Proton-promoted Dissolution Research Articles

Fractionation of yttrium and holmium during basaltic soil weathering

The anomalously low affinity of yttrium (Y) for iron (Fe) (oxyhydr)oxides relative to lanthanides with similar ionic radius (e.g., Ho) has been demonstrated in experiments with isolated Fe minerals and in a variety of marine systems that contain high concentrations of solid phase Fe. However, it has not previously been demonstrated to occur during soil genesis, despite the common observation that many soils become enriched in Fe over time. We hypothesized that Y would become progressively depleted in soils relative to Ho with increased weathering. Since, trivalent Y has an anomalously low Misono softness relative to other trivalent ions included in the rare earth element and yttrium group (REY3+), we also investigated whether soil REY fractionation reflects variation in Misono softness. To test this, we measured trends in total REY concentrations for Hawaiian soils derived from basaltic parent materials aged 0.3–4100ky, and measured REYs released from the same samples during short-time (3h) dissolution experiments conducted as part of a previous investigation linking dissolution with surface charge properties (Chorover et al., 2004). The chondrite-normalized Y/Ho ratios in the parent Hawaiian basalt (Chond[Y/Ho]=0.998) and continental dust (Chond[Y/Ho]=0.994) inputs are remarkably similar, and thus we can interpret deviations from Chond[Y/Ho]∼1.0 to result from soil biogeochemical processes and not source mixing. Between 0.3 and 20ky, the Chond[Y/Ho] ratio of the subsurface soils decreased from 0.96±0.07(2σ) to 0.71±0.05, and then remained unchanged across the rest of the weathering sequence. In contrast, the Chond[Y/Ho] ratio of the surface soils decreased from 0.99±0.07 to 0.76±0.05 at 150ky and then, most likely due to continued dust inputs, increased to 1.04±0.07 in the oldest soils. Analysis of the short-time dissolution experiments revealed preferential release of Y relative to Ho (and also La relative Pr) at intermediate pH where aqueous REY concentrations are governed by proton competition for adsorption sites. Proton-competition-control over REY release is bounded at high pH by the onset of colloidal dispersion—represented by the point of minimum dissolution (p.m.d.) of Al—and at low pH by the soil’s point of zero net charge (p.z.n.c.) and/or when proton-promoted dissolution of REY-containing solids, including Fe-(oxyhydr)oxides, control REY release. Results of our dissolution experiments suggest that complexation of REYs by dissolved organic matter (DOM) does not drive Y–Ho fractionation during pedogenesis, but rather may suppress it. Synthesis of these field and laboratory experiments suggests the Y/Ho ratio decreases early in soil development (<20ky) when weathering rates are high and competitive proton adsorption affects REY fractionation. Given that Fe-(oxyhydr)oxide sorbents exhibit greater affinity for Ho relative to Y, their prevalent neo-formation during incipient pedogenesis likely plays a central role in Y–Ho fractionation in these soils. Persistence of low Chond[Y/Ho] ratios in the subsurface soils even at 4100ky suggests Y–Ho fractionation continues, albeit at a slower rate, as weathering proceeds.

Quantitative Localized Proton-Promoted Dissolution Kinetics of Calcite Using Scanning Electrochemical Microscopy (SECM)

Scanning electrochemical microscopy (SECM) has been used to determine quantitatively the kinetics of proton-promoted dissolution of the calcite (1014) cleavage surface (from natural “Iceland Spar”) at the microscopic scale. By working under conditions where the probe size is much less than the characteristic dislocation spacing (as revealed from etching), it has been possible to measure kinetics mainly in regions of the surface which are free from dislocations, for the first time. To clearly reveal the locations of measurements, studies focused on cleaved “mirror” surfaces, where one of the two faces produced by cleavage was etched freely to reveal defects intersecting the surface, while the other (mirror) face was etched locally (and quantitatively) using SECM to generate high proton fluxes with a 25 μm diameter Pt disk ultramicroelectrode (UME) positioned at a defined (known) distance from a crystal surface. The etch pits formed at various etch times were measured using white light interferometry to ascertain pit dimensions. To determine quantitative dissolution kinetics, a moving boundary finite element model was formulated in which experimental time-dependent pit expansion data formed the input for simulations, from which solution and interfacial concentrations of key chemical species, and interfacial fluxes, could then be determined and visualized. This novel analysis allowed the rate constant for proton attack on calcite, and the order of the reaction with respect to the interfacial proton concentration, to be determined unambiguously. The process was found to be first order in terms of interfacial proton concentration with a rate constant k = 6.3 (± 1.3) × 10–4 m s–1. Significantly, this value is similar to previous macroscopic rate measurements of calcite dissolution which averaged over large areas and many dislocation sites, and where such sites provided a continuous source of steps for dissolution. Since the local measurements reported herein are mainly made in regions without dislocations, this study demonstrates that dislocations and steps that arise from such sites are not needed for fast proton-promoted calcite dissolution. Other sites, such as point defects, which are naturally abundant in calcite, are likely to be key reaction sites.

Proton-promoted dissolution of α-FeOOH nanorods and microrods: Size dependence, anion effects (carbonate and phosphate), aggregation and surface adsorption

Iron-containing oxide nanoparticles are of great interest from a number of technological perspectives and they are also present in the natural environment. Although recent evidence suggests that particle size plays an important role in the dissolution of metal oxides, a detailed fundamental understanding of the influence of particle size is just beginning to emerge. In the current study, we investigate whether nanoscale size-effects are observed for the dissolution of iron oxyhydroxide under different conditions. The dissolution of two particle sizes of goethite, α-FeOOH in the nanoscale and microscale size regimes (herein referred to as nanorods and microrods), in aqueous suspensions at pH 2 is investigated. It is shown here that in the presence of nitrate, nanorods shows greater dissolution on both a per mass and per surface area basis relative to microrods, in agreement with earlier studies. In the presence of carbonate and phosphate, however, dissolution of α-FeOOH nanorods at pH 2 is significantly inhibited, despite the fact that these anions result in a three- to fivefold enhancement of the dissolution of microrods relative to the nitrate anion. Light scattering techniques and electron microscopy show that nanorod suspensions are less stable compared to microrod suspensions resulting in nanorod aggregation under conditions where microrods stay more dispersed. Furthermore, spectroscopic studies using ATR–FTIR spectroscopy show distinct differences in phosphate and carbonate adsorption on nanorods compared to microrods. These results demonstrate that aggregation and the details of surface adsorption are important in the dissolution behavior of nanoscale materials.

Efficient Adsorption and Combined Heterogeneous/Homogeneous Fenton Oxidation of Amaranth Using Supported Nano-FeOOH As Cathodic Catalysts

Iron oxyhydroxide (FeOOH) as heterogeneous catalyst has been widely used in Fenton-like advanced oxidation processes due to its attractive properties such as wide-operating pH range and controllable iron leaching into solution. However, little is known about the Fe3+/Fe2+ transformation of supported FeOOH catalyst under the external electrical field condition, which is of the essence in electro-Fenton-like oxidation reactions. In this study, activated carbon-supported nano-FeOOH (FeOOH/AC) catalysts were prepared by the air oxidation of ferrous hydroxide suspension method. The as-prepared catalyst was characterized with various characterization techniques and identified as goethite and lepidocrocite mixed crystals. Adsorption and electrochemically assisted oxidation of amaranth with the FeOOH/AC heterogeneous catalysts were investigated at pH 4.0 using graphite felt as cathode. Under weak acidic and external electric field conditions, the supported nano-FeOOH catalyst undergoes proton-promoted dissolution and electrochemical reductive dissolution processes, which facilitates Fe3+/Fe2+ transformation and produces a beneficial enhancement of the heterogeneous/homogeneous electro-Fenton reaction rates. Experimental results demonstrated that the FeOOH/AC heterogeneous catalyst possesses admirable adsorbability, and the electrochemically assisted oxidation of amaranth takes place not only through the heterogeneous Fenton reaction on catalyst/solution interface but also through the homogeneous Fenton reaction in bulk solution due to iron liberation from the supported nano-FeOOH. In addition, a possible electrochemically assisted oxidation mechanism is also proposed.

Effect of lactate, glycine, and citrate on the kinetics of montmorillonite dissolution

The montmorillonite dissolution in saline solutions that mimic synthetic lung fluids (SLF) was investigated to gain knowledge on the clearance mechanisms of inhaled clay particles. Dissolution rates were measured at pH 4 (macrophages) and 7.5 (interstitial fluids) at 37 °C in flow-through reactors. The effect of organic acids was investigated through the addition of lactate, citrate, and glycine (0.15, 1.5, and 15 mmol/L). Lactate or glycine does not markedly affect the montmorillonite dissolution rates at pH 4, but at pH 7.5 there exists a slight inhibitory effect of lactate on the dissolution, probably due to a reduction in the number of reactive surface sites caused by lactate adsorption. Citrate enhances the dissolution rate by 0.5 order of magnitude at pH 4 and more than 1 order of magnitude at pH 7.5, thus indicating the prevalence of the ligand-promoted over the proton-promoted dissolution mechanism under these experimental conditions. The kinetic data were used to estimate the reduction in size of an inhaled clay particle. At pH 7.5, a particle 500 nm in diameter could be reduced 25% in the presence of citrate, whereas the reduction in saline solution would only be 10% after 10 years.

GILDES Model Simulations of the Atmospheric Corrosion of Copper Induced by Low Concentrations of Carboxylic Acids

A computer simulation with a GILDES-based model using the COMSOL multiphysics software was performed for copper exposed to low concentrations of carboxylic acids in humidified air at room temperature. GILDES is a six-regime computer model (Gas, the Interface between gas and liquid, the Liquid, the Deposition layer, the Electrodic region near the surface and the Solid). The simulations were compared to previously published in-situ results for copper at the same conditions analysed by a quartz crystal microbalance (QCM) and infrared reflection absorption spectroscopy (IRAS). Experimental and calculated results agree with each other with respect to the effect of corrosion, showing formic acid as the most aggressive followed by acetic and propionic acid. This is supported by a higher ligand- and proton-promoted dissolution found in formic acid exposures, followed by acetic and propionic exposures. The dominating precipitated phases were Cu2O, Cu(OH)2, Cu(CH3COO)2 · H2O, Cu(HCOO)2 · 4H2O and Cu(CH3CH2COO)2 · H2O. Besides Cu2O, the simulations suggest that the hydrated form of the respective carboxylates is the most likely compound to be formed in this type of atmospheres.

Dissolution rates of phyllosilicates as a function of bacterial metabolic diversity

Weathering experiments using biotite and phlogopite in the presence of bacteria were conducted to better understand biotic dissolution kinetics and processes (proton- and ligand-promoted dissolution) under aerobic conditions. Miniature batch reactors (300 μl in microplate wells) were used at 24 °C for 3 days with and without bacterial strains. Abiotic experiments were performed with organic and nitric acids in order to calibrate the biotite–phlogopite chemical dissolution. An empirical model was used to fit the pH dependence for iron release rate (r Fe) considering the influence of both protons and ligands from acidic to neutral conditions (pH ranging from 3 to 7): r Fe = k H ( a H + ) m + k L ( a L ) 1 where k is the apparent rate constant, a H+ and a L are the activities of protons and ligands, and m and l are the reaction orders. For both minerals in most cases at a given pH, the iron release rates in the presence of bacteria were in good agreement with rates determined by the chemical model and could be explained by a combination of proton- and ligand-promoted processes. Bacteria affect mineral dissolution and iron release rates through the quantities and nature of the organic acids they produce. Three domains were differentiated and proposed as biochemical models of mica dissolution: (1) below pH 3, only proton-promoted dissolution occurred, (2) in weakly acidic solutions both ligand- and proton-promoted mechanisms were involved, and (3) iron immobilization occured, at pH values greater than 4 for biotite and greater than 5 for phlogopite. This model allows us to distinguish the “weathering pattern phenotypes” of strains. Bacteria that are isolated from horizons poor in carbon appear more efficient at weathering micas than bacterial strains isolated from environments rich in carbon. Moreover, our results suggest that the mineral could exert a control on the release of organic acids and the “weathering pattern phenotypes” of bacteria.

Mobilization of metals and phosphorus from intact forest soil cores by dissolved inorganic carbon

Increased dissolved inorganic carbon (DIC) enhances the mobilization of metals and nutrients in soil solutions. Our objective was to investigate the mobilization of Al, Ca, Fe, and P in forest soils due to fluctuating DIC concentrations. Intact soil cores were taken from the O and B horizons at the Bear Brook Watershed in Maine (BBWM) to conduct soil column transport experiments. Solutions with DIC concentrations (∼20-600 ppm) were introduced into the columns. DIC was reversibly sorbed and its migration was retarded by a factor of 1.2 to 2.1 compared to the conservative sodium bromide tracer, corresponding to a log K (D) = -0.82 to -0.07. Elevated DIC significantly enhanced the mobilization of all Al, Fe, Ca, and P. Particulate (>0.4 μm) Al and Fe were mobilized during chemical and flow transitions, such as increasing DIC and dissolved organic carbon (DOC), and resumption of flow after draining the columns. Calcium and P were primarily in dissolved forms. Mechanisms such as ion exchange (Al, Fe, Ca), ligand- and proton-promoted dissolution (Al and Fe), and ligand exchange (P) were the likely chemical mechanisms for the mobilization of these species. One column was packed with dried and sieved B-horizon soil. The effluent from this column had DOC, Al, and Fe concentrations considerably higher than those in the intact columns, suggesting that these species were mobilized from soil's microporous structure that was otherwise not exposed to the advective flow. Calcium and P concentrations, however, were similar to those in the intact columns, suggesting that these elements were less occluded in soil particles.

Simulation of adsorption processes on the glass surface in aqueous solutions containing oxalic acid

In this study we develop a kinetic model for the simulation of adsorption processes on a glass surface in the presence of oxalic acid, which is subsequently used for an investigation of strategies to inhibit glass corrosion by means of surface oxalate complexes. The behavior of individual adsorbing species is resolved by a Kinetic Monte Carlo method (KMC). Kinetic parameters for different process specifications were chosen from experimental data or were calculated ab initio by the density functional theory (DFT). Our simulations indicate that surface complexation occurs at pH < 8 for the Al containing glass and at pH < 6 for the diopside glass. Moreover it reveals, that on the one hand the surface protonation catalyses the surface complexation, which can inhibit the glass corrosion. On the other hand the formation of magnesium and aluminium surface complexes catalyses the proton-promoted dissolution. The overall effect leads to the inhibition of corrosion at pH values <5 for diopside glass due to formation of stable calcium–magnesium oxalate complexes.

Aerobic oxidation of mackinawite (FeS) and its environmental implication for arsenic mobilization

Abstract Oxidation of mackinawite (FeS) and concurrent mobilization of arsenic were investigated as a function of pH under oxidizing conditions. At acidic pH, FeS oxidation is mainly initiated by the proton-promoted dissolution, which results in the release of Fe(II) and sulfide in the solution. While most of dissolved sulfide is volatilized before being oxidized, dissolved Fe(II) is oxidized into green rust-like precipitates and goethite ( α -FeOOH). At basic pH, the development of Fe(III) (oxyhydr)oxide coating on the FeS surface inhibits the solution-phase oxidation following FeS dissolution. Instead, FeS is mostly oxidized into lepidocrocite ( γ -FeOOH) via the surface-mediated oxidation without dissolution. At neutral pH, FeS is oxidized via both the solution-phase oxidation following FeS dissolution and the surface-mediated oxidation mechanisms. The mobilization of arsenic during FeS oxidation is strongly affected by FeS oxidation mechanisms. At acidic pH (and to some extent at neutral pH), the rapid FeS dissolution and the slow precipitation of Fe (oxyhydr)oxides results in arsenic accumulation in water. In contrast, the surface-mediated oxidation of FeS at basic pH leads to the direct formation of Fe (oxyhydr)oxides, which provides effective adsorbents for As under oxic conditions. At acidic and neutral pH, the solution-phase oxidation of dissolved Fe(II) accelerates the oxidation of the less adsorbing As(III) to the more adsorbing As(V). This study reveals that the oxidative mobilization of As may be a significant pathway for arsenic enrichment of porewaters in sulfidic sediments.

Iron isotope fractionation during proton- and ligand-promoted dissolution of primary phyllosilicates

We studied stable iron isotope fractionation during dissolution of a biotite and chlorite enriched mineral fraction from granite by HCl and 5 mM oxalic acid in a pH range of 4–5.9. Batch experiments covered a time period from 2 h to 100 days and were performed at initial potassium concentrations of 0, 0.5, and 5 mM to induce different levels of biotite exfoliation. All experiments were kept anoxic to investigate solely the dissolution step without the influence of oxidation and precipitation of secondary Fe oxyhydroxides. Oxalic acid increased the release of Fe by a factor of ∼15 compared with the HCl experiments. Addition of 0.5 mM K to initial solutions in proton-promoted dissolution decreased the release of Fe by 30–65% depending on the dissolution stage. In ligand-controlled dissolution, K reduced the Fe release only to a minor extent. All solutions of the early dissolution stages were enriched in light Fe isotopes by up to −1.4‰ in δ56Fe compared with the isotopic composition of biotite and chlorite mineral separates, which we explained by a kinetic isotope effect. In proton-promoted dissolution, early released fractions of K-enriched experiments were significantly lighter (−0.7‰ to −0.9‰) than in the initially K-free experiments. The evolution of Fe isotope ratios in solution was modeled by a linear combination of kinetic isotope effects during two independent dissolution processes attacking different crystallographic sites. In ligand-controlled dissolution, K did not influence the kinetic isotope effect and the Fe isotope composition in solution in the late dissolution stages remained slightly lighter than the bulk composition of the biotite/chlorite enriched mineral fraction. This study demonstrates that the initial Fe weathering flux should be enriched in light Fe isotopes and that Fe isotope data in combination with dissolution kinetics and stoichiometry provide new insights into dissolution mechanisms.

Surface complexation and proton-promoted dissolution in aqueous apatite systems

Abstract The dissolution of hydroxyapatite (HAP) and fluorapatite (FAP) has been studied (25 °C, 0.1 M NaCl medium) within the pH ranges 2–11 (FAP) and 4–10 (HAP). A range of techniques has been utilized to achieve understanding in how these two abundant minerals may interact with their natural surroundings (e.g., body fluids and soil environments). Synthetic crystalline HAP and FAP were prepared, and both minerals were found to undergo a phase transformation generated during a dialysis step of the synthetic routes. Surface-deficient layers with the nonstoichiometric compositions Ca8.4(HPO4)1.6(PO4)4.4(OH)0.4 and Ca9(HPO4)2(PO4)4F2 were identified. The equilibrium analysis of experimental solubility data of the two apatite systems was based upon potentiometric titration data, batch experiments, and zeta-potential measurements in combination with information provided by X-ray photoelectron spectroscopy (XPS) and attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. The analysis required, besides the two solubility equilibria, the formation of surface protonation/deprotonation reactions, re-adsorption processes involving phosphate and fluoride ions as well as an ion exchange reaction (≡F + H2O ⇋ ≡OH + H+ + F–) to fully describe the dissolution characteristics of the two apatite systems. The resulting model also agrees with observations from XPS and solubility data, claiming the formation of CaF2(s) in the most acidic pH range of the FAP system. In addition, calculated isoelectric points (pHiep) are in agreement with values from surface charge measurements showing pHiep (HAP) = 8.1 and pHiep (FAP) = 5.7.

The preparation and characterization of vanadium-substituted goethite: The importance of temperature

Despite a close geo-chemical association between vanadium (V) and iron (Fe) in natural environments, there is little research on the substitution of V in goethite. To assess the effect of temperature on V-substitution in goethite, a series of V-substituted goethite were prepared under varying synthesis temperatures, and analysed using wet chemical and multi-spectroscopic techniques. Vanadium substitution was inversely related to synthesis temperatures and was hindered by the oxidation of V 3+ to V 4+/5+ as indicated by X-ray absorption near-edge spectroscopy. The presence of V (V 5+ > V 4+ > V 3+) at high temperature hindered the nucleation of goethite and crystal growth along particular faces resulting in large-sized and twinned crystals as shown by transmission electron microscopy. The large-sized goethite crystals released more Fe (mmoles) per unit surface area during proton-promoted dissolution than the smaller-sized crystals, which could be due to distorted V 4+/5+ local coordination environments in the mineral structure. The dissolution studies showed a heterogeneous distribution of V and/or crystal defects in goethite crystals. The results show that low synthesis temperatures preserved the oxidation state of V 3+, which has ionic radius and hydrolytic properties similar to Fe 3+, and hence resulted in as much as 13.3 mol per cent substitution. The structural stability of the goethite decreased upon V-substitution in order; V 3+ > V 4+ > V 5+. This research provides important information about the interaction between temperature, V incorporation, and crystal structure properties of goethite for V sequestration and other potentially toxic metal cations.

Probing the molecular-level control of aluminosilicate dissolution: A sensitive solid-state NMR proxy for reactive surface area

For two suites of volcanic aluminosilicate glasses, the accessible and reactive sites for covalent attachment of the fluorine-containing (3,3,3-trifluoropropyl)dimethylchlorosilane (TFS) probe molecule were measured by quantitative 19F nuclear magnetic resonance (NMR) spectroscopy. The first set of samples consists of six rhyolitic and dacitic glasses originating from volcanic activity in Iceland and one rhyolitic glass from the Bishop Tuff, CA. Due to differences in the reactive species present on the surfaces of these glasses, variations in the rate of acid-mediated dissolution (pH 4) for samples in this suite cannot be explained by variations in geometric or BET-measured surface area. In contrast, the rates scale directly with the surface density of TFS-reactive sites as measured by solid-state NMR. These data are consistent with the inference that the TFS-reactive M-OH species on the glass surface, which are known to be non-hydrogen-bonded Q 3 groups, represent loci accessible to and affected by proton-mediated dissolution. The second suite of samples, originating from a chronosequence in Kozushima, Japan, is comprised of four rhyolites that have been weathered for 1.1, 1.8, 26, and 52 ka. The number of TFS-reactive sites per gram increases with duration of weathering in the laboratory for the “Icelandic” samples and with duration of field weathering for both “Icelandic” and Japanese samples. One hypothesis is consistent with these and published modeling, laboratory, and field observations: over short timescales, dissolution is controlled by fast-dissolving sites, but over long timescales, dissolution is controlled by slower-dissolving sites, the surface density of which is proportional to the number of TFS-reactive Q 3 sites. These latter sites are not part of a hydrogen-bonded network on the surface of the glasses, and measurement of their surface site density allows predictions of trends in reactive surface area. The TFS treatment method, which is easily monitored by quantitative 19F solid-state NMR, therefore provides a chemically specific and quantifiable proxy to understand the nature of how sites on dissolving silicates control dissolution. Furthermore, 27Al NMR techniques are shown here to be useful in identifying clays on the glass surfaces, and these methods are therefore effective for quantifying concentrations of weathering impurities. Our interpretations offer a testable hypothesis for the mechanism of proton-promoted dissolution for low-iron aluminosilicate minerals and glasses and suggest that future investigations of reactive surfaces with high-sensitivity NMR techniques are warranted.

Enhancement of arsenic mobility by indigenous bacteria from mine tailings as response to organic supply

Arsenic leaching by indigenous bacteria in abandoned Au–Ag mine tailings which contained approximately 3200 mg/kg of As was investigated after supply of various organic substrates. Sequential extraction analysis designed to determine the mode of As occurrence in the tailings revealed that most As (90%) was closely associated with the Fe fraction. When glucose was supplied as a C source, indigenous bacteria significantly enhanced the extent of As release from the tailings into solution under both aerobic and anaerobic conditions. Anaerobic indigenous bacteria leached more amount of As from the tailings than aerobes. Highly positive correlation between the extracted amounts of As and Fe implied that microbial dissolution of Fe(III)-oxides, whether it was ligand- and proton-promoted dissolution or reductive dissolution, might be dominantly responsible for the As release. Bacterial strains which were resistant to up to 100 mM As(V) was aerobically isolated from the tailings. One of the isolates appeared to reduce some aqueous As(V) to likely As(III) in a batch type experiment, which indicated that indigenous bacteria can mediate the electrochemical speciation and thus the mobility of As in the tailings. The results suggest that indigenous bacteria in As-contaminated tailings can increase As mobility from the solid media when microbially available organic substrates are supplied, and thus enhance the risk of As dispersion to nearby soil, sediment and groundwater.

Free Energies for Acid Attack Reactions of Lithium Cobaltate

The attack of lithium-ion battery cathodes by stray aqueous HF, with resultant dissolution, protonation, and possibly other unintended reactions, can be a significant source of capacity fade. We explore the calculation of reaction free energies of lithium cobaltate in acid by a “hybrid” method, in which solid-phase free energies are calculated from first principles at the generalized gradient approximation intrasite coulomb interaction () level and tabulated values of ionization potentials and hydration energies are employed for the aqueous species. Analysis of the dissolution of the binary oxides and CoO suggests that the atomic energies for Co and Li should be shifted from values calculated by first principles to yield accurate reaction free energies within the hybrid method. With the shifted atomic energies, the hybrid method was applied to analyze proton-promoted dissolution and protonation reactions of in aqueous acid. Reaction free energies for the dissolution reaction, the reaction to form spinel, and the proton-for-lithium exchange reaction are obtained and compared to empirical values. An extension of the present treatment to consider partial reactions is proposed, with a view to investigating interfacial and environmental effects on the dissolution reaction.

Characterization of elemental release during microbe–granite interactions at T = 28 °C

This study used batch reactors to characterize the mechanisms and rates of elemental release (Al, Ca, K, Mg, Na, F, Fe, P, Sr, and Si) during interaction of a single bacterial species ( Burkholderia fungorum) with granite at T = 28 °C for 35 days. The objective was to evaluate how actively metabolizing heterotrophic bacteria might influence granite weathering on the continents. We supplied glucose as a C source, either NH 4 or NO 3 as N sources, and either dissolved PO 4 or trace apatite in granite as P sources. Cell growth occurred under all experimental conditions. However, solution pH decreased from ∼7 to 4 in NH 4-bearing reactors, whereas pH remained near-neutral in NO 3-bearing reactors. Measurements of dissolved CO 2 and gluconate together with mass-balances for cell growth suggest that pH lowering in NH 4-bearing reactors resulted from gluconic acid release and H + extrusion during NH 4 uptake. In NO 3-bearing reactors, B. fungormum likely produced gluconic acid and consumed H + simultaneously during NO 3 utilization. Over the entire 35-day period, NH 4-bearing biotic reactors yielded the highest release rates for all elements considered. However, chemical analyses of biomass show that bacteria scavenged Na, P, and Sr during growth. Abiotic control reactors followed different reaction paths and experienced much lower elemental release rates compared to biotic reactors. Because release rates inversely correlate with pH, we conclude that proton-promoted dissolution was the dominant reaction mechanism. Solute speciation modeling indicates that formation of Al–F and Fe–F complexes in biotic reactors may have enhanced mineral solubilities and release rates by lowering Al and Fe activities. Mass-balances further reveal that Ca-bearing trace phases (calcite, fluorite, and fluorapatite) provided most of the dissolved Ca, whereas more abundant phases (plagioclase) contributed negligible amounts. Our findings imply that during the incipient stages of granite weathering, heterotrophic bacteria utilizing glucose and NH 4 only moderately elevate silicate weathering reactions that consume atmospheric CO 2. However, by enhancing the dissolution of non-silicate, Ca-bearing trace minerals, they could contribute to high Ca/Na ratios commonly observed in granitic watersheds.

Dissolution of hausmannite (Mn 3O 4) 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 Mn 2+ 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.

Mechanisms Controlling the Leaching Kinetics of Fixated Flue Gas Desulfurization (FGD) Material under Neutral and Acidic Conditions

A number of agricultural and engineering uses for fixated flue gas desulfurization (FGD) material exist; however, the potential for leaching of hazardous elements has limited widespread application and the processes controlling the leaching of this material are poorly understood. In this study, a flow-through rotating-disk system was applied to elucidate the relative importance of bulk diffusion, pore diffusion, and surface chemical reaction in controlling the leaching of fixated FGD material under pH conditions ranging from 2.2 to 6.8. Changing the hydrodynamics in the rotating disk system did not affect the leaching kinetics at both pH 2.2 and 6.8, indicating that bulk diffusion was not the kinetic-limiting step. Application of the shrinking core model (SCM) to the data suggested a surface reaction-controlled mechanism, rather than a pore diffusion mechanism. The leaching of fixated FGD material increased with decreasing pH, suggesting it can be described by a combination of an intrinsic hydration reaction and a proton-promoted dissolution reaction. X-ray diffraction (XRD) and elemental composition analyses before and after leaching suggests that for most elements a number of solid phases controlled the leaching process.

Characterization of elemental release during microbe–basalt interactions at T = 28 °C

This study used batch reactors to characterize the rates and mechanisms of elemental release during the interaction of a single bacterial species ( Burkholderia fungorum) with Columbia River Flood Basalt at T = 28 °C for 36 days. We primarily examined the release of Ca, Mg, P, Si, and Sr under a variety of biotic and abiotic conditions with the aim of evaluating how actively metabolizing bacteria might influence basalt weathering on the continents. Four days after inoculating P-limited reactors (those lacking P in the growth medium), the concentration of viable planktonic cells increased from ∼10 4 to 10 8 CFU (Colony Forming Units)/mL, pH decreased from ∼7 to 4, and glucose decreased from ∼1200 to 0 μmol/L. Mass-balance and acid–base equilibria calculations suggest that the lowered pH resulted from either respired CO 2, organic acids released during biomass synthesis, or H + extrusion during NH 4 + uptake. Between days 4 and 36, cell numbers remained constant at ∼10 8 CFU/mL and pH increased to ∼5. Purely abiotic control reactors as well as control reactors containing inert cells (∼10 8 CFU/mL) showed constant glucose concentrations, thus confirming the absence of biological activity in these experiments. The pH of all control reactors remained near-neutral, except for one experiment where the pH was initially adjusted to 4 but rapidly rose to 7 within 2 days. Over the entire 36 day period, P-limited reactors containing viable bacteria yielded the highest Ca, Mg, Si, and Sr release rates. Release rates inversely correlate with pH, indicating that proton-promoted dissolution was the dominant reaction mechanism. Both biotic and abiotic P-limited reactors displayed low P concentrations. Chemical analyses of bacteria collected at the end of the experiments, combined with mass-balances between the biological and fluid phases, demonstrate that the absence of dissolved P in the biotic reactors resulted from microbial P uptake. The only P source in the basalt is a small amount of apatite (∼1.2%), which occurs as needles within feldspar grains and glass. We therefore conclude that B. fungorum utilized apatite as a P source for biomass synthesis, which stimulated elemental release from coexisting mineral phases via pH lowering. The results of this study suggest that actively metabolizing bacteria have the potential to influence elemental release from basalt in continental settings.