PseudomonasputidaMnB1氧化分解菱锰矿的实验研究

自然界中,菱锰矿氧化形成锰的氧化物矿物是非常普遍的现象,在菱锰矿被氧化分解发生物相转变的过程中,碳酸 盐溶解和锰的氧化往往同时发生,微生物可能起着催化作用。选取锰氧化模式菌株PseudomonasputidaMnB1和广西梧州菱 锰矿,通过菱锰矿在该细菌作用下发生转变的实验,利用场发射扫描电镜、扫描透射X射线显微成像等分析方法,研究了 矿石表面形貌变化以及锰元素在细胞上的分布特征。结果表明细菌显著促进的菱锰矿的溶解,在此基础上,进一步探讨了 细菌在菱锰矿氧化过程中的贡献,本实验结果丰富了次生锰矿床的微生物成因研究。     

Chromite oxidation by manganese oxides in subseafloor basalts and the presence of putative fossilized microorganisms

Chromite is a mineral with low solubility and is thus resistant to dissolution. The exception is when manganese oxides are available, since they are the only known naturally occurring oxidants for chromite. In the presence of Mn(IV) oxides, Cr(III) will oxidise to Cr(VI), which is more soluble than Cr(III), and thus easier to be removed. Here we report of chromite phenocrysts that are replaced by rhodochrosite (Mn(II) carbonate) in subseafloor basalts from the Koko Seamount, Pacific Ocean, that were drilled and collected during the Ocean Drilling Program (ODP) Leg 197. The mineral succession chromite-rhodochrosite-saponite in the phenocrysts is interpreted as the result of chromite oxidation by manganese oxides. Putative fossilized microorganisms are abundant in the rhodochrosite and we suggest that the oxidation of chromite has been mediated by microbial activity. It has previously been shown in soils and in laboratory experiments that chromium oxidation is indirectly mediated by microbial formation of manganese oxides. Here we suggest a similar process in subseafloor basalts.     

Role of extracellular polymeric substances in metal ion complexation on Shewanella oneidensis: Batch uptake, thermodynamic modeling, ATR-FTIR, and EXAFS study

The effect of cell wall-associated extracellular polymeric substances (EPS) of the Gram-negative bacterium Shewanella oneidensis strain MR-1 on proton, Zn(II), and Pb(II) adsorption was investigated using a combination of titration/batch uptake studies, surface complexation modeling, attenuated total reflectance - Fourier transform infrared (ATR-FTIR) spectroscopy, and Zn K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy. Both unmodified (wild-type (WT) strain) and genetically modified cells with inhibited production of EPS (ΔEPS strain) were used. Three major types of functional groups (carboxyl, phosphoryl, and amide groups) were identified in both strains using ATR-FITR spectroscopy. Potentiometric titration data were fit using a constant capacitance model (FITEQL) that included these three functional groups. The fit results indicate less interaction of Zn(II) and Pb(II) with carboxyl and amide groups and a greater interaction with phosphoryl groups in the ΔEPS strain than in the WT strain. Results from Zn(II) and Pb(II) batch adsorption studies and surface complexation modeling, assuming carboxyl and phosphoryl functional groups, also indicate significantly lower Zn(II) and Pb(II) uptake and binding affinities for the ΔEPS strain. Results from Zn K-edge EXAFS spectroscopy show that Zn(II) bonds to phosphoryl and carboxyl ligands in both strains. Based on batch uptake and modeling results and EXAFS spectral analysis, we conclude that the greater amount of EPS in the WT strain enhances Zn(II) and Pb(II) uptake and hinders diffusion of Zn(II) to the cell walls relative to the ΔEPS strain.     

The solubility of rhodochrosite (MnCO3) and siderite (FeCO3) in anaerobic aquatic environments

Natural groundwaters are often reported to be highly supersaturated with the carbonate minerals siderite (FeCO₃) and rhodochrosite (MnCO₃). The kinetics of precipitation and dissolution were determined in the light of new determinations of the solubility products of siderite and rhodochrosite. Laboratory experiments showed that the precipitation kinetics of siderite and rhodochrosite were much slower than that of calcite, and also much slower than their dissolution kinetics. Experiments with supersaturated solutions failed to reach steady state within 474 days in the case of siderite, whereas steady state for rhodochrosite was reached after 140 days. Suspensions of siderite and rhodochrosite crystals reached steady state after 10 and 80 days, respectively. The solubility product of siderite (−log K_S0(FeCO₃)) was 11.03 ± 0.10 for dried crystals and 10.43 ± 0.15 for wet crystals. For rhodochrosite the solubility product (−log K_S0(MnCO₃)) was 11.39 ± 0.14 for dried crystals and 12.51 ± 0.07 for wet crystals. The solubility product determined from supersaturated solutions was −log K_S0(MnCO₃)=11.65 ± 0.14. The observed slow precipitation kinetics of siderite and rhodochrosite might explain the apparent supersaturation that is often reported for anaerobic aquatic environments.     

Kinetics of Mn(II) oxidation by Leptothrix discophora SS1

The kinetics of Mn(II) oxidation by the bacterium Leptothrix discophora SS1 was investigated in this research. Cells were grown in a minimal mineral salts medium in which chemical speciation was well defined. Mn(II) oxidation was observed in a bioreactor under controlled conditions with pH, O₂, and temperature regulation. Mn(II) oxidation experiments were performed at cell concentrations between 24 mg/L and 35 mg/L, over a pH range from 6 to 8.5, between temperatures of 10°C and 40°C, over a dissolved oxygen range of 0 to 8.05 mg/L, and with L. discophora SS1 cells that were grown in the presence of Cu concentrations ranging from zero to 0.1 μM. Mn(II) oxidation rates were determined when the cultures grew to stationary phase and were found to be directly proportional to O₂ and cell concentrations over the ranges investigated. The optimum pH for Mn(II) oxidation was approximately 7.5, and the optimum temperature was 30°C. A Cu level as low as 0.02 μM was found to inhibit the growth rate and yield of L. discophora SS1 observed in shake flasks, while Cu levels between 0.02 and 0.1 μM stimulated the Mn(II) oxidation rate observed in bioreactors. An overall rate law for Mn(II) oxidation by L. discophora as a function of pH, temperature, dissolved oxygen concentration (D.O.), and Cu concentration is proposed. At circumneutral pH, the rate of biologically mediated Mn(II) oxidation is likely to exceed homogeneous abiotic Mn(II) oxidation at relatively low (≈μg/L) concentrations of Mn oxidizing bacteria.     

Experimental study on weathering of seafloor volcanic glass by bacteria (Pseudomonas fluorescens) – Implications for the contribution of bacteria to the water–rock reaction at the Mid-Oceanic Ridge setting

The biologically mediated weathering of the ocean crust has received increasing attention in recent decades, but the rates and the possible mechanism of elemental release during microbe–basalt interactions occurring below the seafloor have not been studied in detail. In this study, we established an experimental weathering study of seafloor natural basaltic glass comparing the effect of microbial activity (Pseudomonas fluorescens) in P-rich and P-poor media with parallel controls containing either nonviable cells or organic acid. The changes in the chemical parameters, including pH, bacterial densities, and ion concentrations (Ca, Mg, Si, Mn, Al, Fe, and P) in the solution, were examined during the different batch experiments. The results showed that the pH decreased from 7.0 to 3.5 and the bacterial density increased from 10⁵ to 10⁸ cells/ml during the first 120 h, and the cell numbers remained constant at 10⁸ cells/ml and the pH increased from 3.5 to 6 between 120 h and 864 h in the P-bearing reactors containing bacteria. In contrast, during all the experimental time, the pH remained close to neutral condition in the abiotic control systems and the dissolution rates increased markedly with a decrease in pH and became minimal at near-neutral pH in P-bearing reactors containing bacteria, where Ca, Si, and Mg release rates were 2- to 4-fold higher than those obtained in chemical systems and biotic P-limited systems. Furthermore, the surfaces of the natural volcanic glass from the biotic systems were colonized by bacteria. Simultaneously, the etch pits were observed by Scanning Electron Microscope, which further indicate that the bacteria may promote the mineral dissolution for energy gain. Some elements (e.g., Fe, Mn, and Al) releasing from natural volcanic glass are likely an important source of the elemental budget in the ocean, and thus the element release and its possible mechanism conducted in this experimental study have potential implications on the biogeochemical cycling process in the Mid-Oceanic Ridge setting.     

On the role of Mn(IV) vacancies in the photoreductive dissolution of hexagonal birnessite

Photoreductive dissolution of layer type Mn(IV) oxides (birnessite) under sunlight illumination to form soluble Mn(II) has been observed in both field and laboratory settings, leading to a consensus that this process is a key driver of the biogeochemical cycling of Mn in the euphotic zones of marine and freshwater ecosystems. However, the underlying mechanisms for the process remain unknown, although they have been linked to the semiconducting characteristics of hexagonal birnessite, the ubiquitous Mn(IV) oxide produced mainly by bacterial oxidation of soluble Mn(II). One of the universal properties of this biogenic mineral is the presence of Mn(IV) vacancies, long-identified as strong adsorption sites for metal cations. In this paper, the possible role of Mn vacancies in photoreductive dissolution is investigated theoretically using quantum mechanical calculations based on spin-polarized density functional theory (DFT). Our DFT study demonstrates unequivocally that Mn vacancies significantly reduce the band-gap energy for hexagonal birnessite relative to a hypothetical vacancy-free MnO₂ and thus would increase the concentration of photo-induced electrons available for Mn(IV) reduction upon illumination of the mineral by sunlight. Calculations of the charge distribution in the presence of vacancies, although not fully conclusive, show a clear separation of photo-induced electrons and holes, implying a slow recombination of these charge-carriers that facilitates the two-electron reduction of Mn(IV) to Mn(II).     

Adsorption to goethite of extracellular polymeric substances from Bacillus subtilis

Extracellular polymeric substances (EPS) are heterogeneous biopolymers produced by Gram-negative and Gram-positive bacterial cells. Adsorption of EPS to minerals can alter the substrata physico-chemistry and influence initial bacterial adhesion processes via conditioning film formation, but the effects of solution chemistry on uptake of EPS remain poorly understood. In this study, the adsorption to goethite (α-FeOOH) of EPS isolated from the early stationary growth-phase culture of Bacillus subtilis was investigated as a function of pH and ionic strength (I) in NaCl background electrolyte using batch studies coupled with Fourier transform infrared spectroscopy and size-exclusion high-performance liquid chromatography. Proteins, particularly those of higher molar mass, and phosphorylated macromolecules were adsorbed preferentially. Increasing solution I (1-100 mM NaCl) or pH (3.0-9.0) resulted in a decrease in the mass of EPS adsorbed. Batch studies and diffuse reflectance infrared Fourier transform spectra are consistent with ligand exchange of EPS phosphate groups for surface hydroxyls at Fe metal centers. The data indicate that both electrostatic and chemical bonding interactions contribute to selective fractionation of the EPS solution. Proteins and phosphate groups in phosphodiester bridges of nucleic acids likely play an important role in conditioning film formation at Fe oxide surfaces.     

Defining manganese(II) removal processes in passive coal mine drainage treatment systems through laboratory incubation experiments

Oxic limestone beds are commonly used for the passive removal of Mn(II) from coal mine drainage (CMD). Aqueous Mn(II) is removed via oxidative precipitation of Mn(III/IV) oxides catalyzed by Mn(II)-oxidizing microbes and Mn oxide (MnO_x) surfaces. The relative importance of these two processes for Mn removal was examined in laboratory experiments conducted with sediments and CMD collected from eight Mn(II)-removal beds in Pennsylvania and Tennessee, USA. Sterile and non-sterile sediments were incubated in the presence/absence of air and presence/absence of fungicides to operationally define the relative contributions of Mn removal processes. Relatively fast rates of Mn removal were measured in four of the eight sediments where 63–99% of Mn removal was due to biological oxidation. In contrast, in the four sediments with slow rates of Mn(II) removal, 25–63% was due to biological oxidation. Laboratory rates of Mn(II) removal were correlated (R² = 0.62) to bacterial biomass concentration (measured by phospholipid fatty acids (PLFA)). Furthermore, laboratory rates of Mn(II) removal were correlated (R² = 0.87) to field-scale performance of the Mn(II)-removal beds. A practical recommendation from this study is to include MnO_x-coated limestone (and associated biomass) from an operating bed as “seed” material when constructing new Mn(II)-removal beds.     

Manganese(II) oxidation driven by lateral oxygen intrusions in the western Black Sea

Mn(II) oxidation in the suboxic zone of the water column was studied at four stations in the western Black Sea. We measured Mn(II) oxidation rates using ⁵⁴Mn tracer and tested the hypothesis of alternative oxidants for Mn(II) other than dissolved oxygen. In anoxic incubation experiments with water from different depths of the chemocline, Mn(II) was not oxidized by nitrite, nitrate, or iodate. In the presence of light, Mn(II) also was not oxidized under anoxic conditions as well. Anaerobic Mn(II) oxidizing microorganisms could not be enriched. In oxic incubation experiments, the addition of alternative oxidants did not significantly increase the Mn(II) oxidation rate. The lack of an anaerobic Mn(II) oxidation in our experiments does not unambiguously prove the absence of anaerobic Mn(II) oxidation in the Black Sea but suggests that dissolved oxygen is the only oxidant for biologically catalyzed Mn(II) oxidation. Lateral intrusions of modified Bosphorus water were shown to be the main mechanism providing dissolved oxygen in the suboxic and the upper anoxic zones and explaining observed Mn(II) oxidation rates. Maximum in situ Mn(II) oxidation rates in the suboxic zone were 1.1 nM Mn(II) per h in the central Black Sea, 25 nM Mn(II) per h on the Romanian continental slope and 60 nM Mn(II) per h on the Anatolian continental slope. These rates correlate with the amount of particulate Mn and the number of Mn-oxide particles and are in agreement with rates measured 13 yr before. Our study highlights the importance of lateral intrusions of oxygen for the ventilation of the suboxic zone and the anoxic interior and for the regulation of different oxidation-reduction processes in the chemocline, including Mn(II) oxidation, which may be significant for other anoxic basins as well.     

Cd adsorption onto Pseudomonas putida in the presence and absence of extracellular polymeric substances

The role of bacterial extracellular polymeric substances (EPS) in metal adsorption was determined by studying Cd adsorption onto the gram-negative bacterial species Pseudomonas putida with and without enzymatic removal of EPS from the biomass material. A range of experimental approaches were used to characterize the Cd adsorption reactions, including bulk proton and Cd adsorption measurements, FTIR spectroscopy, and fluorescence microscopy. The proton-reactivities of the biomass samples with EPS are not significantly different from those obtained for EPS-free biomass. Similarly, the presence of EPS does not significantly affect the extent of Cd removal from solution by the biomass on a mass-normalized basis, based on bulk Cd adsorption measurements conducted as a function of pH, nor does it appear to strongly affect the Cd-binding groups as observed by FTIR. However, fluorescence microscopy indicates that Cd, although concentrated on cell walls, is also bound to some extent to EPS. Together, the results from this study suggest that the P. putida EPS can bind significant concentrations of Cd from solution, and that the nature and mass-normalized extent of the binding is similar to that of the cell wall. Therefore, the EPS-bearing systems do not exhibit enhanced mass-normalized removal of Cd from solution relative to the EPS-free systems. The presence of the EPS effectively increases the viability of cells exposed to aqueous Cd, likely due to sequestration of the Cd away from the cells due to Cd-EPS binding.     

Structural characterization and chemical reactivity of synthetic Mn-goethites and hematites

Several goethites were obtained through the hydrolysis at 60 °C of Fe(III) solutions containing variable amounts of Mn(II) ions. The obtained samples were thermally treated at temperatures ranging from 180 to 310 °C until the complete phase transformation to hematite was achieved. The effect of Mn in the dehydroxylation process was investigated using X-ray diffraction (XRD) and the Rietveld refinement of XRD data together with scanning electron microscopy (SEM), differential thermogravimetric analysis (DTA) and Fourier transform infrared spectroscopy (FTIR). In all cases, the formed hematites retained the acicular shape of the precursor goethite. The dehydroxylation temperature increased with the increase of the Mn content in the parent goethite. The cell parameters of both phases decreased with the thermal treatment, however the decrease in the goethite b-parameter was more pronounced. This fact could be attributed to the distortion in the goethite structure by the presence of manganese. The band shifts in the FT-IR spectra of the goethites with different Mn substitution were analysed. The intensities of the hydroxyl vibrations were indicative of the degree of dehydroxylation.The chemical reactivity of all the samples, before and after the thermal treatment, was also studied. The kinetic experiments were carried out at 40 °C in 4 mol dm^− 3 HCl. The acid dissolution of all Mn-goethites showed a congruent behavior indicative of a homogeneous distribution of Mn in the goethite crystals, this trend was not observed in the formed hematites presenting a high Mn content. The dissolution rate in goethites increased with the increase of Mn content, the opposite effect was observed in the corresponding hematites. The activation energy in both phases was also obtained and indicated that the Mn substitution produces an opposite effect on goethite- and hematite-phases. Different kinetic laws were applied in order to explain the dissolution behavior, but the modified first-order Kabai equation described the dissolution data best.     

Influence of Mn oxides on the reduction of uranium(VI) by the metal-reducing bacterium Shewanella putrefaciens

The potential for Mn oxides to modify the biogeochemical behavior of U during reduction by the subsurface bacterium Shewanella putrefaciens strain CN32 was investigated using synthetic Mn(III/IV) oxides (pyrolusite [β-MnO₂], bixbyite [Mn₂O₃] and K⁺-birnessite [K₄Mn₁₄O₂₇ · 8H₂O]). In the absence of bacteria, pyrolusite and bixbyite oxidized biogenic uraninite (UO₂[s]) to soluble U(VI) species, with bixbyite being the most rapid oxidant. The Mn(III/IV) oxides lowered the bioreduction rate of U(VI) relative to rates in their absence or in the presence of gibbsite (Al[OH]₃) added as a non-redox-reactive surface. Evolved Mn(II) increased with increasing initial U(VI) concentration in the biotic experiments, indicating that valence cycling of U facilitated the reduction of Mn(III/IV). Despite an excess of the Mn oxide, 43 to 100% of the initial U was bioreduced after extended incubation. Analysis of thin sections of bacterial Mn oxide suspensions revealed that the reduced U resided in the periplasmic space of the bacterial cells. However, in the absence of Mn(III/IV) oxides, UO₂(s) accumulated as copious fine-grained particles external to the cell. These results indicate that the presence of Mn(III/IV) oxides may impede the biological reduction of U(VI) in subsoils and sediments. However, the accumulation of U(IV) in the cell periplasm may physically protect reduced U from oxidation, promoting at least a temporal state of redox disequilibria.     

Leaching experiments on a Mn-rich slag from the recycling of alkaline batteries – Solid phase characterization and geochemical modeling

Square sections of a Mn-rich slag from an alkaline battery recycling plant were submitted to 6-month batch leaching procedures. High-Purity Water (HPW), acidic (pH 4) and alkaline (pH 12) conditions were used in order to observe the behavior of primary solid phases as well as the constituent elements (Mn, Mg, Al, Si, Ca). The experiments were coupled with both KINDIS(P) modeling and mineralogical study (SEM-EDS). Experimental results showed that the Mn-rich slag was sensitive to acidic conditions which induced the dissolution of primary phases. Moreover, pH 4 conditions did not result in the formation of newly formed solid products, leading to the greatest mobilization of metallic elements (especially Mn). Alkaline conditions favored the precipitation of secondary phases, especially rhodochrosite, calcite and Mg-saponite, inducing low mobilization of the contained elements. The KINDIS(P) modeling allowed the stability of primary phases and newly formed products to be predicted. Although the modeled results have to be considered with caution, they allow the assessment and understanding of future environmental behavior of the solid material in given conditions. In this case, the reuse of Mn-rich slag in acidic conditions has to be avoided because of the acidic dissolution of the primary phases.     

Analysis of long-term bacterial vs. chemical Fe(III) oxide reduction kinetics

Data from studies of dissimilatory bacterial (10⁸ cells mL⁻¹ of Shewanella putrefaciens strain CN32, pH 6.8) and ascorbate (10 mM, pH 3.0) reduction of two synthetic Fe(III) oxide coated sands and three natural Fe(III) oxide-bearing subsurface materials (all at ca. 10 mmol Fe(III) L⁻¹) were analyzed in relation to a generalized rate law for mineral dissolution (J_t/m₀ = k′(m/m₀)^γ, where J_t is the rate of dissolution and/or reduction at time t, m₀ is the initial mass of oxide, and m/m₀ is the unreduced or undissolved mineral fraction) in order to evaluate changes in the apparent reactivity of Fe(III) oxides during long-term biological vs. chemical reduction. The natural Fe(III) oxide assemblages demonstrated larger changes in reactivity (higher γ values in the generalized rate law) compared to the synthetic oxides during long-term abiotic reductive dissolution. No such relationship was evident in the bacterial reduction experiments, in which temporal changes in the apparent reactivity of the natural and synthetic oxides were far greater (5-10 fold higher γ values) than in the abiotic reduction experiments. Kinetic and thermodynamic considerations indicated that neither the abundance of electron donor (lactate) nor the accumulation of aqueous end-products of oxide reduction (Fe(II), acetate, dissolved inorganic carbon) are likely to have posed significant limitations on the long-term kinetics of oxide reduction. Rather, accumulation of biogenic Fe(II) on residual oxide surfaces appeared to play a dominant role in governing the long-term kinetics of bacterial crystalline Fe(III) oxide reduction. The experimental findings together with numerical simulations support a conceptual model of bacterial Fe(III) oxide reduction kinetics that differs fundamentally from established models of abiotic Fe(III) oxide reductive dissolution, and indicate that information on Fe(III) oxide reactivity gained through abiotic reductive dissolution techniques cannot be used to predict long-term patterns of reactivity toward enzymatic reduction at circumneutral pH.     

Lepidocrocite-catalyzed Mn(II) oxygenation by air and its effect on the oxidation and mobilization of As(III)

Manganese (oxy)hydroxides (MnO_X) play important roles in the oxidation and mobilization of toxic As(III) in natural environments. Abiotic oxidation of Mn(II) to MnO_X in the presence of Fe minerals has been proved to be an important pathway in the formation of Mn(III, IV) (oxy)hydroxides. However, interactions between Mn(II) and As(III) in the presence of Fe minerals are still poorly understood. In this study, abiotic oxidation of Mn(II) on lepidocrocite, and its effect on the oxidation and mobilization of As(III) were investigated. The results show that MnO_X species are detected on lepidocrocite and their contents increase with increasing pH values ranging from 7.5 to 8.4. After 10 days, an MnOx component, groutite (α-MnOOH) was found on lepidocrocite. During the simultaneous oxidation of Mn(II) and As(III), and the As(III) pre-adsorbed processes, the presence and oxidation of Mn(II) significantly promotes the removal of soluble As(III). In addition, MnOx formed on lepidocrocite also contributes to the oxidation of soluble and adsorbed As(III) to As(V), the latter being subsequently released into solution. In the process where Mn(II) is pre-adsorbed on lepidocrocite, less As(III) is removed, given that the active sites occupied by MnOx inhibit the adsorption of As(III). In all experiments, the removal percentages of As(III) and the release of As(V) are correlated positively with pH values and initial concentrations of Mn(II), although they are not apparent in the Mn(II) pre-adsorbed system.     

Dissolution of hausmannite (Mn3O4) in the presence of the trihydroxamate siderophore desferrioxamine B

That microbial siderophores may be mediators of Mn(III) biogeochemistry is suggested by recent studies showing that these well known Fe(III)-chelating ligands form very stable Mn(III) aqueous complexes. In this study, we examine the influence of desferrioxamine B (DFOB), a trihydroxamate siderophore, on the dissolution of hausmannite, a mixed valence Mn(II, III) oxide found in soils and freshwater sediments. Batch dissolution experiments were conducted both in the absence (pH 4-9) and in the presence of 100 μM DFOB (pH 5-9). In the absence of the ligand, there is a sharp decrease in the extent of proton-promoted dissolution above pH 5 and no appreciable dissolution above pH 8. The resulting aqueous Mn²⁺ activities were in good agreement with previous studies, indirectly supporting the accepted two-step mechanism involving the formation of manganite and reprecipitation of hausmannite. Desferrioxamine B enhanced hausmannite dissolution over the entire pH range investigated, both via the formation of a Mn(III) complex and through surface-catalyzed reductive dissolution. Above pH 8, non-reductive ligand-promoted dissolution dominated, whereas below pH 8, dissolution was non-stoichiometric with respect to DFOB. Concurrent proton-promoted, ligand-promoted, reductive, and induced dissolution was observed, with Mn release by either reductive or induced dissolution increasing linearly with decreasing pH. The fast kinetics of the DFOB-promoted dissolution of hausmannite, as compared to iron oxides, suggest that the siderophore-promoted dissolution of Mn(III)-bearing minerals may compete with the siderophore-promoted dissolution of Fe(III)-bearing minerals.     

Migration and transformation of manganese during the artificial recharging of a deep confined aquifer

Field tests and laboratory experiments were performed, using an artificial groundwater recharging site in Southeast China as an example, to investigate the migration and transformation of manganese during the artificial recharging of a deep confined aquifer. The migration and transformation of total manganese and divalent manganese (Mn(II)) were influenced by mixing, oxidation reactions, and the dissolution of minerals containing manganese, and increasing the dissolved oxygen (DO) concentration was found to promote the dissolution of minerals containing manganese. The laboratory experiments showed that the retardation factors were higher upstream than downstream of the recharging hole. The amount of dissolution that occurred decreased, and the amount of mixing that occurred increased as the distance from the recharging hole increased. The DO concentration decreased as the amount of dissolution of minerals containing manganese that occurred decreased. A high temperature, a high DO concentration, and the presence of microorganisms were found to promote the dissolution of minerals containing manganese, which caused the total manganese and Mn(II) concentrations to increase.     

Effects of desferrioxamine-B on the release of arsenic from volcanic rocks

Microorganisms play an important role in As mobilization into groundwater by directly influencing As speciation or indirectly inducing solubilisation from As-bearing phases, such as Fe, Mn and Al oxides. Iron oxide dissolution could also be induced by siderophores, small-molecule compounds produced by microorganisms to favour Fe uptake. Well waters exceeding the potable water limit of 10 μg As L⁻¹ (0.133 μM) have been widely reported in geothermal areas. Mechanisms responsible for these high As concentrations have not yet been thoroughly elucidated and the complexity of As mobilization in volcanic aquifers is still open to multiple interpretations. The present study was based on batch release experiments aimed at verifying and quantifying the effect of siderophores on As mobilization from volcanic rocks (lava, tuff, peperino and fallout deposit) at different pH and ligand concentration. In the experiments the siderophore trihydroxamate desferroxamine B (Dfob) was used and its effect on As release from volcanic rocks was manifest after the first days. The most favourable pH for As release was pH 6 while concentrations above 250 μM Dfob considerably enhanced As and Fe concentrations in solution. The As release from rocks was between 2.0–10% at pH 6 and 2.4–8.8% at pH 8. The As/Fe ratio in solution changed with time suggesting different release mechanisms and higher mobility of As compared to Fe during the first phase of the experiment. The presence of siderophore increased Fe dissolution rates up to 10 orders of magnitude. The As release correlated with Al, Mn, Fe, Si, V, Ga and Sb and the release of all these elements increased with increasing Dfob concentration. In alkaline environments also Cu, Zn and Pb were mobilized. The presence of siderophores represents a possible trigger for As mobilization from iron binding minerals to the water phase, with interesting implications for groundwater quality, plant uptake and bacterial communities.     

Hydrochemical evolution and arsenic release in shallow aquifer in the Titas Upazila,Eastern Bangladesh

Groundwater arsenic (As) concentrations above 10 μg/L (World Health Organization; WHO standard) are frequently found in the Titas Upazila in Bangladesh. This paper evaluates the groundwater chemistry and the mechanisms of As release acting in an underground aquifer in the middle-northeast part of the Titas Upazila in Bangladesh. Previous measurements and analyses of 43 groundwater samples from the region of interest (ROI) are used. Investigation is based on major ions and important trace elements, including total As and Fe in groundwater samples from shallow (8–36 m below ground level: mbgl) and deep (85–295 mbgl) tube wells in the aforementioned ROI. Principal hydrochemical facies are Ca–HCO₃, with circumneutral pH. The different redox-sensitive constituents (e.g., As, Fe, Mn, NH₄, and SO₄) indicate overlapping redox zones, leading to differences regarding the redox equilibrium. Multivariate statistical analysis (factor analysis) was applied to reduce 20 chemical variables to four factors but still explain 81% of the total variance. The component loadings give hints as to the natural processes in the shallow aquifers, in which organic matter is a key reactant. The observed chemistry of As, Fe, and Mn can be explained by simultaneous equilibrium between Fe-oxide and SO₄ reduction and an equilibrium of rhodochrosite precipitation/dissolution. A correlation test indicates the likeliness of As release by the reductive dissolution of Fe-oxides driven by the degradation of sediments organic matter. Other mechanisms could play a role in As release, albeit to a lesser extent. Reactive transport modeling using PHREEQC reproduced the observed chemistry evolution using simultaneous equilibrium between Fe-oxide and SO₄ reduction and the equilibrium of rhodochrosite dissolution/precipitation alongside organic matter oxidation.