Showing papers on "Goethite published in 2010"

Redox Transformation of Arsenic by Fe(II)-Activated Goethite (α-FeOOH)

Abstract: The redox state and speciation of the metalloid arsenic (As) determine its environmental fate and toxicity. Knowledge about biogeochemical processes influencing arsenic redox state is therefore necessary to understand and predict its environmental behavior. Here we quantified arsenic redox changes by pH-neutral goethite [alpha-Fe(III)OOH] mineral suspensions amended with Fe(II) using wet-chemical and synchrotron X-ray absorption (XANES) analysis. Goethite itself did not oxidize As(III) and, in contrast to thermodynamic predictions, Fe(II)-goethite systems did not reduce As(V). However, we observed rapid oxidation of As(III) to As(V) in Fe(II)-goethite systems. Mossbauer spectroscopy showed initial formation of (57)Fe-goethite after (57)Fe(II) addition plus a so far unidentified additional Fe(II) phase. No other Fe(III) phase could be detected by Mossbauer, EXAFS, SEM, XRD, or HR-TEM. This suggests that reactive Fe(III) species form as an intermediate Fe(III) phase upon Fe(II) addition and electron transfer into bulk goethite but before crystallization of the newly formed Fe(III) as goethite. In summary this study indicates that in the simultaneous presence of Fe(III) oxyhydroxides and Fe(II), as commonly observed in environments inhabited by iron-reducing microorganisms, As(III) oxidation can occur. This potentially explains the presence of As(V) in reduced groundwater aquifers.

Identification of iron-reducing microorganisms in anoxic rice paddy soil by 13C-acetate probing

Abstract: In anoxic rice field soil, ferric iron reduction is one of the most important terminal electron accepting processes, yet little is known about the identity of iron-reducing microorganisms. Here, we identified acetate-metabolizing bacteria by RNA-based stable isotope probing in the presence of iron(III) oxides as electron acceptors. After reduction of endogenous iron(III) for 21 days, isotope probing with (13)C-labeled acetate (2 mM) and added ferric iron oxides (ferrihydrite or goethite) was performed in rice field soil slurries for 48 and 72 h. Ferrihydrite reduction coincided with a strong suppression of methanogenesis (77%). Extracted RNA from each treatment was density resolved by isopycnic centrifugation, and analyzed by terminal restriction fragment length polymorphism, followed by cloning and sequencing of 16S rRNA of bacterial and archaeal populations. In heavy, isotopically labeled RNAs of the ferrihydrite treatment, predominant (13)C-assimilating populations were identified as Geobacter spp. (approximately 85% of all clones). In the goethite treatment, iron(II) formation was not detectable. However, Geobacter spp. (approximately 30%), the delta-proteobacterial Anaeromyxobacter spp. (approximately 30%), and novel beta-Proteobacteria were predominant in heavy rRNA fractions indicating that (13)C-acetate had been assimilated in the presence of goethite, whereas none were detected in the control heavy RNA. For the first time, active acetate-oxidizing iron(III)-reducing bacteria, including novel hitherto unrecognized populations, were identified as a functional guild in anoxic paddy soil.

Antimony(V) incorporation into synthetic ferrihydrite, goethite, and natural iron oxyhydroxides.

Abstract: In this study, we investigated local structures of Sb species in synthetic SbV-coprecipitated and -adsorbed ferrihydrite and goethite, which are common iron(III) oxyhydroxides in environment, at various Sb/Fe molar ratios by extended X-ray absorption fine structure (EXAFS) analyses. The EXAFS analyses showed that SbV is adsorbed on ferrihydrite and goethite by the formation of an inner-sphere surface complex at pH 7.5. In the EXAFS spectra of the coprecipitated ferrihydrite and goethite, some features of the spectra significantly differed from those in the adsorbed samples. The EXAFS simulation indicated that the difference is due to the larger coordination number of the Fe atom to the Sb atom in the coprecipitation samples, indicating a structural incorporation (heterovalent substitution) of SbV into ferrihydrite and goethite. The incorporation of SbV into the structure was also confirmed in natural iron(III) oxyhydroxides in contaminated soil near an Sb mine tailing using μ-EXAFS. This study directly pr...

Impact of Uranyl−Calcium−Carbonato Complexes on Uranium(VI) Adsorption to Synthetic and Natural Sediments

Abstract: Adsorption on soil and sediment solids may decrease aqueous uranium concentrations and limit its propensity for migration in natural and contaminated settings. Uranium adsorption will be controlled in large part by its aqueous speciation, with a particular dependence on the presence of dissolved calcium and carbonate. Here we quantify the impact of uranyl speciation on adsorption to both goethite and sediments from the Hanford Clastic Dike and Oak Ridge Melton Branch Ridgetop formations. Hanford sediments were preconditioned with sodium acetate and acetic acid to remove carbonate grains, and Ca and carbonate were reintroduced at defined levels to provide a range of aqueous uranyl species. U(VI) adsorption is directly linked to UO22+ speciation, with the extent of retention decreasing with formation of ternary uranyl−calcium−carbonato species. Adsorption isotherms under the conditions studied are linear, and Kd values decrease from 48 to 17 L kg−1 for goethite, from 64 to 29 L kg −1 for Hanford sediments, ...

On the goethite to hematite phase transformation

Abstract: This study deals with some microstructural and crystallographic aspects of the thermally induced transformation of goethite (α-FeOOH) into hematite (α-Fe2O3), occurring at about 300 °C. Powder specimens of goethite have been annealed in air at different temperatures, ranging from 200 °C up to 1,000 °C. The resulting products have been analyzed for a complete characterization of the changes brought about by the thermal treatments, using a multianalytical approach, based on: thermogravimetry, differential thermal analysis, transmission electron microscopy, Raman spectroscopy, and X-ray diffraction. At lower temperatures, the transition to hematite produces no important changes in size and shape of the original goethite grains. Recrystallization, and partial sintering, occurs only at temperatures in excess of 800 °C. The relevant evolution of pores present in both phases has been also considered, as it may provide important indications on the actual formation mechanism of hematite.

Nanosized Iron Oxide Colloids Strongly Enhance Microbial Iron Reduction

Abstract: Microbial iron reduction is considered to be a significant subsurface process. The rate-limiting bioavailability of the insoluble iron oxyhydroxides, however, is a topic for debate. Surface area and mineral structure are recognized as crucial parameters for microbial reduction rates of bulk, macroaggregate iron minerals. However, a significant fraction of iron oxide minerals in the subsurface is supposed to be present as nanosized colloids. We therefore studied the role of colloidal iron oxides in microbial iron reduction. In batch growth experiments with Geobacter sulfurreducens, colloids of ferrihydrite (hydrodynamic diameter, 336 nm), hematite (123 nm), goethite (157 nm), and akaganeite (64 nm) were added as electron acceptors. The colloidal iron oxides were reduced up to 2 orders of magnitude more rapidly (up to 1,255 pmol h 1 cell 1 ) than bulk macroaggregates of the same iron phases (6 to 70 pmol h 1 cell 1 ). The increased reactivity was not only due to the large surface areas of the colloidal aggregates but also was due to a higher reactivity per unit surface. We hypothesize that this can be attributed to the high bioavailability of the nanosized aggregates and their colloidal suspension. Furthermore, a strong enhancement of reduction rates of bulk ferrihydrite was observed when nanosized ferrihydrite aggregates were added. Dissimilatory iron reduction is an important anaerobic respiration process in anoxic subsurface environments. However, the reactivity of ferric iron is mostly limited by the reduction kinetics of the poorly soluble, extracellular iron minerals. Electron transfer from microorganisms to iron oxides can occur via direct contact or by electron shuttling compounds (46). Trans

Arsenic effects and behavior in association with the Fe(II)-catalyzed transformation of schwertmannite.

Abstract: In acid-mine drainage and acid-sulfate soil environments, the cycling of Fe and As are often linked to the formation and fate of schwertmannite (Fe(8)O(8)(OH)(8-2x)(SO(4))(x)). When schwertmannite-rich material is subjected to near-neutral Fe(III)-reducing conditions (e.g., in reflooded acid-sulfate soils or mining-lake sediments), the resulting Fe(II) can catalyze transformation of schwertmannite to goethite. This work examines the effects of arsenic(V) and arsenic(III) on the Fe(II)-catalyzed transformation of schwertmannite and investigates the associated consequences of this mineral transformation for arsenic mobilization. A series of 9-day anoxic transformation experiments were conducted with synthetic schwertmannite and various additions of Fe(II), As(III), and As(V). X-ray diffraction (XRD) and Fe K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy demonstrated that, in the absence of Fe(II), schwertmannite persisted as the dominant mineral phase. Under arsenic-free conditions, 10 mM Fe(II) catalyzed rapid and complete transformation of schwertmannite to goethite. However, the magnitude of Fe(II)-catalyzed transformation decreased to 72% in the presence of 1 mM As(III) and to only 6% in the presence of 1 mM As(V). This partial Fe(II)-catalyzed transformation of As(III)-sorbed schwertmannite did not cause considerable As(III) desorption. In contrast, the formation of goethite via partial transformation of As(III)- and As(V)-sorbed schwertmannite significantly decreased arsenic mobilization under Fe(III)-reducing conditions. This implies that the Fe(II)-catalyzed transformation of schwertmannite to goethite may help to stabilize solid-phase arsenic and retard its subsequent release to groundwater.

Photoreductive dissolution of iron oxides trapped in ice and its environmental implications.

Abstract: The availability of iron has been thought to be a main limiting factor for the productivity of phytoplankton and related with the uptake of atmospheric CO_2 and algal blooms in fresh and sea waters. In this work, the formation of bioavailable iron (Fe(II)_(aq)) from the dissolution of iron oxide particles was investigated in the ice phase under both UV and visible light irradiation. The photoreductive dissolution of iron oxides proceeded slowly in aqueous solution (pH 3.5) but was significantly accelerated in polycrystalline ice, subsequently releasing more bioavailable ferrous iron upon thawing. The enhanced photogeneration of Fe(II)_(aq) in ice was confirmed regardless of the type of iron oxides [hematite, maghemite (γ-Fe_2O_3), goethite (α-FeOOH)] and the kind of electron donors. The ice-enhanced dissolution of iron oxides was also observed under visible light irradiation, although the dissolution rate was much slower compared with the case of UV radiation. The iron oxide particles and organic electron donors (if any) in ice are concentrated and aggregated in the liquid-like grain boundary region (freeze concentration effect) where protons are also highly concentrated (lower pH). The enhanced photodissolution of iron oxides should occur in this confined boundary region. We hypothesized that electron hopping through the interconnected grain boundaries of iron oxide particles facilitates the separation of photoinduced charge pairs. The outdoor experiments carried out under ambient solar radiation of Ny-Alesund (Svalbard, 78°55′N) also showed that the generation of dissolved Fe(II)_(aq) via photoreductive dissolution is enhanced when iron oxides are trapped in ice. Our results imply that the ice(snow)-covered surfaces and ice-cloud particles containing iron-rich mineral dusts in the polar and cold environments provide a source of bioavailable iron when they thaw.

Sorption of radionickel to goethite: Effect of water quality parameters and temperature

Abstract: In this work, sorption of Ni(II) from aqueous solution to goethite as a function of various water quality parameters and temperature was investigated. The results indicated that the pseudo-second-order rate equation fitted the kinetic sorption well. The sorption of Ni(II) to goethite was strongly dependent on pH and ionic strength. A positive effect of HA/FA on Ni(II) sorption was found at pH 8.0. The Langmuir, Freundlich, and D-R models were applied to simulate the sorption isotherms at three different temperatures of 293.15 K, 313.15 K and 333.15 K. The thermodynamic parameters (ΔH 0, ΔS 0 and ΔG 0) were calculated from the temperature dependent sorption, and the results indicated that the sorption was endothermic and spontaneous. At low pH, the sorption of Ni(II) was dominated by outer-sphere surface complexation or ion exchange with Na+/H+ on goethite surfaces, whereas inner-sphere surface complexation was the main sorption mechanism at high pH.

Iron hydroxides in soils: A review of publications

Abstract: Iron hydroxides are subdivided into thermodynamically unstable (ferrihydrite, feroxyhyte, and lepidocrocite) and stable (goethite) minerals. Hydroxides are formed either from Fe3+ (as ferrihydrite) or Fe2+ (as feroxyhyte and lepidocrocite). The high amount of feroxyhyte in ferromanganic concretions is proved, which points to the leading role of variable redox conditions in the synthesis of hydroxides. The structure of iron hydroxides is stabilized by inorganic elements, i.e., ferrihydrite, by silicon; feroxyhyte, by manganese; lepidocrocite, by phosphorus; and goethite, by aluminum. Ferrihydrite and feroxyhyte are formed with the participation of biota, whereas the abiotic formation of lepidocrocite and goethite is possible. The iron hydroxidogenesis is more pronounced in podzolic soils than in chernozems, and it is more pronounced in iron-manganic nodules than in the fine earth. Upon the dissolution of iron hydroxides, iron isotopes are fractioned with light-weight 54Fe atoms being dissolved more readily. Unstable hydroxides are transformed into stable (hydr)oxides, i.e., feroxyhyte is spontaneously converted to goethite, and ferrihydrite, to hematite or goethite.

Formation of green rust sulfate : a combined in situ time-resolved X-ray scattering and electrochemical study.

Abstract: The mechanism of green rust sulfate (GR-SO4) formation was determined using a novel in situ approach combining time-resolved synchrotron-based wide-angle X-ray scattering (WAXS) with highly controlled chemical synthesis and electrochemical (i.e., Eh and pH) monitoring of the reaction. Using this approach,GR-SO4 was synthesized under strictly anaerobic conditions by coprecipitation from solutions with known FeII/FeIII ratios (i.e., 1.28 and 2) via the controlled increase of pH. The reaction in both systems proceeded via a three-stage precipitation and transformation reaction. During the first stage,schwertmannite (Fe8O8(OH)4.5(SO4)1.75) precipitated directly from solution at pH 2.8−4.5. With increasing pH (>5), Fe2+ ions adsorb to the surface of schwertmannite and catalyze its transformation to goethite (α-FeOOH) during the second stage of the reaction. In the third stage, the hydrolysis of the adsorbed Fe2+ ions on goethite initiates its transformation to GR-SO4 at pH >7. The GR-SO4 then continues to crys...

Heterogeneous Catalytic Oxidation of Phenanthrene by Hydrogen Peroxide in Soil Slurry: Kinetics, Mechanism, and Implication

Abstract: The degradation of phenanthrene sorbed on soil has been carried out using a H2O2/goethite heterogeneous catalytic oxidation process. The effect of operating variables, such as the goethite concentration, pH, H2O2 concentration, soil organic matter, and bicarbonate ions has been investigated. The reaction followed pseudo-first order kinetics. The rate constants were evaluated and varied between 2.0×10−4 and 1.1×10−3 min−1 depending on the H2O2 concentration. The highest rate of degradation of phenanthrene was observed at a H2O2 concentration of 5 M and 134.0 g/kg goethite. The intermediate product formed during the degradation of phenanthrene was identified to be salicylic acid that finally degraded to CO2 and H2O. H2O2 consumption continued as the OH radical attacked the salicylic acid. More than 80% consumption of the 5 M H2O2 took place within 30 min, and the degradation was almost complete after 3 h of reaction. Neutral pH was found to be effective in the removal of phenanthrene. Both soil organic matt...

Hydrolysis of cellobiose by β-glucosidase in the presence of soil minerals – Interactions at solid–liquid interfaces and effects on enzyme activity levels

Abstract: Extracellular enzymatic activities in soils are essential for the cycling of organic matter. These activities take place in multiphase environments where solid phases profoundly affect biocatalytic activities. Aspergillus niger is ubiquitous in soils; its β-glucosidase plays an important role in the degradation of cellulose, and therefore in the global carbon cycle and in the turnover of soil organic matter. However, the information on the interactions of this protein with soil minerals is very limited, and even less is known about their consequences for the hydrolysis of the natural substrate cellobiose. We therefore characterised the sorptive interactions of this enzyme with the soil minerals montmorillonite, kaolinite and goethite and quantified the resulting changes in the hydrolysis rate of cellobiose. Fractions of adsorbed protein, and the resulting catalytic activity loss, were lower for montmorillonite than for kaolinite and goethite at given experimental conditions; adsorption was 9.7 ± 7.3% for montmorillonite, 70.3 ± 3.1% for kaolinite and 71.4 ± 1.8% for goethite, respectively. Adsorption of the protein to the minerals caused a total decrease in the catalytic activity of 18.8 ± 3.4% for kaolinite and 17.9 ± 4.7% for goethite whereas it was not significant for montmorillonite. The average catalytic activity lost by the pool of adsorbed molecules was 26.8% for kaolinite and 25.0% for goethite. Both the amount of adsorbed protein and the resulting loss of catalytic activity were found to be independent of the specific surface areas yet were influenced by the electrical properties of the mineral surfaces. Under the experimental conditions, montmorillonite and kaolinite are negatively charged whereas goethite is positively charged. However, because of the adsorption of phosphate anions from the buffer, a charge reversal took place at the surface of goethite. This was confirmed by zeta ( ζ )-potential measurements in phosphate buffer, revealing negative values for all the tested minerals. Indeed goethite interacted with the enzyme as a negatively charged surface: the amount of adsorbed protein and the resulting catalytic activity loss were very similar to those of kaolinite. Our results show that, even if an important fraction of β-glucosidase is adsorbed to the minerals, the catalytic activity is largely retained. We suggest that this strong activity retention in presence of soil minerals results from a selective pressure on A. niger , which benefits from the activity of the adsorbed, and thus stabilized, enzyme pool.