Assessing the propensity of landfill soils to undergo reductive iron dissolution

Naturally occurring iron from soil and aquifer sediments at waste disposal sites often becomes liberated into groundwater as a result of reductive dissolution. Research was conducted to evaluate an appropriate procedure for assessing a soil’s propensity to undergo iron reductive dissolution. Soil samples collected from waste disposal sites in Florida were characterized by pH, organic carbon content, total iron content, amorphous iron content, citrate-dithionite-bicarbonate extractable iron, and qualitative X-ray diffraction analysis, followed by a series of extraction tests designed to simulate the reductive dissolution process. Over a 30-day period, biological reducing tests released 13–260 mg/kg Fe(II) from soils, and a chemical reducing test released 2.2–178 mg/kg Fe(II) from soils. Soil amorphous iron content was shown to be the most effective parameter for assessment of iron reductive dissolution potential through standard soil characterization. These results suggest that biological reducing tests may be helpful for assessing long-term soil iron reductive dissolution potential, and that soil amorphous iron content provides a good indication of the potential for a soil to undergo reductive dissolution at a landfill site.     

The effect of oxalate on the dissolution rates of oligoclase and tremolite

The effect of oxalate, a strong chelator for Al and other cations, on the dissolution rates of oligoclase feldspar and tremolite amphibole was investigated in a flow-through reactor at 22°C. Oxalate at concentrations of 0.5 and 1 mM has essentially no effect on the dissolution rate of tremolite, nor on the steady-state rate of release of Si from oligoclase. The fact that oxalate has no effect on dissolution rate suggests that detachment of Si rather than Al or Mg is the rate-limiting step. At pH 4 and 9, oxalate has no effect on the steady-state rate of release of Al, and dissolution is congruent. At pH 5 and 7, oligoclase dissolution is congruent in the presence of oxalate, but in the absence of oxalate Al is preferentially retained in the solid relative to Si.Large transient “spikes” of Al or Si are observed when oxalate is added to or removed from the system. The cause of the spikes is unknown; we suggest adsorption on feldspar surfaces away from sites of active dissolution as a possibility. Solutions in the reactors are undersaturated with respect to both gibbsite and kaolinite, so neither the spikes nor the incongruent dissolution can be explained by formation of a secondary precipitate.The rate of dissolution of tremolite is independent of pH over the pH range 2–5, and decreases at higher pH. The rate of dissolution of oligoclase in our experiments was independent of pH over the pH range 4–9. Since the dissolution rate of these minerals is independent of pH and organic ligand concentration, the effect of acid deposition from the atmosphere on the rate of supply of cations from weathering of granitic rocks should be minor.     

Electronic structures of iron(III) and manganese(IV) (hydr)oxide minerals: Thermodynamics of photochemical reductive dissolution in aquatic environments

Sunlight-induced reduction and dissolution of colloidal Fe-Mn (hydr)oxide minerals yields elevated concentrations of Fe²⁺ and Mn²⁺ in natural waters. Since these elements may be biolimiting micronutrients, photochemical reactions might play a significant role in biogeochemical cycles. Reductive photodissolution of Fe (hydr)oxide minerals may also release sorbed metals. The reactivity of Fe-Mn (hydr)oxide minerals to sunlight-induced photochemical dissolution is determined by the electronic structure of the mineral-water interface. In this work, oxygen K-edge absorption and emission spectra were used to determine the electronic structures of iron(III) (hydr)oxides (hematite, goethite, lepidocrocite, akaganeite and schwertmannite) and manganese(IV) oxides (pyrolusite, birnessite, cryptomelane). The band gaps in the iron(III) (hydr)oxide minerals are near 2.0-2.5 eV; the band gaps in the manganese (IV) oxide phases are 1.0-1.8 eV. Using published values for the electrochemical flat-band potential for hematite together with experimental pH_pzc values for the (hydr)oxides, it is possible to predict the electrochemical potentials of the conduction and valence bands in aqueous solutions as a function of pH. The band potentials enable semiquantitative predictions of the susceptibilities of these minerals to photochemical dissolution in aqueous solutions. At pH 2 (e.g., acid-mine waters), photoreduction of iron(III) (hydr)oxides could yield millimolal concentrations of aqueous Fe²⁺ (assuming surface detachment of Fe²⁺ is not rate limiting). In seawater (pH 8.3), however, the direct photo-reduction of colloidal iron(III) (hydr)oxides to give nanomolal concentrations of dissolved, uncomplexed, Fe²⁺ is not thermodynamically feasible. This supports the hypothesis that the apparent photodissolution of iron(III) (hydr)oxides in marines systems results from Fe³⁺ reduction by photochemically produced superoxide. In contrast, the direct photoreduction of manganese oxides should be energetically feasible at pH 2 and 8.3.     

Siderophore-promoted dissolution of cobalt from hydroxide minerals

Recent research has revealed that siderophores, a class of biogenic ligands with high affinities for Fe(III), can also strongly complex Co(III), an element essential to the normal metabolic function of microbes and animals. This study was conducted to quantify the rates and identify the products and mechanisms of the siderophore-promoted dissolution of Co from synthetic Co-bearing minerals. The dissolution reactions of heterogenite (CoOOH) and four Co-substituted goethites (Co-FeOOH) containing different Co concentrations were investigated in the presence of a trihydroxamate siderophore, desferrioxamine B (DFOB), using batch and flow-through experiments. Results showed that DFOB-promoted dissolution of Co from Co-bearing minerals may occur via pH-dependent ligand-promoted or reductive dissolution mechanisms. For heterogenite, ligand-promoted dissolution was the dominant pathway at neutral to alkaline pH, while production of dissolved Co(II) for pH <6. It was not possible from our data to decouple the separate contributions of homogenous and heterogeneous reduction reactions to the aqueous Co(II) pool. Cobalt substitution in Co-substituted goethite, possibly caused by distortion of goethite structure and increased lattice strain, resulted in enhanced total dissolution rates of both Co and Fe. The DFOB-promoted dissolution rates of Co-bearing minerals, coupled with the high affinity of Co(III) for DFOB, suggest that siderophores may be effective for increasing Co solubility, and thus possibly Co bioavailability. The results also suggest that siderophores may contribute to the mobilization of radioactive ⁶⁰Co from Co-bearing mineral phases through mineral weathering and dissolution processes.     

Kinetics of brucite dissolution at 25°C in the presence of organic and inorganic ligands and divalent metals

Brucite (Mg(OH)₂) dissolution rate was measured at 25°C in a mixed-flow reactor at various pH (5 to 11) and ionic strengths (0.01 to 0.03 M) as a function of the concentration of 15 organic and 5 inorganic ligands and 8 divalent metals. At neutral and weakly alkaline pH, the dissolution is promoted by the addition of the following ligands ranked by decreasing effectiveness: EDTA ≥ H₂PO₄⁻ > catechol ≥ HCO₃⁻ > ascorbate > citrate > oxalate > acetate ∼ lactate and it is inhibited by boric acid. At pH >10.5, it decreases in the presence of PO₄³⁻, CO₃²⁻, F⁻, oxine, salicylate, lactate, acetate, 4-hydroxybenzoate, SO₄²⁻ and B(OH)₄⁻ with orthophosphate and borate being the strongest and the weakest inhibitor, respectively. Xylose (up to 0.1 M), glycine (up to 0.05 M), formate (up to 0.3 M) and fulvic and humic acids (up to 40 mg/L DOC) have no effect on brucite dissolution kinetics. Fluorine inhibits dissolution both in neutral and alkaline solutions. From F sorption experiments in batch and flow-through reactors and the analysis of reacted surfaces using X-ray Photoelectron Spectroscopy (XPS), it is shown that fluorine adsorption is followed by its incorporation in brucite lattice likely via isomorphic substitution with OH. The effect of eight divalent metals (Sr, Ba, Ca, Pb, Mn, Fe, Co and Ni) studied at pH 4.9 and 0.01 M concentration revealed brucite dissolution rates to be correlated with the water molecule exchange rates in the first hydration sphere of the corresponding cation.The effect of investigated ligands on brucite dissolution rate can be modelled within the framework of the surface coordination approach taking into account the adsorption of ligands on dissolution-active sites and the molecular structure of the surface complexes they form. The higher the value of the ligand sorption constant, the stronger will be its catalyzing or inhibiting effect. As for Fe and Al oxides, bi- or multidentate mononuclear surface complexes, that labilize Mg-O bonds and water coordination to Mg atoms at the surface, enhance brucite dissolution whereas bi- or polynuclear surface complexes tend to inhibit dissolution by bridging two or more metal centers and extending the cross-linking at the solid surface. Overall, results of this study demonstrate that very high concentrations of organic ligands (0.01-0.1 M) are necessary to enhance or inhibit brucite dissolution. As a result, the effect of extracellular organic products on the weathering rate of Mg-bearing minerals is expected to be weak.     

Selective chemical extraction of Cu from selected mineral and soil samples: enhancement of Cu geochemical anomalies in Southern Portugal

The study described herein concerns the application of selective chemical extractions on metal-bearing minerals and soils to geochemical exploration. Specifically, the study aims at the detection of anomalous soils in the vicinity of two mineralized zones in Southern Portugal.A kinetic study of the selectivity of partial chemical extractions applied to Cu minerals has been carried out in order to establish a systematic procedure (reagents, extraction plateau, etc.) which could be recommended for soils of the two study zones. It is shown that: (1) NH₄ acetate dissolves malachite, azurite and cuprite completely and chrysocolla, conicalcite and atacamite only partially; (2) hydroxylamine hydrochloride dissolves chrysocolla and conicalcite only partially; (3) H₂O₂ dissolves chalcopyrite only partially; (4) NH₄ oxalate (U.V.) dissolves conicalcite and atacamite only partially; (5) mixed-acid attack dissolves residual chalcopyrite, chrysocolla, atacamite and conicalcite.A total of 740 soil samples were collected from the Salgadinho and Tinoca areas. The Cu mineralization in the Salgadinho area is situated in an Upper-Devonian Volcanic-Siliceous Complex. The weathering products of the mineralization are mainly amorphous iron oxides, goethite and hematite. The Cu mineralization in Tinoca area is located in the Arronches-Campo Maior belt, where stratiform Cu mineralization is found. The weathering products of the mineralization are mainly malachite, amorphous iron oxides, goethite and hematite.In order to identify the Cu-bearing phases and the extraction plateau, the −80 mesh fraction of two soil samples was submitted to an extraction procedure using the following reagents in sequence: NH₄ acetate, hydroxylamine hydrochloride, NH₄ oxalate (dark), NH₄ oxalate (U.V.) and finally strong acids.In soils from the Salgadinho and Tinoca areas, the use of NH₄ oxalate (U.V.) in single dissolution which would incorporate those phases dissolved by NH₄ acetate and NH₄ oxalate (dark), gives the broadest anomalous surface and higher contrast for Cu than acid digestion. The analysis of NH₄ oxalate (U.V.) extractions, instead of acid digestion, can thus be recommended for both areas.     

Siderophore adsorption to and dissolution of kaolinite at pH 3 to 7 and 22°C

Siderophores are Fe(III)-specific ligands produced by many aerobic microorganisms under conditions of iron stress. This study examined adsorption of the commercial trihydroxamate siderophore, desferrioxamine B (DFO-B), to an iron-containing kaolinite (0.1 bulk wt.% Fe) and examined DFO-B effects on initial kaolinite dissolution and iron release rates. Adsorption experiments were conducted at pH 3 to 8 in 0.01-M NaClO₄ in the dark and at 22°C; batch initial dissolution experiments were conducted to 96 h.The adsorption envelope (i.e., adsorption as a function of pH) of DFO-B on kaolinite was consistent with cation-like behavior, with adsorption increasing above kaolinite’s pH_pznpc of 4.9. DFO-B enhanced aluminum release from kaolinite at pH 3 to 7, relative to HNO₃, which is consistent with the ligand’s high binding affinity for Al. Correlation between DFO-B adsorption and aluminum release suggested a surface-controlled, ligand-promoted dissolution mechanism. DFO-B had no effect relative to HNO₃ on silicon release at pH 3 and 5, but moderately enhanced silicon release at pH 7. DFO-B enhanced iron release from kaolinite, with dissolved iron concentrations in the 10-ppb range at 96-h reaction time. These results show that kaolinite may serve as a source of iron to aerobic microorganisms in iron-limited conditions and that siderophores may affect kaolinite dissolution and iron content.     

矿物流体包裹体中的羧酸

矿物流体包裹体中的羧酸曾贻善刘家齐（北京大学地质系，北京１００８７１）（地矿部宜昌地质矿产研究所，宜昌４４３００３）关键词矿物包裹体浸取液羧酸离子色谱分析分子中含有羧基官能团（—ＣＯＯＨ）的物质称为羧酸。Ｆｅｉｎ［１］和Ｓｈｏｃｋ［２］曾概述羧酸在自...     

The effects of organic acids on the dissolution of silicate minerals: A case study of oxalate catalysis of kaolinite dissolution

Most studies agree that the dissolution rate of aluminosilicates in the presence of oxalic and other simple carboxylic acids is faster than the rate with non-organic acid under the same pH. However, the mechanisms by which organic ligands enhance the dissolution of minerals are in debate. The main goal of this paper was to study the mechanism that controls the dissolution rate of kaolinite in the presence of oxalate under far from equilibrium conditions (−29 < ΔG_r < −18 kcal mol⁻¹). Two types of experiments were performed: non-stirred flow-through dissolution experiments and batch type adsorption isotherms. All the experiments were conducted at pH 2.5-3.5 in a thermostatic water-bath held at a constant temperature of 25.0, 50.0 or 70.0 ± 0.1 °C. Kaolinite dissolution rates were obtained based on the release of silicon and aluminum at steady state. The results show good agreement between these two estimates of kaolinite dissolution rate. At constant temperature, there is a general trend of increase in the overall dissolution rate as a function of the total concentration of oxalate in solution. The overall kaolinite dissolution rates in the presence of oxalate was up to 30 times faster than the dissolution rate of kaolinite at the same temperature and pH without oxalate as was observed in our previous study. Therefore, these rate differences are related to differences in oxalate and aluminum concentrations. Within the experimental variability, the oxalate adsorption at 25, 50, and 70 °C showed the same dependence on the sum of the activities of oxalate and bioxalate in solution. The change of oxalate concentration on the kaolinite surface (C_s,ox) as a function of the sum of the activities of the oxalate and bioxalate in solution may be described by the general adsorption isotherm:

     

Kinetics and mechanisms of kaolinite dissolution: effects of organic ligands

The effect of protons, low molecular weight organic ligands, soil humic acid (HA), and stream water dissolved organic matter (DOM) on the rate of dissolution of kaolinite was examined. In acid solution (no ligands present) the rate of dissolution increased with increasing [H⁺] and the rate of Si dissolution was generally faster than Al. Low molecular weight organic ligands markedly increased the dissolution rates of both Al and Si in the following order: oxalate > malonate ≈ salicylate > o-phthalate. In the presence of organic ligands, the rate of Al dissolution was generally much greater than Si. Soil HA and stream water DOM did not promote the dissolution of kaolinite under the experimental conditions examined in this study.

The dissolution kinetics of Al were interpreted in terms of a surface complexation model and the rate equations described in terms of the concentrations of specific (i.e. inner sphere) surface complexes.     

The chemical composition of specular hematite from Tilkerode, Harz, Germany: implications for the genesis of hydrothermal hematite and comparison with the Quadrilátero Ferrífero of Minas Gerais, Brazil

The black shale-hosted selenide vein-type deposit at Tilkerode, eastern Harz, Germany, has specular hematite enclosed in clausthalite (PbSe). The specular hematite has Ti and V in amounts of up to ～1 wt.% TiO₂ and ～3 wt.% V₂O₅, and subordinate, but important, contents of Mo (22–372 ppm) and B (up to 68 ppm). The Tilkerode hematite serves as a reference for hydrothermal hematite formed at relatively low temperatures (<150 °C). The composition of the Tilkerode hematite is compared with that of two generations of specular hematite from itabirite-hosted iron-ore deposits in the Quadrilátero Ferrífero of Minas Gerais, Brazil. The first generation of specular hematite represents an early tectonic hematitisation of dolomitic itabirite at Águas Claras and occurs as fine-grained crystals. Reconnaissance data indicate that the Águas Claras hematite is poorer in Ti and V, relative to the Tilkerode hematite, but has ～5–10 ppm B and ～7–11 ppm Li. The second generation of specular hematite defines the pervasive tectonic foliation of the Gongo Soco iron ore. This hematite has Ti contents of up to ～2 wt.% TiO₂ and subordinate amounts of V (62–367 ppm); its B and Li concentrations are mostly below <2 ppm B and <1 ppm Li. The presence of Ti and B in the Tilkerode hematite can be explained by highly saline, B-bearing fluids that were capable of mobilising otherwise immobile Ti. The Mo signature of the Tilkerode hematite suggests that Mo was derived from the host black shale. In Minas Gerais, B and Li were incorporated into the early tectonic hematite from saline fluids at relatively low temperatures (Águas Claras) and then released during metamorphic hematite growth at higher temperatures, as suggested by the foliation-defining hematite without B–Li signature (Gongo Soco).     

Fe isotopic fractionation during mineral dissolution with and without bacteria

Fe released into solution is isotopically lighter (enriched in the lighter isotope) than hornblende starting material when dissolution occurs in the presence of the siderophore desferrioxamine mesylate (DFAM). In contrast, Fe released from goethite dissolving in the presence of DFAM is isotopically unchanged. Furthermore, Δ⁵⁶Fe_{solution-hornblende} for Fe released to solution in the presence of ligands varies with the affinity of the ligand for Fe. The extent of isotopic fractionation of Fe released from hornblende also increases when experiments are agitated continuously. The Fe isotope fractionation observed during hornblende dissolution with organic ligands is attributed predominantly to retention of ⁵⁶Fe in an altered surface layer, while the lack of isotopic fractionation during goethite dissolution in DFAM is consistent with the lack of an altered layer. When a siderophore-producing soil bacterium is added to the system (without added organic ligands), Fe released to solution from both hornblende and goethite differs isotopically from Fe in the bulk mineral: Δ⁵⁶Fe_{solution-starting material} = −0.56 ± 0.19 (hornblende) and −1.44 ± 0.16 (goethite). Increased isotopic fractionation is attributed in this case to the fact that as bacterial respiration depletes the system in oxygen and aqueous Fe is reduced, equilibration between aqueous ferrous and ferric iron creates a pool of isotopically heavy ferric iron that is assimilated by bacterial cells. Adsorption of isotopically heavy ferrous iron (Fe(II) enriched in the heavier isotope) or precipitation of isotopically heavy Fe minerals may also contribute to observed fractionations.To test whether these Fe isotope signatures are recorded in natural systems, we also investigated extractions of samples of soils from which the bacteria were isolated. These extractions show variability in the isotopic signatures of exchangeable Fe and Fe oxyhydroxide fractions from one soil sample to another, but exchangeable Fe is observed to be lighter than Fe in soil Fe oxyhydroxides and hornblende. This observation is consistent with isotopically light Fe-organic complexes in soil pore water derived from the Fe-silicate starting materials in the presence of growing microorganisms, as documented in experiments reported here. The contributions from phenomena including organic ligand-promoted nonstoichiometric dissolution of Fe silicates, uptake of ferric iron by organisms, adsorption of isotopically heavy ferrous iron, and precipitation of iron minerals should create complex isotopic signatures in soils. Better understanding of these processes and the timescales over which they contribute to fractionation is needed.     

Hydrochemical characteristics of shallow groundwater in aquifer containing uranyl phosphate minerals, in the Köprübaşı (Manisa) area, Turkey

The concentrations of uranium, iron and the major constituents were determined in groundwater samples from aquifer containing uranyl phosphate minerals (meta-autunite, meta-torbernite and torbernite) in the Köprüba?? area. Groundwater samples from wells located at shallow depths (0.5–6 m) show usually near neutral pH values (6.2–7.1) and oxidizing conditions (Eh = 119–275 mV). Electrical conductivity (EC) values of samples are between 87 and 329 μS/cm^?1. They are mostly characterized by mixed cationic Ca dominating bicarbonate types. The main hydrogeochemical process is weathering of the silicates in the shallow groundwater system. All groundwater in the study area are considered undersaturated with respect to torbernite and autunite. PHREEQC predicted UO₂(HPO₄) ₂ ^2? as the unique species. The excellent positive correlation coefficient (r = 0.99) between U and PO₄ indicates the dissolved uranium in groundwater would be associated with the dissolution of uranyl phosphate minerals. The groundwater show U content in the range 1.71–70.45 μg/l but they are mostly lower than US EPA (2003) maximum contaminant level of 30 μg/l. This low U concentrations in oxic groundwater samples is attributed to the low solubility of U(VI) phosphate minerals under near neutral pH and low bicarbonate conditions. Iron closely associated with studied sediments, were also detected in groundwater. The maximum concentration of Fe in groundwater samples was 2837 μg/l, while the drinking water guidelines of Turkish (TSE 1997) and US EPA (2003) were suggested 200 and 300 μg/l, respectively. Furthermore, iron and uranium showed a significant correlation to each other with a correlation coefficient (r) of 0.94. This high correlation is probably related to the iron-rich sediments which contain also significant amounts of uranium mineralization. In addition to pH and bicarbonate controlling dissolution of uranyl phosphates, association of uranyl phosphates with iron (hydr) oxides seems to play important role in the amount of dissolved U in shallow groundwater.     

The behavior of arsenic and antimony at Pezinok mining site,southwestern part of the Slovak Republic

Arsenic and antimony contamination is found at the Pezinok mining site in the southwest of the Slovak Republic. Investigation of this site included sampling and analysis of water, mineralogical analyses, sequential extraction, in addition to flow and geochemical modeling. The highest dissolved arsenic concentrations correspond to mine tailings (up to 90,000 μg/L) and the arsenic is present predominately as As(V). The primary source of the arsenic is the dissolution of arsenopyrite. Concentration of antimony reaches 7,500 μg/L and its primary source is the dissolution of stibnite. Pore water in mine tailings is well-buffered by the dissolution of carbonates (pH values between 6.6 and 7.0) and arsenopyrite grains are surrounded by reaction rims composed of ferric iron minerals. Based on sequential extraction results, most solid phase arsenic is in the reducible fraction (i.e. ferric oxyhydroxides), sulfidic fraction, and residual fraction. Distribution of antimony in the solid phase is similar, but contents are lower. The principal attenuation mechanism for As(V) is adsorption to ferric oxide and hydroxides, but the adsorption seems to be limited by the competition with Sb(V) produced by the oxidation of stibnite for adsorption sites. Water in mine tailings is at equilibrium with gypsum and calcite, but far from equilibrium with any arsenic and antimony minerals. The concentrations of arsenic and antimony in the surrounding aquifer are much lower, with maximum values of 215 and 426 μg/L, respectively. Arsenic and antimony are transported by ground water flow towards the Blatina Creek, but their loading from ground water to the creek is much lower compared with the input from the mine adits. In the Blatina Creek, arsenic and antimony are attenuated by dilution and by adsorption on ferric iron minerals in stream sediments with resulting respective concentrations of 93 and 45 μg/L at the site boundary south of mine tailing ponds.     

Kurnakovite deposits on the Qinghai-Tibet Plateau (II): an investigation from chemical kinetics of chloropinnoite dissolution

Lakes on the Qinghai-Tibet Plateau (QTP) are of particular interest to researchers because of their unusual high concentrations of lithium (Li), boron (B), and potassium (K). Kurnakovite, a member of the inderite group, is well-distributed on the QTP, however, the geochemical mechanisms of kurnakovite transformation requires further identification and clarification. This study aims to elucidate the geochemical mechanisms of kurnakovite deposits on the QTP from chloropinnoite dissolution using chemical kinetic and spectroscopic techniques. The new borate, chloropinnoite 2MgO · 2B₂O₃ · MgCl₂ · 14H₂O, was obtained from the natural concentrated salt lake brine on the QTP. The kinetics of chloropinnoite dissolved in 4.5 % (wt%) boric acid solution at 303, 313, and 323 K were investigated. The characterization of the phase transitions and the kinetics were carried out by chemical titration analysis, X-ray powder diffraction spectrometry, Fourier Transform Infrared (FT-IR), and Raman spectrometry. The results demonstrate that similar kinetic processes occur at all three temperatures and can be divided into dissolution, supersaturation, and precipitation, according to three distinct kinetic curves. Kurnakovite was the final phase transition (terminal secondary mineral) within the chloropinnoite-boric acid solution. The dissolution rate of chloropinnoite (the dissolution stage) could be described by second order pseudo-homogeneous reaction model. According to the spectroscopy data, geochemical mechanism of kurnakovite was identified. The new geochemical hypothesis well explains the geochemical mechanism of kurnakovite minerals on the QTP.     

Mechanism and kinetics of hydrothermal replacement of magnetite by hematite

The replacement of magnetite by hematite was studied through a series of experiments under mild hydrothermal conditions(140 -220℃, vapour saturated pressures) to quantify the kinetics of the transformation and the relative effects of redox and non-redox processes on the transformation. The results indicate that oxygen is not an essential factor in the replacement reaction of magnetite by hematite, but the addition of excess oxidant does trigger the oxidation reaction, and increases the kinetics of the transformation. However, even under high O_2(aq) environments, some of the replacement still occurred via Fe²⁺ leaching from magnetite. The kinetics of the replacement reaction depends upon temperature and solution parameters such as pH and the concentrations of ligands, all of which are factors that control the solubility of magnetite and affect the transport of Fe²⁺ (and the oxidant) to and from the reaction front. Reaction rates are fast at ~200℃, and in nature transport properties of Fe and,in the case of the redox-controlled replacement, the oxidant will be the rate-limiting control on the reaction progress. Using an Avrami treatment of the kinetic data and the Arrhenius equation, the activation energy for the transformation under non-redox conditions was calculated to be 26 ± 6 kJ mol^-1.This value is in agreement with the reported activation energy for the dissolution of magnetite, which is the rate-limiting process for the transformation under non-redox conditions.     

Onboard experiment investigating metal leaching of fresh hydrothermal sulfide cores into seawater

We observed the initial release rate of metals from four fresh (i.e., without long time exposure to the atmosphere) hydrothermal sulfide cores into artificial seawater. The sulfide samples were collected by seafloor drilling from the Okinawa Trough by D/V Chikyu, powdered under inert gas, and immediately subjected to onboard metal-leaching experiments at different temperatures (5 °C and 20 °C), and under different redox conditions (oxic and anoxic), for 1–30 h. Zinc and Pb were preferentially released from sulfide samples containing various metals (i.e., Mn, Fe, Cu, Zn, Cd, and Pb) into seawater. Under oxic experimental conditions, Zn and Pb dissolution rates from two sulfide samples composed mainly of iron disulfide minerals (pyrite and marcasite) were higher than those from two other sulfide samples with abundant sphalerite, galena, and/or silicate minerals. Scanning electron microscopy confirmed that the high metal-releasing sample contained several galvanic couples of iron disulfide with other sulfide minerals, whereas the low metal-releasing sample contained fewer galvanic couples or were coated by a silicate mineral. The experiments overall confirmed that the galvanic effects with iron disulfide minerals greatly induce the initial release of Zn and Pb from hydrothermal sulfides into seawater, especially under warm oxic conditions.     

Evaluation of mineral substrates for in situ iron removal from groundwater

Calcium carbonate-based materials (CCBM) have been found to remove Fe(II) and other divalent metal cations from aqueous solution and thus have the potential for incorporation into remediation systems to remove Fe(II) from groundwater at landfills. Research was conducted to examine the ability of a range of CCBM to remove Fe(II) and assess the mechanism of removal. Different CCBM (limestone, concrete, dolomite, marble), as well as gypsum, witherite, and quartz sand, were tested for their ability to remove Fe(II) from water using batch tests conducted under anaerobic conditions. Limestone (specific surface area of approximately 0.46 m²/g) was found to have the best removal effectiveness, and the final Fe(II) concentration was reduced from 50 to <0.01 mg/L. Kinetics experiments conducted over a 72 h period indicated that the removal process of Fe(II) by CCBM was a two-step process. The first step is rapid sorption of Fe(II) onto the CCBM surfaces within the first hour, and the second step is relatively slow co-precipitation of iron-containing solids formed through various chemical reactions. The two best performing CCBM (limestone and concrete) were evaluated for their removal ability based on media particle size (diameters of 3–5, 7–10, 15–25, and 40–50 mm) and revealed statistically significant (p < 0.01) increases in Fe(II) removal for each particle size class examined. SEM analysis of reacted materials revealed visible precipitates on the reactive material surface; XRD analysis was not able to detect crystalline Fe minerals on limestone surface.     

Experimental and numerical simulation study of the mineral sequestration mechanism of the Shiqianfeng saline aquifers in the Ordos Basin,Northwest China

This study focused on typical injection layers of deep saline aquifers in the Shiqianfeng Formation used in the Carbon Capture and Sequestration Demonstration Projects in the Ordos Basin, Northwest China. The study employed experiments and numerical simulations to investigate the mechanism of CO₂ mineral sequestration in these deep saline aquifers. The experimental results showed that the dissolved minerals are plagioclase, hematite, illite–smectite mixed layer clay and illite, whereas the precipitated minerals are quartz (at 55, and 70 °C) and kaolinite (at 70 °C). There are rare carbonate mineral precipitations at the experimental time scale, while the precipitation of quartz as a product of the dissolution of silicate minerals and some intermediate minerals rich in K and Mg that transform to clay minerals, reveals the possibility of carbonate precipitation at the longer time scale. These results are consistent with some results previously reported in the literature. We calibrated the kinetic parameters of mineral dissolution and precipitation by these experimental results and then simulated the CO₂ mineral sequestration under deep saline aquifer conditions. The simulation results showed that the dissolved minerals are albite, anorthite and minor hematite, whereas the precipitated minerals are calcite, kaolinite and smectite at 55 and 70 °C. The geochemical reaction of illite is more complex. At 55 °C, illite is dissolved at the relatively lag time and transformed to dawsonite; at 70 °C, illite is precipitated in the early reaction period and then transformed to kaolinite. Based on this research, sequestrated CO₂ minerals, which are mainly related to the temperature of deep saline aquifers in Shiqianfeng Fm., are calcite and dawsonite at lower temperature, and calcite at higher temperature. The simulation results also establish that calcite could precipitate over a time scale of thousands of years, and the higher the temperature the sooner such a process would occur due to increased reaction rates. These characteristics are conducive, not only to the earlier occurrence of mineral sequestration, but also increase the sequestration capacity of the same mineral components. For a sequestration period of 10,000 years, we determined that the mineral sequestration capacity is 0.786 kg/m³ at 55 °C, and 2.180 kg/m³ at 70 °C. Furthermore, the occurrence of mineral sequestration indirectly increases the solubility of CO₂ in the early reaction period, but this decreases with the increase in temperature.