Effect of Mn(II) photochemical oxidation on Cd immobilization in hematite.

Hematite, a commonly stable iron oxide in the environment, which can not only adsorb Cd in the environment, but also catalyze the photochemical oxidation of Mn(II) in the environment. However, the impact of Mn(II) on the structure of hematite and the adsorption of Cd during the surface oxidation of hematite remains unknown. In this study, we investigated the surface and structural changes of hematite after the photochemical oxidation of Mn(II), as well as the geochemical behavior of Cd during this process. The results demonstrate that Mn(II) was oxidized to Mn(III/IV) on the hematite surface, with some Mn(III) being incorporated into the hematite structure. Simulations using XRD data showed that higher Mn(II) concentrations resulted in increased levels of Mn doping, leading to significant variations in the hematite unit cell. This was further confirmed through FTIR and Raman spectroscopy characterization. The oxidation of Mn(II) on the hematite surface resulted in a shift in surface charge from positive to negative, enhancing the adsorption capacity of Cd. However, when Mn(II) exceeded 0.4 mM, the immobilization of Cd within the system decreased. This was attributed to the competitive adsorption of Mn(II) and a reduction in the relative abundance of Mn(IV) oxides.

Influence of tartaric acid on the electron transfer between oxyanions and lepidocrocite.

Iron oxide minerals control the environmental behavior of trace elements. However, the potential effects of electron transfer directions by iron oxides between organic acids and trace elements remain unclear. This study investigates the redox capacity of tartaric acid (TA) with chromate (Cr(Ⅵ)) or arsenate (As(V)) on lepidocrocite (Lep) from the perspective of electron transfer. The results demonstrated the configurations of TA (bidentate binuclear (BB)), As(V) (BB), and Cr(Ⅵ) (BB and protonated monodentate binuclear (HMB)) on Lep. Frontier molecular orbital calculations and X-ray photoelectron spectroscopy (XPS) binding energy shifts further indicated different electron transfer directions between TA and the oxyanions on Lep. The iron of Lep might act as electron acceptors when TA is adsorbed, whereas the iron and oxygen of Lep act as electron donors when As(V) is adsorbed. The iron of Lep might accept electrons from its oxygen and subsequently transfer these electrons to Cr(Ⅵ). Macroscopic validation experiments showed the reduction of Cr(VI), whereas no reduction of As(V). The XPS analysis showed a peak shift, with the possible formation of As-Fe-TA ternary complexes and electron transfer on Lep. These findings indicate that mineral interfacial electron transfer considerably influences the transport and transformation of oxyanions.

Effect of biochar-derived DOM on contrasting redistribution of chromate during Schwertmannite dissolution and recrystallization.

Biochar-derived dissolved organic matter (BDOM), is extensively involved in the recrystallization of minerals and the speciation alteration of associated toxic metals. This study investigates how BDOM extracted from tobacco petiole (TP) or tobacco stalk (TS) biochar influences the speciation repartitioning of Cr(VI) in environments impacted by acid mine drainage (AMD), focusing on interactions with secondary minerals during Schwertmannite (Sch) dissolution and recrystallization. TP-BDOM, rich in lignin-like substances, slowed down the Cr-Sch dissolution and Cr release under acidic conditions compared to TS-BDOM. TP-BDOM's higher O/C component exerts a delayed impact on Cr-Sch stability and Cr(VI) reduction. In-situ ATR-FTIR and 2D-COS analysis showed that carboxylic and aromatic N-OH groups in BDOM could interact with Cr-Sch surfaces, affecting sulfate and Cr(VI) release. It was also observed that slight recrystallization occurred from Cr-Sch to goethite, along with increased Cr incorporation into secondary minerals within TS-BDOM. This enhances our understanding of BDOM's role in Cr(VI) speciation changes in AMD-contaminated sites.

Sulfidation of Cd-Sch during the microbial sulfate reduction: Nanoscale redistribution of Cd.

Schwertmannite (Sch) is found in environments abundant in iron and sulfate. Microorganisms that utilize iron or sulfate can induce the phase transition of Schwertmannite, consequently leading to the redistribution of coexisting pollutants. However, the impact of the molar ratio of sulfate to iron (S/Fe) on the microbial-mediated transformation of Schwertmannite and its implications for the fate of cadmium (Cd) have not been elucidated. In this study, we examined how S/Fe influenced mineral transformation and the fate of Cd during microbial reduction of Cd-loaded Schwertmannite by Desulfovibrio vulgaris. Our findings revealed that an increase in the S/Fe ratio facilitated sulfate-reducing bacteria (SRB) in mitigating the toxicity of Cd, thereby expediting the generation of sulfide (S(-II)) and subsequently triggering mineral phase transformation. As the S/Fe ratio increased, the predominant minerals in the system transitioned from prismatic-cluster vivianite to rose-shaped mackinawite. The Cd phase and distribution underwent corresponding alterations. Cd primarily existed in its oxidizable state, with its distribution being directly linked not only to FeS content but also showing a robust correlation with phosphorus. The coexistence of vivianite and FeS minerals proved to be more favorable for Cd immobilization. These findings have significant implications for understanding the biogeochemistry of iron (oxyhydr)oxides and Cd fate in anaerobic environments.

Arsenic redistribution associated with Fe(II)-induced jarosite transformation in the presence of polygalacturonic acid.

Jarosite exists widely in acid-sulfate soil and acid mine drainage polluted areas and acts as an important host mineral for As(V). As a metastable Fe(III)-oxyhydoxysulfate mineral, its dissolution and transformation have a significant impact on the biogeochemical cycle of As. Under reducing conditions, the trajectory and degree of abiotic Fe(II)-induced jarosite transformation may be greatly influenced by coexisting dissolved organic matter (DOM), and in turn influencing the fate of As. Here, we explored the impact of polygalacturonic acid (PGA) (0-200 mg·L-1) on As(V)-coprecipitated jarosite transformation in the presence of Fe(II) (1 mM) at pH 5.5, and investigated the repartitioning of As between aqueous and solid phase. The results demonstrated that in the system without both PGA and Fe(II), jarosite gradually dissolved, and lepidocrocite was the main transformation product by 30 d; in Fe(II)-only system, lepidocrocite appeared by 1 d and also was the mainly final product; in PGA-only systems, PGA retarded jarosite dissolution and transformation, jarosite might be directly converted into goethite; in Fe(II)-PGA systems, the presence of PGA retarded Fe(II)-induced jarosite dissolution and transformation but did not alter the pathway of mineral transformation, the final product mainly still was lepidocrocite. The retarding effect on jarosite dissolution enhanced with the increase of PGA content. The impact of PGA on Fe(II)-induced jarosite transformation mainly was related to the complexation of carboxyl groups of PGA with Fe(II). The dissolution and transformation of jarosite drove pre-incorporated As transferred into the phosphate-extractable phase, the presence of PGA retarded jarosite dissolution and maintained pre-incorporated As stable in jarosite. The released As promoted by PGA was retarded again and almost no As was released into the solution by the end of reactions in all systems. In systems with Fe(II), no As(III) was detected and As(V) was still the dominant redox species.

Prediction of Cr(VI) and As(V) adsorption on goethite using hybrid surface complexation-machine learning model.

This study aimed to develop surface complexation modeling-machine learning (SCM-ML) hybrid model for chromate and arsenate adsorption on goethite. The feasibility of two SCM-ML hybrid modeling approaches was investigated. Firstly, we attempted to utilize ML algorithms and establish the parameter model, to link factors influencing the adsorption amount of oxyanions with optimized surface complexation constants. However, the results revealed the optimized chromate or arsenate surface complexation constants might fall into local extrema, making it unable to establish a reasonable mapping relationship between adsorption conditions and surface complexation constants by ML algorithms. In contrast, species-informed models were successfully obtained, by incorporating the surface species information calculated from the unoptimized SCM with the adsorption condition as input features. Compared with the optimized SCM, the species-informed model could make more accurate predictions on pH edges, isotherms, and kinetic data for various input conditions (for chromate: root mean square error (RMSE) on test set = 5.90 %; for arsenate: RMSE on test set = 4.84 %). Furthermore, the utilization of the interpretable formula based on Local Interpretable Model-Agnostic Explanations (LIME) enabled the species-informed model to provide surface species information like SCM. The species-informed SCM-ML hybrid modeling method proposed in this study has great practicality and application potential, and is expected to become a new paradigm in surface adsorption model.

Speciation and Possible Origins of Organosulfur Compounds in Rice Paddy Soils Affected by Acid Mine Drainage.

Although sulfur cycling in acid mine drainage (AMD)-contaminated rice paddy soils is critical to understanding and mitigating the environmental consequences of AMD, potential sources and transformations of organosulfur compounds in such soils are poorly understood. We used sulfur K-edge X-ray absorption near edge structure (XANES) spectroscopy to quantify organosulfur compounds in paddy soils from five AMD-contaminated sites and one AMD-uncontaminated reference site near the Dabaoshan sulfide mining area in South China. We also determined the sulfur stable isotope compositions of water-soluble sulfate (δ34SWS), adsorbed sulfate (δ34SAS), fulvic acid sulfur (δ34SFAS), and humic acid sulfur (δ34SHAS) in these samples. Organosulfate was the dominant functional group in humic acid sulfur (HAS) in both AMD-contaminated (46%) and AMD-uncontaminated paddy soils (42%). Thiol/organic monosulfide contributed a significantly lower proportion of HAS in AMD-contaminated paddy soils (8%) compared to that in AMD-uncontaminated paddy soils (21%). Within contaminated soils, the concentration of thiol/organic monosulfide was positively correlated with cation exchange capacity (CEC), moisture content (MC), and total Fe (TFe). δ34SFAS ranged from -6.3 to 2.7‰, similar to δ34SWS (-6.9 to 8.9‰), indicating that fulvic acid sulfur (FAS) was mainly derived from biogenic S-bearing organic compounds produced by assimilatory sulfate reduction. δ34SHAS (-11.0 to -1.6‰) were more negative compared to δ34SWS, indicating that dissimilatory sulfate reduction and abiotic sulfurization of organic matter were the main processes in the formation of HAS.

Divergent redistribution behavior of divalent metal cations associated with Fe(II)-mediated jarosite phase transformation.

The Fe(II)/Fe(III) cycle is an important driving force for dissolution and transformation of jarosite. Divalent heavy metals usually coexist with jarosite; however, their effects on Fe(II)-induced jarosite transformation and different repartitioning behavior during mineral dissolution-recrystallization are still unclear. Here, we investigated Fe(II)-induced (1 mM Fe(II)) jarosite conversion in the presence of Cd(II), Mn(II), Co(II), Ni(II) and Pb(II) (denoted as Me(II), 1 mM), respectively, under anaerobic condition at neutral pH. The results showed that all co-existing Me(II) retarded Fe(II)-induced jarosite dissolution. In the Fe(II)-only system, jarosite first rapidly transformed to lepidocrocite (an intermediate product) and then slowly to goethite; lepidocrocite was the main product. In Fe(II)-Cd(II), -Mn(II), and -Pb(II) systems, coexisting Cd(II), Mn(II) and Pb(II) retarded the above process and lepidocrocite was still the dominant conversion product. In Fe(II)-Co(II) system, coexisting Co(II) promoted lepidocrocite transformation into goethite. In Fe(II)-Ni(II) system, jarosite appeared to be directly converted into goethite, although small amounts of lepidocrocite were detected in the final product. In all treatments, the appearance or accumulation of lepidocrocite may be also related to the re-adsorption of released sulfate. By the end of reaction, 6.0 %, 4.0 %, 76.0 % 11.3 % and 19.2 % of total Cd(II), Mn(II), Pb(II) Co(II) and Ni(II) were adsorbed on the surface of solid products. Up to 49.6 %, 44.3 %, and 21.6 % of Co(II), Ni(II), and Pb(II) incorporated into solid product, with the reaction indicating that the dynamic process of Fe(II) interaction with goethite may promote the continuous incorporation of Co(II), Ni(II), and Pb(II).

Prediction of adsorption of metal cations by clay minerals using machine learning.

Adsorption of heavy metals by clay minerals occurs widely at the solid-liquid interface in natural environments, and in this paper, the phenomenon of adsorption of Cd2+, Cu2+, Pb2+, Zn2+, Ni2+ and Co2+ by montmorillonite, kaolinite and illite was simulated using machine learning. We firstly used six machine learning models including Random Forest(R), Extremely Forest(E), Gradient Boosting Decision Tree(G), Extreme Gradient Boosting(X), Light Gradient Boosting(LGB) and Category Boosting(CAT) to feature engineer the metal cations and the parameters of the minerals, and based on the feature engineering results, we determined the first order hydrolysis constant(log K), solubility product constant(SPC), and higher hydrolysis constant (HHC) as the descriptors of the metal cations, and site density(SD) and cation exchange capacity(CEC) as the descriptors of the clay minerals. After comparing the predictive effects of different data cleaning methods (pH50 method, Box method and pH50-Box method) and six model combinations, it was finally concluded that the best simulation results could be achieved by using the pH 50-Box method for data cleaning and Extreme Gradient Boosting for modelling (RMSE = 4.158 %, R2 = 0.977). Finally, model interpretation was carried out using Shapley explanation plot (SHAP) and partial dependence plot(PDP) to analyse the potential connection between each input variable and the output results. This study combines machine learning with geochemical analysis of the mechanism of heavy metal adsorption by clay minerals, which provides a different research perspective from the traditional surface complexation model.

Prediction of heavy metal removal performance of sulfate-reducing bacteria using machine learning.

A robust modeling approach for predicting heavy metal removal by sulfate-reducing bacteria (SRB) is currently missing. In this study, four machine learning models were constructed and compared to predict the removal of Cd, Cu, Pb, and Zn as individual ions by SRB. The CatBoost model exhibited the best predictive performance across the four subsets, achieving R2 values of 0.83, 0.91, 0.92, and 0.83 for the Cd, Cu, Pb, and Zn models, respectively. Feature analysis revealed that temperature, pH, sulfate concentration, and C/S (the mass ratio of chemical oxygen demand to sulfate) had significant impacts on the outcomes. These features exhibited the most effective metal removal at 35 °C and sulfate concentrations of 1000-1200 mg/L, with variations observed in pH and C/S ratios. This study introduced a new modeling approach for predicting the treatment of metal-containing wastewater by SRB, offering guidance for optimizing operational parameters in the biological sulfidogenic process.

Using machine learning to explore oxyanion adsorption ability of goethite with different specific surface area.

In this study, we developed prediction models for the adsorption of divalent and trivalent oxyanions on goethite based on machine learning algorithms. After verifying the reliability of the models, the importance of goethite specific surface area (SSA) and the average oxyanion adsorption capacities of goethite with different SSAs were calculated by shapley additive explanations (SHAP) importance analysis and partial dependence (PD) analysis. Despite there were differences in the feature importance of divalent and trivalent oxyanions, the contribution of goethite's SSA to the adsorption amount ranked the fourth based on SHAP importance, indicating SSA played the important role in oxyanion adsorption. Meanwhile, the PD values of SSA and the optimized complexation constants from surface complexation modeling (SCM) both indicated a non-monotonic relationship between the goethite with different SSA and its oxyanions binding capacity. When the total site concentration and crystal face composition were used as the machine learning model input features, the SHAP importance values of crystal faces and the PD decomposition results indicated that the (001) face showed the crucial influence on oxyanions adsorption amount. These findings demonstrated the important role of crystal face composition in goethite's adsorption ability, and provided a theoretical explanation for the variations of oxyanions adsorption amount on different SSA goethite.

Facet-Dependent Competitive Adsorption Mechanisms of Chromate and Oxalic Acid on γ-FeO(OH) Nanocrystals.

Facet-dependent toxic metal adsorption of iron oxides widely occurred in natural environments. It is known that organic acids can alter the adsorption behaviors of trace elements by cooperative or competitive effects. However, the coadsorption mechanisms of the specific facets are still not fully understood. In the current investigation, Cr(VI) adsorption onto the lepidocrocite (γ-FeO(OH))-exposed facets in the presence of oxalic acid (OA) was studied using macroexperiments, in situ attenuated total reflectance Fourier transform infrared spectroscopy, X-ray adsorption fine structure, and density functional theory calculations. Rod-like lepidocrocite (R-LEP) with a high ratio of {001}/{010} facet showed excellent Cr(VI) adsorption capacity than that of plate-like lepidocrocite (P-LEP, the dominant facet is {010}) in the absence/presence of OA. Interestingly, OA reacted with R-LEP would be easier to diminish Cr(VI) adsorption than with P-LEP. The competitive adsorption occurred on the {001} facet due to the formation of inner-sphere OA configurations (monodentate mononuclear and bidentate mononuclear structures) and a bidentate binuclear Cr(VI) complex. However, OA coordinated with {010} facets via the outer-sphere complexes, while Cr(VI) could form a protonated monodentate binuclear configuration. These observations suggest that the competitive adsorption processes between OA and Cr(VI) exhibit facet dependence. Furthermore, lepidocrocite-exposed facets determine the interfacial interactions and geochemical behaviors of Cr(VI) in polluted environments.

Divergent repartitioning of antimony and arsenic during jarosite transformation: A comparative study under aerobic and anaerobic conditions.

Jarosite is the host mineral of Sb(V) and As(V) in mining environments. However, the repartitioning of Sb and As during its transformation is poorly understood. Additionally, the mutual effect between the redistribution behavior of As and Sb during jarosite conversion remains unclear. Here, we investigated the transformation of Sb(V)-, As(V)- and Sb(V)-As(V)-jarosite at pH 5.5 under aerobic and anaerobic conditions without a reductant. The results indicated that co-precipitated Sb(V) promotes jarosite dissolution, and the final products were mainly goethite and hematite. In contrast, the co-precipitated As(V) retarded jarosite dissolution and altered the transformation pathway, mainly forming lepidocrocite, which might be attributed to the formation of As-Fe complexes on the jarosite surface. The inhibiting or promoting effect increased with the increase in co-precipitated As or Sb concentration. In the treatment with Sb(V)-As(V)-jarosite, the inhibition effect of co-precipitated As(V) on mineral dissolution was predominant, but the end-products were mainly goethite and hematite. Compared with the aerobic system, the dissolution and transformation of jarosite in treatments in the anaerobic system occurred faster, although without a reductant, which was possibly associated with the reduced CO2 content in the reaction solutions after degassing. In all treatments, the release of Sb(aq) and As(aq) into the solution was negligible during jarosite transformation. The transformation processes drove As into the surface-bound exchangeable and poorly crystalline phases, while Sb was typically redistributed in the poorly crystalline phase. During the transformation of Sb(V)-As(V)-jarosite, the co-existence of As significantly increased the proportion of Sb distributed on the solid surface and in the poorly crystalline phase. These findings are valuable for predicting the long-term fate of Sb and As in mining environments.

Extracellular polymeric substances sustain photoreduction of Cr(VI) by Shewanella oneidensis-CdS biohybrid system.

Photosensitized biohybrid system (PBS) enables bacteria to exploit light energy harvested by semiconductors for rapid pollutants transformation, possessing a promising future for water reclamation. Maintaining a biocompatible environment under photocatalytic conditions is the key to developing PBS-based treatment technologies. Natural microbial cells are surrounded by extracellular polymeric substances (EPS) that either be tightly bound to the cell wall (i.e., tightly bound EPS, tbEPS) or loosely associated with cell surface (i.e., loosely bound EPS, lbEPS), which provide protection from unfavorable environment. We hypothesized that providing EPS fractions can enhance bacterial viability under adverse environment created by photocatalytic reactions. We constructed a model PBS consisting of Shewanella oneidensis and CdS using Cr(VI) as the target pollutant. Results showed complete removal of 25 mg/L Cr(VI) within 90 min without an electron donor, which may mainly rely on the synergistic effect of CdS and bacteria on photoelectron transfer. Long-term cycling experiment of pristine PBS and PBS with extra EPS fractions (including lbEPS and tbEPS) for Cr(VI) treatment showed that PBS with extra lbEPS achieved efficient Cr(VI) removal within five consecutive batch treatment cycles, compared to the three cycles both in pristine PBS and PBS with tbEPS. After addition of lbEPS, the accumulation of reactive oxygen species (ROS) was greatly reduced via the EPS-capping effect and quenching effect, and the toxic metal internalization potential was lowered by complexation with Cd and Cr, resulting in enhanced bacterial viability during photocatalysis. This facile and efficient cytoprotective method helps the rational design of PBS for environmental remediation.

Nanoplastics impacts on Thiobacillus denitrificans: Effects of size and dissolved organic matter.

The widespread distribution of nanoplastics and dissolved organic matter (DOM) in sewage raises concerns about the potential impact of DOM on the bioavailability of nanoplastics. In this study, the effects of different sizes (100 nm and 350 nm) of polystyrene nanoplastics (PS-NPs, 50 mg/L) and combined with 10 mg/L or 50 mg/L DOMs (fulvic acid, humic acid and sodium alginate) on the growth and denitrification ability of Thiobacillus denitrificans were investigated. Results showed that 100 nm PS-NPs (50 mg/L) cause a longer delay in the nitrate reduction (3 days) of T. denitrificans than 350 nm PS-NPs (2 days). Furthermore, the presence of DOM exacerbated the adverse effect of 100 nm PS-NPs on denitrification, resulting in a delay of 1-4 days to complete denitrification. Fulvic acid (50 mg/L) and humic acid (50 mg/L) had the most significant adverse effect on increasing 100 nm PS-NPs (50 mg/L), causing a reduction of 20 mmol/L nitrate by T. denitrificans in nearly 7 days. It is noteworthy that the presence of DOM did not modify the adverse effect of 350 nm PS-NPs on denitrification. Further analysis of toxicity mechanism of PS-NPs revealed that they could induce reactive oxygen species (ROS) and suppressed denitrification gene expression. The results suggested that DOM may assist in the cellular internalization of PS-NPs by inhibiting PS-NPs aggregation, leading to the increased ROS levels and accelerated T. denitrificans death. This study highlights the potential risk of nanoplastics to autotrophic denitrifying bacteria in the presence of DOM and provides new insights for the treatment of nitrogen-containing wastewater by T. denitrificans.

S(-II) reactivates Cd2+-stressed Shewanella oneidensis via promoting low-molecular-weight thiols synthesis and activating antioxidant defense.

Efficient remedies for living organisms including bacteria to counteract cadmium (Cd2+) toxicity are still highly needed. Plant toxicity studies have showed that exogenous S(-II) (including hydrogen sulfide and its ionic forms, i.e., H2S, HS-, and S2-) application can effectively alleviate adverse effects of Cd stress, but whether S(-II) could mitigate bacterial Cd toxicity remains unclear. In this study, S(-II) was applied exogenously to Cd-stressed Shewanella oneidensis MR-1 and the results showed that S(-II) can significantly reactivate impaired physiological processes including growth arrest and enzymatic ferric (Fe(III) reduction inhibition. The efficacy of S(-II) treatment is negatively correlated with the concentration and time length of Cd exposure. Energy-dispersive X-ray (EDX) analysis suggested the presence of cadmium sulfide inside cells treated with S(-II). Both compared proteomic analysis and RT-qPCR showed that enzymes associated with sulfate transport, sulfur assimilation, methionine, and glutathione biosynthesis were up-regulated in both mRNA and protein levels after the treatment, indicating S(-II) may induce the biosynthesis of functional low-molecular-weight (LMW) thiols to counteract Cd toxicity. Meanwhile, the antioxidant enzymes were positively modulated by S(-II) and thus the activity of intracellular reactive oxygen species was attenuated. The study demonstrated that exogenous S(-II) can effectively alleviate Cd stress for S. oneidensis likely through inducing intracellular trapping mechanisms and modulating cellular redox status. It suggested that S(-II) may be a highly effective remedy for bacteria such as S. oneidensis under Cd-polluted environments.

Colloidal stability and aggregation behavior of CdS colloids in aquatic systems: Effects of macromolecules, cations, and pH.

Redox-dynamic environments such as river floodplains and paddy fields have been demonstrated to be important sources of CdS colloids. To date, the aggregation kinetics of CdS colloids had not yet been studied, and the structure and properties of macromolecules on the interaction between different macromolecules and CdS colloids, as well as the aggregation behavior of CdS colloids are unclear. This study investigated the colloidal stability of CdS colloids in model aqueous systems with various solution chemistry and representative of macromolecules. The results showed that increased electrolyte concentration destabilized CdS colloids by charge screening, with the cationic effect following Ca2+ > Mg2+ > K+ > Na+; Higher solution pH stabilized CdS colloids by raising the critical coagulation concentration from 33 to 56 mM NaCl. Electron microscopy and spectroscopy verified the strong interaction between macromolecules and CdS colloids, and macromolecule adsorbed on the surface of CdS to form a protective layer called "NOM corona". The interaction between macromolecules and CdS induced distinct aggregation behaviors in NaCl and CaCl2 solutions. The steric repulsion generated by "NOM corona" significantly stabilized CdS colloids in NaCl solution, and the stabilizing order was consistent with the adsorbing capacity of macromolecules on CdS colloids, namely Bovine serum albumin (BSA) > sodium alginate (SA) > calf thymus DNA (DNA) > Suwannee River humic acid (HA). BSA and DNA also inhibited CdS colloids aggregation in the CaCl2 solution due to the balance of steric hindrance, cation bridging, and electrostatic repulsion. For HA and SA, Ca2+ bridging and EDL compression contributed to their destabilization of CdS colloids in CaCl2 solution. Macromolecules concentration affect corona formation that alter stability of CdS colloids. There results showed that the complex influences of solution chemistry and macromolecules on fate and transport of CdS colloids in environment. The findings will help to understand the potential risks of CdS colloids in environment.

Microbial reduction of schwertmannite by co-cultured iron- and sulfate-reducing bacteria.

Schwertmannite (Sch) is an iron-hydroxysulfate mineral commonly found in acid mine drainage contaminated environment. The transformation mechanism of Sch mediated by pure cultured iron-reducing bacteria (FeRB) or sulfate-reducing bacteria (SRB) has been studied. However, FeRB and SRB widely coexist in the environment, the mechanism of Sch transformation by the consortia of FeRB and SRB is still unclear. This study investigated the Sch reduction by co-cultured Shewanella oneidensis (FeRB) and Desulfosporosinus meridiei (SRB). The results showed that co-culture of FeRB and SRB could accelerate the reductive dissolution of Sch, but not synergistically, and there were two distinct phases in the reduction of Sch mediated by FeRB and SRB: an initial phase in which FeRB predominated and Fe3+ in Sch was reduced, accompanied with the release of SO42-, and the detected secondary minerals were mainly vivianite; the second phase in which SRB predominated and mediated the reduction of SO42-, producing minerals including mackinawite and siderite in addition to vivianite. Compared to pure culture, the abundance of FeRB and SRB in the consortia decreased, and more minerals aggregated inside and outside the cell; correspondingly, the transcription levels of genes (cymA, omcA, and mtrCBA) related to Fe3+ reduction in co-culture was down-regulated, while the transcription levels of SO42--reducing genes (sat, aprAB, dsr(C)) was generally up-regulated. These phenomena suggested that secondary minerals produced in co-culture limited but did not inhibit bacterial growth, and the presence of SRB was detrimental to dissimilatory Fe3+ reduction, while existed FeRB was in favor of dissimilatory SO42- reduction. SRB mediated SO42- reduction by up-regulating the expression of SO42- reduction-related genes when its abundance was limited, which may be a strategy to cope with external coercion. These findings allow for a better understanding of the process and mechanism of microbial mediated reduction of Sch in the environment.

Fe(II)-mediated transformation of schwertmannite associated with calcium from acid mine drainage treatment.

Schwertmannite is an important Fe(III)-oxyhydroxysulfate in acid mine drainage (AMD) polluted areas and its stability depends on surrounding environmental factors and previously bound elements. The treatment and neutralization of AMD normally involve the use of lime, which leads to the discharge of abundant Ca in the mining area. Such an environmental disturbance brings up an important and less considered problem of how the reductive transformation of schwertmannite associated with coexisting Ca occurred. Here, the Fe(II)-mediated transformation of Ca-adsorbed schwertmannite and subsequent Ca repartitioning behaviors were investigated. Results showed that adsorbed Ca had a weak inhibitory effect on Fe(II)-mediated schwertmannite transformation. Release of SO42- and SEM images both indicated that transformation rates of schwertmannite decreased under the influence of adsorbed Ca. XRD patterns indicated that adsorbed Ca altered schwertmannite transformation pathways and product compositions upon treatment with 0.4 mmol/L Fe(II). The end products of Sch notably contained both goethite and lepidocrocite; however, transformation products of SchCa only contained goethite all along. Approximately 33.5% of the surface adsorbed-Ca was released into solution within 6 hr after Fe(II) injection. Aqueous Ca behaved in a "first release and then im-mobilization" manner, which indicated dissolution and secondary mineralization drove Ca migration during the Fe(II)-mediated transformation of SchCa. Adsorbed Ca blocked the surface sites for subsequent Fe(II) adsorption, limited the Fe(II)-Fe(III) ETAE, and decreased the transformation rates. This work sheds light on the complex geochemical behavior of schwertmannite under the influences of environmental perturbations in AMD environments.

Mechanisms of Cr(VI) adsorption on schwertmannite under environmental disturbance: Changes in surface complex structures.

Hexavalent chromium (Cr(VI)) mobility, reactivity and bioavailability in the acid mine drainage (AMD) are restricted by adsorption reactions on schwertmannite. However, the Cr(VI) adsorption mechanisms remain unclear. In this study, batch adsorption/desorption experiments, X-ray photoelectron spectroscopy (XPS), and in‒situ attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) in combination with a multivariate curve resolution- alternating least squares (MCR-ALS) analysis were employed to characterize Cr(VI) adsorption on schwertmannite. The results of batch experiments suggested that two kinds of anion exchange reactions occurred on Sch surface: the outer-sphere complexes and the inner-sphere complexes of sulfate were successively substituted by aqueous Cr(VI) to form inner-sphere complexes. XPS analysis showed that the adsorbed Cr (VI) tended to exchange with sulfate rather than with surface hydroxyl groups on schwertmannite. In-situ ATR-FTIR spectroscopic results confirmed that the Cr(VI) coordination species contained bidentate inner-sphere (C2ν) and monodentate inner-sphere complexes (C3ν). MCR-ALS analysis revealed that monodentate complexes were dominant at pH 5.0-8.0. The proportion of bidentate complexes decreased from 47% to 25% when pH increased from 5.0 to 8.0. Thus, we concluded that a transition occurred between bidentate to monodentate complexes. In addition, the Cr(VI) concentration exerted little influence on the change of surface complexes.