditions. This study provides essential information about the mechanisms of Pb(II) removal by TiO2 and develops a model to predict adsorption behaviors, especially in the presence of PO4.

Mechanistic Study of Lead Adsorption on Activated Carbon.

Activated carbon (AC) is a carbonaceous material broadly applied in filters to remove lead (Pb(II)) from drinking water through adsorption. However, the chemical interactions between Pb(II) and the reactive sites on AC or other carbonaceous materials are not well understood, yet. The understanding of the mechanism of Pb(II) adsorption onto AC would allow to optimally design AC-based materials even in the presence of a complex liquid phase. Here, the interaction between Pb(II) and functional groups on AC was investigated at the molecular scale to help identifying the chemical reactions at the solid-liquid interface. Spectroscopic analyses and chemical quantum calculations were performed and indicated the formation of monodentate mononuclear Pb(II)-phenol and bidentate mononuclear Pb(II)-carboxyl complexes on AC. Competitive adsorption behavior was observed between Pb(II) and calcium (Ca(II)) because of their similar adsorption configurations on AC. In contrast, anions, including sulfate and phosphate, were observed to enhance Pb(II) adsorption on AC by forming ternary complexes. On the basis of these observations, a new surface complexation model of Pb(II) adsorption onto AC was formulated and validated with batch tests. Overall, this work presents a new set of chemical reactions at the solid-liquid interface between Pb(II) and AC under various conditions of interest for the application of AC or other carbonaceous materials in water treatment.

Competing Interactions of As Adsorption and Fe(III) Polymerization during Ferric Coprecipitation Treatment.

This study revealed the effect of As on the formation and dissolution of iron (hydr)oxides and its further impact on the As removal efficacy of FeCl3 treatment. Adding 6.7 mg/L FeCl3 into 325 µg/L As solution (coprecipitation) resulted in more As removal (99% As(V) and 75% As(III)) at 2 min than adding As into aged FeCl3 solution (preaged, 52-87% As(V) and 7-42% As(III)) at pH 7. However, soluble As gradually increased in the coprecipitation system and decreased in the preaged system to give similar concentrations during 800 h aging. The particle size of the iron (hydr)oxides increased more slowly in the coprecipitation than in the preaged systems. These results suggest the rapid adsorption of As on Fe polymer during the initial polymerization process, which delays the growth of iron (hydr)oxides. Thermodynamically, quantum chemical calculations implied that iron ions adsorption on iron (hydr)oxide polymer was more stable than As adsorption, which is the main driving force for the As release during aging process. This study improved our understanding of the kinetic and thermodynamic processes of As adsorption and iron (hydr)oxide precipitation in the coprecipitation treatment of As, and the potential for As release during aging of sludge generated in the treatment.

Removal Mechanisms of Phosphate by Lanthanum Hydroxide Nanorods: Investigations using EXAFS, ATR-FTIR, DFT, and Surface Complexation Modeling Approaches.

Lanthanum-based materials are effective for sequestering phosphate in water, however, their removal mechanisms remain unclear, and the effects of environmentally relevant factors have not yet been studied. Hereby, this study explored the mechanisms of phosphate removal using La(OH)3 by employing extended X-ray absorption spectroscopy (EXAFS), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), density functional theory (DFT) and chemical equilibrium modeling. The results showed that surface complexation was the primary mechanism for phosphate removal and in binary phosphate configurations, namely diprotonated bidentate mononuclear (BM-H2) and bidentate binuclear (BB-H2), coexisting on La(OH)3 in acidic conditions. By increasing the pH to 7, BM-H1 and BB-H2 were the two major configurations governing phosphate adsorption on La(OH)3, whereas BB-H1 was the dominant configuration of phosphate adsorption at pH 9. With increasing phosphate loading, the phosphate configuration of on La(OH)3 transforms from binary BM-H1 and BB-H2 to BB-H1. Amorphous Ca3(PO4)2 forms in the presence of Ca, leading to enhanced phosphate removal at alkaline conditions. The contributions of different mechanisms to the overall phosphate removal were successfully simulated by a chemical equilibrium model that was consistent with the spectroscopic results. This study provides new insights into the molecular-level mechanism of phosphate removal by La(OH)3.

Effect of Arsenic on the Formation and Adsorption Property of Ferric Hydroxide Precipitates in ZVI Treatment.

Treatment of arsenic by zerovalent iron (ZVI) has been studied extensively. However, the effect of arsenic on the formation of ferric hydroxide precipitates in the ZVI treatment has not been investigated. We discovered that the specific surface area (ca. 187 m2/g) and arsenic content (ca. 67 mg/g) of the suspended solids (As-containing solids) generated in the ZVI treatment of arsenic solutions were much higher than the specific surface area (ca. 37 m2/g) and adsorption capacity (ca.12 mg/g) of the suspended solids (As-free solids) generated in the arsenic-free solutions. Arsenic in the As-containing solids was much more stable than the adsorbed arsenic in As-free solids. XRD, SEM, TEM, and selected area electron diffraction (SAED) analyses showed that the As-containing solids consisted of amorphous nanoparticles, while the As-free solids were composed of micron particles with weak crystallinity. Extended X-ray absorption fine structure (EXAFS) analysis determined that As(V) was adsorbed on the As-containing suspended solids and magnetic solid surfaces through bidentate binuclear complexation; and As(V) formed a mononuclear complex on the As-free suspended solids. The formation of the surface As(V) complexes retarded the bonding of free FeO6 octahedra to the oxygen sites on FeO6 octahedral clusters and prevented the growth of the clusters and their development into 3-dimensional crystalline phases.

Groundwater Arsenic Adsorption on Granular TiO2: Integrating Atomic Structure, Filtration, and Health Impact.

A pressing challenge in arsenic (As) adsorptive filtration is to decipher how the As atomic surface structure obtained in the laboratory can be used to accurately predict the field filtration cycle. The motivation of this study was therefore to integrate molecular level As adsorption mechanisms and capacities to predict effluent As from granular TiO2 columns in the field as well as its health impacts. Approximately 2,955 bed volumes of groundwater with an average of 542 µg/L As were filtered before the effluent As concentration exceeded 10 µg/L, corresponding to an adsorption capacity of 1.53 mg As/g TiO2. After regeneration, the TiO2 column could treat 2,563 bed volumes of groundwater, resulting in an As load of 1.36 mg/g TiO2. Column filtration and EXAFS results showed that among coexisting ions present in groundwater, only Ca(2+), Si(OH)4, and HCO3(-) would interfere with As adsorption. The compound effects of coexisting ions and molecular level structural information were incorporated in the PHREEQC program to satisfactorily predict the As breakthrough curves. The total urinary As concentration from four volunteers of local residences, ranging from 972 to 2,080 µg/L before groundwater treatment, decreased to the range 31.7-73.3 µg/L at the end of the experimental cycle (15-33 days).

Arsenic biotransformation in solid waste residue: comparison of contributions from bacteria with arsenate and iron reducing pathways.

Arsenic- and iron-reducing bacteria play an important role in regulating As redox transformation and mobility. The motivation of this study was to compare the contributions of different As- and Fe-reducing bacteria to As biotransformation. In this work, three bacteria strains with different functional genes were employed including Pantoea sp. IMH with the arsC gene, Alkaliphilus oremlandii OhILAs possessing the arrA gene, and Shewanella oneidensis MR-1, an iron reducer. The incubation results showed that Pantoea sp. IMH aerobically reduced 100% of As(V) released from waste residues, though total As release was not enhanced. Similarly, strain OhILAs anaerobically reduced dissolved As(V) but could not enhance As release. In contrast, strain MR-1 substantially enhanced As mobilization because of iron reduction, but without changing the As speciation. The formation of the secondary iron mineral pyrite in the MR-1 incubation experiments, as evidenced by the X-ray absorption near-edge spectroscopy (XANES) analysis, contributed little to the uptake of the freed As. Our results suggest that the arsC gene carriers mainly control the As speciation in the aqueous phase in aerobic environments, whereas in anaerobic conditions, the As speciation should be regulated by arrA gene carriers, and As mobility is greatly enhanced by iron reduction.

Arsenate removal using titanium dioxide-doped cementitious composites: Mixture design, mechanisms, and simulated sewer application.

Arsenate (As(V)) in municipal wastewater leads to a public health problem due to its contamination of natural water sources. Here, we proposed to use sewer pipe made of TiO2-doped cementitious composite (TCC) for As(V) removal from municipal wastewater. The optimum composition of TCC, the performance for As(V) removal in the simulated sewer system, and the molecular-level As(V) removal mechanisms were investigated. To obtain the optimum composition, variables were adjusted to maximize the As(V) removal using TCC. Results show that the TiO2 and water contents were the dominant factors. Simulated sewer pipes made of TCC removed As(V) from 100 µg/L to <10 µg/L, which performed better than plain cementitious composite. Moreover, extended X-ray absorption fine structure (EXAFS) analysis indicates that both precipitation and adsorption contribute to the As(V) removal by TCC, while the adsorption is more significant with a lower As(V) concentration (i.e., 1 mg/L). This is the first study evaluating the feasibility to apply TCC for As(V) removal from sewer wastewater. The optimized composition, simulation results, and molecular-level mechanism gained from this study are useful to the future design of TCC for As(V) removal, especially for sewer systems.

Facet-dependent electron transfer induces distinct arsenic reallocations on hematite.

The interfacial electron transfer (ET) between electron shuttling compounds and iron (Fe) oxyhydroxides plays a crucial role in the reductive dissolution of Fe minerals and the fate of surface-bound arsenic (As). However, the impact of exposed facets of highly crystalline hematite on reductive dissolution and As immobilization is poorly understood. In this study, we systematically investigated the interfacial processes of the electron shuttling compound cysteine (Cys) on various facets of hematite and the reallocations of surface-bound As(III) or As(V) on the respective surfaces. Our results demonstrate that the ET process between Cys and hematite generates Fe(II) and leads to reductive dissolution, with more Fe(II) generated on {001} facets of exposed hematite nanoplates (HNPs). Reductive dissolution of hematite leads to significantly enhanced As(V) reallocations on hematite. Nevertheless, upon the addition of Cys, a raipd release of As(III) can be halted by its prompt re-adsorption, leaving the extent of As(III) immobilization on hematite unchanged throughout the course of reductive dissolution. This is due to that Fe(II) can form new precipitates with As(V), a process that is facet-dependent and influenced by water chemistry. Electrochemical analysis reveals that HNPs exhibit higher conductivity and ET ability, which is beneficial for reductive dissolution and As reallocations on hematite. These findings highlight the facet-dependent reallocations of As(III) and As(V) facilitated by electron shuttling compounds and have implications for the biogeochemical processes of As in soil and subsurface environments.

Leaching of valuable metals from cathode active materials in spent lithium-ion batteries by levulinic acid and biological approaches.

Recycling of valuable metals from spent lithium-ion batteries (LIBs) is of paramount importance for the sustainable development of consumer electronics and electric vehicles. This study comparatively investigated two eco-friendly leaching methods for recovering Li, Ni, Co, and Mn from waste NCM523 (LiNi0.5Co0.2Mn0.3O2) cathode materials in spent LIBs, i.e., chemical leaching by a green organic solvent, levulinic acid (LA) and bioleaching by an enriched microbial consortium. In chemical leaching, mathematical models predicting leaching efficiency from liquid-to-solid ratio (L/S; L/kg), temperature (°C), and duration (h) were established and validated. Results revealed that LA of 6.86 M was able to achieve complete leaching of all target metals in the absence of reductants at the optimal conditions (10 L/kg, 90 °C, and 48 h) identified by the models. The evaluation of direct one- and two-step and indirect bioleaching indicated that the latter was more feasible for metal extraction from waste NCM523. L/S was found to impact the indirect bioleaching most significantly among the three operating variables. Pretreatment of waste NCM523 by washing with 1 vol% methanesulfonic acid significantly improved indirect bioleaching. The side-by-side comparison of these two leaching approaches on the same cathode active material (CAM) thus provided the technical details for further comparison with respect to cost and environmental impact.

Mechanistic insights into Cr(VI) removal by a combination of zero-valent iron and pyrite.

Recent studies have revealed that a combination of zero-valent iron (ZVI) and pyrite (FeS2) can effectively remove (Cr(VI)) from water, but the reasons behind this synergistic effect are still unclear. Our batch experiments showed that dissolved oxygen (DO) is a critical factor in the improved removal of Cr(VI) by ZVI and pyrite. When 0.08 g/L pyrite was combined with 0.5 g/L ZVI in the presence of DO, total Cr was reduced from 10 mg/L to 0.02 mg/L within 6 h. Conversely, in the absence of DO, total Cr was only reduced to 5.6 mg/L. DO oxidation of pyrite produced protons that promote ZVI corrosion, and mixing pyrite with water creates dissolved sulfide, which also contributes to the improved removal of Cr(VI). Electron microscopy images and X-ray absorption near edge structure analyses revealed that the presence of dissolved sulfide led to the formation of ferrous sulfide precipitates on the ZVI surface, preventing the formation of a passivating layer.

Factors Affecting the Detection of Hexavalent Chromium in Cr-Contaminated Soil.

The alkali digestion pretreatment method in the United States Environmental Protection Agency (USEPA) Method 3060A could underestimate the content of Cr(VI) in Cr-contaminated soils, especially for soils mixed with chromite ore processing residue (COPR), which leads to a misjudgment of the Cr(VI) level in soils after remediation, causing secondary pollution to the environment. In this study, a new pretreatment method to analyze Cr(VI) concentration in contaminated soils was established. The impacts of soil quality, particle size, alkali digestion time and the rounds of alkali digestion on Cr(VI) detection in contaminated soils was explored and the alkali digestion method was optimized. Compared with USEPA Method 3060A, the alkaline digestion time was prolonged to 6 h and multiple alkali digestion was employed until the amount of Cr(VI) in the last extraction was less than 10% of the total amount of Cr(VI). Because Cr(VI) in COPR is usually embedded in the mineral phase structure, the hydration products were dissolved and Cr(VI) was released gradually during the alkaline digestion process. The amount of Cr(VI) detected showed high correlation coefficients with the percentage of F1 (mild acid-soluble fraction), F2 (reducible fraction) and F4 (residual fraction). The Cr(VI) contents detected by the new alkaline digestion method and USEPA Method 3060A showed significant differences for soil samples mixed with COPR due to their high percentage of residual fraction. This new pretreatment method could quantify more than 90% of Cr(VI) in Cr-contaminated soils, especially those mixed with COPR, which proved to be a promising method for Cr(VI) analysis in soils, before and after remediation.

New insights into stoichiometric efficiency and synergistic mechanism of persulfate activation by zero-valent bimetal (Iron/Copper) for organic pollutant degradation.

Extensive studies have been devoting to investigating the catalytic efficiency of zero-valent iron (Fe0)-based bimetals with persulfate (PS), while little is known in the stoichiometric efficiency, underlying mechanisms and reaction center of zero-valent bimetallic catalysts in activating PS. Herein, nanoscale zero-valent Fe/Cu catalysts in decomposing 2,4-dichlorophenol (DCP) have been investigated. The results show that the increase of Cu ratio from 0 to 0.75 significantly enhances the DCP degradation with a rate constant of 0.025 min-1 for Fe0 to 0.097 min-1 for Fe/Cu(0.75) at pH ∼3.3, indicating Cu is likely the predominate reaction centers over Fe. The PS decomposition is reduced with the increase of Cu ratios, suggesting the stoichiometric efficiency of Fe/Cu in activating PS is notably enhanced from 0.024 for Fe0 to 0.11 for Fe/Cu(0.75). Analyses indicate Cu atoms are likely the predominant reaction site for DCP decomposition, and Fe atoms synergistically enhance the activity of Cu as indicated by DFT calculations. Both SO4⦁- and ⦁OH radicals are responsible for reactions, and the contribution of SO4⦁- is decreased at higher pH conditions. The findings of this work provide insight into the stoichiometric efficiency and the reaction center of Fe/Cu catalysts to activate PS for pollutant removals.

Oxidation of Arsenite by Epoxy Group on Reduced Graphene Oxide/Metal Oxide Composite Materials.

Reduced graphene oxide/metal oxide (rGO/MO) hybrid has been widely used as a catalyst, while dissolved oxygen or radicals are generally recognized as the oxidant. This study finds that the adsorbed arsenite (As(III)) on rGO/MO is oxidized to arsenate (As(V)) in the absence of other oxidants or radicals. The oxidation of As(III) is observed on varying rGO/MOs, including rGO/MOs composited of different types of reduced graphene oxide (rGO) and metal oxide. The epoxy group on rGO acts as the oxidant, evidenced by the significant correlation between the consumption of epoxy group and oxidation of As(III). Meanwhile, metal oxide provides adsorption sites for As(III) during the adsorption-oxidation process. Based on a combination of spectroscopic measurements and computational calculation, a possible pathway for As(III) oxidation by rGO/MO is proposed: the oxygen atom in the epoxy group is bonded to the adsorbed AsIIIO3, which is consequently oxidized to AsVO4. Overall, this study proves the role of rGO/MO as an oxidant, which opens a new perspective on future studies using rGO/MO as a catalyst for the oxidation reaction.

Surface mole-ratio method to distinguish surface precipitation and adsorption on solid-liquid interface.

The enhancement effects of phosphate (P) on Pb removal by adsorbents have been attributed to co-adsorption of P and Pb, the formation of P-Pb surface ternary surface complexes, and surface precipitation of P and Pb. However, distinguishing adsorption from surface precipitation in multi-adsorbate systems has been a challenge. For the first time, a surface mole-ratio (SMR) method was established and applied for delineating Pb-P precipitation and Pb adsorption on an acrylic amine fiber (AAF) adsorbent. In elaborating the SMR method, we developed Pb removal experiments by mixing solutions containing 0.2 g/L of AAF, 6 and 12 µmol/L P, and 0-35 µmol/L Pb. When the removed Pb/P (µmol/µmol) was plotted as a function of the equilibrium Pb (µmol/L), the SMR diagram exhibited a turning-point similar to the Pb/P mole ratio of 5/3 = 1.67 in pyromorphite (Pb5(PO4)3OH) precipitate. The SMR diagram indicated that when the Pb concentration increased, the precipitate formed first; after all P formed precipitates, Pb was removed by adsorption. The precipitation and adsorption processes were further confirmed by other SMR diagrams, FTIR, SEM-EDX, and XRD analysis. The SMR method will have broad applications in determining the removal mechanisms of multi-adsorbates by adsorbents and coagulants, and stabilization mechanisms of heavy metals in soils. With the development and application of more modern in-situ characterization techniques, SMR method will be more effective.

Identifying the existence and molecular structure of the dissolved HCO3-Ca-As(V) complex in water.

Calcium (Ca2+) and bicarbonate (HCO3-) ions co-exist with arsenic (As) in natural water systems, while Ca-based materials such as lime and cement are widely used to immobilize As(V) in contaminated solids. In this paper, a new dissolved ternary complex, HCO3-Ca-As(V), was discovered and its molecular structure was identified. The results from the batch experiments showed that adding As(V) to the solutions containing Ca2+ and HCO3- increased the dissolved Ca concentration from 4.8 to 73.2 mg/L at pH 11. Both infrared and X-ray absorption spectroscopy indicated the presence of dissolved HCO3-Ca-As(V) complex. Based on the quantitative geometric information obtained from the spectroscopic results, the molecule of (OH)OC-O-(OH2)4Ca-O2-As(OH)2 was identified by the density functional theory (DFT) calculation. Although Ca2+ and As(V) can form complex without HCO3-, the presence of HCO3- further enhanced the stability of the dissolved Ca complex, as evidenced by the lower binding energy (BE) of HCO3-Ca-As(V) (-329.1959 kJ/mol) than Ca-As(V) (4.7171 kJ/mol). The discovery of dissolved HCO3-Ca-As(V) complex is important for understanding the mobility of As(V) in natural water, and the possible release of As(V) in contaminated solids treated with Ca-based materials.