Showing papers on "Goethite published in 2017"

Antimony and arsenic behavior during FE(II)-induced transformation of jarosite

Abstract: Jarosite can be an important scavenger for arsenic (As) and antimony (Sb) in acid mine drainage (AMD) and acid sulfate soil (ASS) environments. When subjected to reducing conditions, jarosite may undergo reductive dissolution, thereby releasing As, Sb, and Fe2+ coincident with a rise in pH. These conditions can also trigger the Fe2+-induced transformation of jarosite to more stable Fe(III) minerals, such as goethite. However, the consequences of this transformation process for As and Sb are yet to be methodically examined. We explore the effects of abiotic Fe2+-induced transformation of jarosite on the mobility, speciation, and partitioning of associated As(V) and Sb(V) under anoxic conditions at pH 7. High concentrations of Fe2+ (10 and 20 mM) rapidly (<10 min) transformed jarosite to a green rust intermediary, prior to the subsequent precipitation of goethite within 24 h. In contrast, lower concentrations of Fe2+ (1 and 5 mM) led to the formation of lepidocrocite. As K-edge XANES spectroscopy revealed s...

Bacillus subtilis biofilm development in the presence of soil clay minerals and iron oxides.

Abstract: Clay minerals and metal oxides, as important parts of the soil matrix, play crucial roles in the development of microbial communities. However, the mechanism underlying such a process, particularly on the formation of soil biofilm, remains poorly understood. Here, we investigated the effects of montmorillonite, kaolinite, and goethite on the biofilm formation of the representative soil bacteria Bacillus subtilis. The bacterial biofilm formation in goethite was found to be impaired in the initial 24 h but burst at 48 h in the liquid-air interface. Confocal laser scanning microscopy showed that the biofilm biomass in goethite was 3-16 times that of the control, montmorillonite, and kaolinite at 48 h. Live/Dead staining showed that cells had the highest death rate of 60% after 4 h of contact with goethite, followed by kaolinite and montmorillonite. Atomic force microscopy showed that the interaction between goethite and bacteria may injure bacterial cells by puncturing cell wall, leading to the swarming of bacteria toward the liquid-air interface. Additionally, the expressions of abrB and sinR, key players in regulating the biofilm formation, were upregulated at 24 h and downregulated at 48 h in goethite, indicating the initial adaptation of the cells to minerals. A model was proposed to describe the effects of goethite on the biofilm formation. Our findings may facilitate a better understanding of the roles of soil clays in biofilm development and the manipulation of bacterial compositions through controlling the biofilm in soils.

Scandium speciation in a world-class lateritic deposit

Abstract: Scandium (Sc) has unique properties, highly valued for many applications. Future supply is expected to rely on unusually high-grade (up to 1000 ppm) lateritic Sc ores discovered in Eastern Australia. To understand the origin of such exceptional concentrations, we investigated Sc speciation in one of these deposits. The major factors are unusually high concentrations in the parent rock together with lateritic weathering over long time scales in a stable tectonic context. At microscopic and atomic scales, by combining X-ray absorption near edge structure spectroscopy, X-ray diffraction and microscopic and chemical analyses, we show that Sc-rich volumes are associated with iron oxides. In particular, Sc adsorbed on goethite accounts for ca 80 % of the Sc budget in our samples. The remaining is incorporated in the crystal structure of hematite, substituting for Fe3+. Scandium grades reflect the high capacity of goethite to adsorb this element. In contrast, the influence of hematite is limited by the low levels of Sc that its structure can incorporate. These crystal-chemical controls play a major role in lateritic Sc deposits developed over ultramafic–mafic rocks.

Adsorption of Selenium and Strontium on Goethite: EXAFS Study and Surface Complexation Modeling of the Ternary Systems.

Abstract: Knowledge of the geochemical behavior of selenium and strontium is critical for the safe disposal of radioactive wastes. Goethite, as one of the most thermodynamically stable and commonly occurring natural iron oxy-hydroxides, promisingly retains these elements. This work comprehensively studies the adsorption of Se(IV) and Sr(II) on goethite. Starting from electrokinetic measurements, the binary and ternary adsorption systems are investigated and systematically compared via batch experiments, EXAFS analysis, and CD-MUSIC modeling. Se(IV) forms bidentate inner-sphere surface complexes, while Sr(II) is assumed to form outer-sphere complexes at low and intermediate pH and inner-sphere complexes at high pH. Instead of a direct interaction between Se(IV) and Sr(II), our results indicate an electrostatically driven mutual enhancement of adsorption. Adsorption of Sr(II) is promoted by an average factor of 5 within the typical groundwater pH range from 6 to 8 for the concentration range studied here. However, the interaction between Se(IV) and Sr(II) at the surface is two-sided, Se(IV) promotes Sr(II) outer-sphere adsorption, but competes for inner-sphere adsorption sites at high pH. The complexity of surfaces is highlighted by the inability of adsorption models to predict isoelectric points without additional constraints.

The Formation of Silicate-Stabilized Passivating Layers on Pyrite for Reduced Acid Rock Drainage

Abstract: Acid and metalliferous release occurring when sulfide (principally pyrite)-containing rock from mining activities and from natural environments is exposed to the elements is acknowledged as a major environmental problem. Acid rock drainage (ARD) management is both challenging and costly for operating and legacy mine sites. Current technological solutions are expensive and focused on treating ARD on release rather than preventing it at source. We describe here a viable, practical mechanism for reduced ARD through the formation of silicate-stabilized iron oxyhydroxide surface layers. Without silicate, oxidized pyrite particles form an overlayer of crystalline goethite or lepidocrocite with porous structure. With silicate addition, a smooth, continuous, coherent and apparently amorphous iron oxyhydroxide surface layer is observed, with consequent pyrite dissolution rates reduced by more than 90% at neutral pH. Silicate is structurally incorporated within this layer and inhibits the phase transformation from ...

The effect of common groundwater anions on the aqueous corrosion of zero-valent iron nanoparticles and associated removal of aqueous copper and zinc

Abstract: This work has investigated the influence of common groundwater anions (Cl-, NO3-, SO42- and HCO3-) on the corrosion behaviour and associated removal of copper (Cu) and zinc (Zn) ions onto nanoscale zero-valent iron particles (nZVI). After 16 week exposure to solutions containing each anion at 10 mM concentrations, nZVI was observed to corrode into different iron (hydr)oxide phases (determined using XRD), depending upon the anion present: HNO3- produced goethite particles; NO3- produced predominantly magnetite/maghemite particles; both SO42- and Cl- produced a mixture of phases, including magnetite/maghemite, lepidocrocite and goethite. For solutions containing the different anions and 0.3 mM concentrations of Cu or Zn, near-total metal removal onto nZVI was recorded in the initial stages of the reaction (e.g. <24 hrs) for all systems tested. However, when Cl- and SO42- were also present significant subsequent desorption was recorded and attributed to the influence of anionic pitting corrosion. In contrast, no Cu or Zn desorption was recorded for batch systems containing NO3-, which was attributed to the enmeshment of Cu or Zn in a mixed-valent iron oxide shell. Results herein therefore demonstrate that NO3- could be utilised alongside nZVI to improve its long-term performance for in situ water treatment applications.

Synthesis of cryptocrystalline magnesite–bentonite clay composite and its application for neutralization and attenuation of inorganic contaminants in acidic and metalliferous mine drainage

Abstract: The primary aim of this study was to synthesize cryptocrystalline magnesite–bentonite clay composite by mechanochemical activation and evaluate its usability as low cost adsorbent for neutralization and attenuation of inorganic contaminants in acidic and metalliferous mine drainage. The composite was synthesized at 1:1 weight to weight ratio. The capacity of the composite to neutralize acidity and remove toxic chemical species from synthetic and field AMD was evaluated at optimized conditions. Interaction of the composite with AMD led to an increase in pH (pH > 11) and lowering of metal concentrations. The removal of chemical species was optimum at 20 min of equilibration and 1 g of dosage. The composite removed ≈99% (Al 3+ , Fe 3+ , and Mn 2+ ) and ≈90% (SO 4 2− ) from raw mine effluent. Adsorption kinetics fitted better to pseudo-second-order kinetic than pseudo-first-order kinetic hence confirming chemisorption. Adsorption data fitted better to Freundlich adsorption isotherm than Langmuir hence confirming multisite adsorption. Gibbs free energy model predicted that the reaction is spontaneous in nature for Al, Fe and sulphate except for Mn. Geochemical model indicated that Fe was removed as Fe(OH) 3 , goethite, and jarosite, Al as basaluminite, boehmite and jurbanite, Al(OH) 3 and as gibbsite and diaspore. Al and Fe precipitated as iron (oxy)-hydroxides and aluminium (oxy)-hydroxides. Mn precipitated as rhodochrosite and manganite. Ca was removed as gypsum. Sulphate was removed as gypsum, and Fe, Al hydroxyl sulphate minerals. Mg was removed as brucite and dolomite. It was concluded that the composite has the potential to neutralize acidity and attenuate potentially toxic chemical species from acidic and metalliferous mine drainage.

Competitive and Cooperative Effects during Nickel Adsorption to Iron Oxides in the Presence of Oxalate

Abstract: Iron oxides are ubiquitous in soils and sediments and play a critical role in the geochemical distribution of trace elements and heavy metals via adsorption and coprecipitation. The presence of organic acids may potentially alter how metals associate with iron oxide minerals through a series of cooperative or competitive processes: solution complexation, ternary surface complexation, and surface site competition. The macroscopic and molecular-scale effects of these processes were investigated for Ni adsorption to hematite and goethite at pH 7 in the presence of oxalate. The addition of this organic acid suppresses Ni uptake on both minerals. Aqueous speciation suggests that this is dominantly the result of oxalate complexing and solubilizing Ni. Comparison of the Ni surface coverage to the concentration of free (uncomplexed) Ni2+ in solution suggests that the oxalate also alters Ni adsorption affinity. EXAFS and ATR-FTIR spectroscopies indicate that these changes in binding affinity are due to the formati...

Trace Uranium Partitioning in a Multiphase Nano-FeOOH System

Abstract: The characterization of trace elements in minerals using extended X-ray absorption fine structure (EXAFS) spectroscopy constitutes a first step toward understanding how impurities and contaminants interact with the host phase and the environment. However, limitations to EXAFS interpretation complicate the analysis of trace concentrations of impurities that are distributed across multiple phases in a heterogeneous system. Ab initio molecular dynamics (AIMD)-informed EXAFS analysis was employed to investigate the immobilization of trace uranium associated with nanophase iron (oxyhydr)oxides, a model system for the geochemical sequestration of radiotoxic actinides. The reductive transformation of ferrihydrite [Fe(OH)3] to nanoparticulate iron oxyhydroxide minerals in the presence of uranyl (UO2)2+(aq) resulted in the preferential incorporation of U into goethite (α-FeOOH) over lepidocrocite (γ-FeOOH), even though reaction conditions favored the formation of excess lepidocrocite. This unexpected result is sup...

Solid Phase Speciation and Solubility of Vanadium in Highly Weathered Soils

Abstract: Vanadium (V) is increasingly recognized both as a medical trace element with essential biological functions and as a potentially toxic environmental pollutant, yet the current knowledge on V speciation in soils is limited. Here, we investigated the chemical speciation and extractability of V in highly weathered tropical soils, which are often rich in V compared to soils of temperate climatic regions. Vanadium K-edge X-ray absorption near edge structure (XANES) spectra of soil samples, along with a range of reference compounds differing in V-oxidation state and coordination chemistry, revealed the predominance of V4+/5+ in a primarily octahedral or tetrahedral coordination. The soil spectra were best fitted with linear combinations of reference spectra of V4+ in the structure of kaolinite, V5+ adsorbed to kaolinite, and other V5+-sorbed solids. Vanadate adsorbed to goethite, ferrihydrite, gibbsite, and/or Fe(III)–natural organic matter complexes and V4+ in the structure of goethite may be present, but cann...

Colloidal behavior of goethite nanoparticles modified with humic acid and implications for aquifer reclamation

Abstract: Nanosized colloids of iron oxide adsorb heavy metals, enhance the biodegradation of contaminants, and represent a promising technology to clean up contaminated aquifers. Goethite particles for aquifer reclamation were recently synthesized with a coating of humic acids to reduce aggregation. This study investigates the stability and the mobility in porous media of this material as a function of aqueous chemistry, and it identifies the best practices to maximize the efficacy of the related remediation. Humic acid-coated nanogoethite (hydrodynamic diameter ∼90 nm) displays high stability in solutions of NaCl, consistent with effective electrosteric stabilization. However, particle aggregation is fast when calcium is present and, to a lesser extent, also in the presence of magnesium. This result is rationalized with complexation phenomena related to the interaction of divalent cations with humic acid, inducing rapid flocculation and sedimentation of the suspensions. The calcium dose, i.e., the amount of calcium ions with respect to solids in the dispersion, is the parameter governing stability. Therefore, more concentrated slurries may be more stable and mobile in the subsurface than dispersions of low particle concentration. Particle concentration during field injection should be thus chosen based on concentration and proportion of divalent cations in groundwater.

Oxidation of a Dimethoxyhydroquinone by Ferrihydrite and Goethite Nanoparticles: Iron Reduction versus Surface Catalysis

Abstract: Hydroquinones are important mediators of electron transfer reactions in soils with a capability to reduce Fe(III) minerals and molecular oxygen, and thereby generating Fenton chemistry reagents. This study focused on 2,6-dimethoxy hydroquinone (2,6-DMHQ), an analogue to a common fungal metabolite, and its reaction with ferrihydrite and goethite under variable pH and oxygen concentrations. Combined wet-chemical and spectroscopic analyses showed that both minerals effectively oxidized 2,6-DMHQ in the presence of oxygen. Under anaerobic conditions the first-order oxidation rate constants decreased by one to several orders of magnitude depending on pH and mineral. Comparison between aerobic and anaerobic results showed that ferrihydrite promoted 2,6-DMHQ oxidation both via reductive dissolution and heterogeneous catalysis while goethite mainly caused catalytic oxidation. These results were in agreement with changes in the reduction potential (EH) of the Fe(III) oxide/Fe(II)aq redox couple as a function of dissolved Fe(II) where EH of goethite was lower than ferrihydrite at any given Fe(II) concentration, which makes ferrihydrite more prone to reductive dissolution by the 2,6-DMBQ/2,6-DMHQ redox couple. This study showed that reactions between hydroquinones and iron oxides could produce favorable conditions for formation of reactive oxygen species, which are required for nonenzymatic Fenton-based decomposition of soil organic matter.