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Showing papers on "Goethite published in 2011"


Journal ArticleDOI
TL;DR: Observations suggest two-line ferrihydrite transforms to hematite via a two-stage crystallization process, with goethite being intermediary.
Abstract: Under oxic aqueous conditions, two-line ferrihydrite gradually transforms to more thermodynamically stable and more crystalline phases, such as goethite and hematite. This temperature- and pH-dependent transformation can play an important role in the sequestration of metals and metalloids adsorbed onto ferrihydrite. A comprehensive assessment of the crystallization of two-line ferrihydrite with respect to temperature (25, 50, 75, and 100 °C) and pH (2, 7, and 10) as a function of reaction time (minutes to months) was conducted via batch experiments. Pure and transformed phases were characterized by X-ray diffraction (XRD), X-ray absorption near-edge spectroscopy (XANES), atomic force microscopy (AFM), and scanning electron microscopy (SEM). The rate of transformation of two-line ferrihydrite to hematite increased with increasing temperature at all pHs studied and followed first-order reaction kinetics. XRD and XANES showed simultaneous formation of goethite and hematite at 50 and 75 °C at pH 10, with hema...

267 citations


Journal ArticleDOI
TL;DR: In this paper, the reversibility of the arsenate adsorption process was studied using chlorides and phosphates as competing ions, and it was shown that arsenate adaption is related to the iron content of adsorbents, and the rate increases in the following order: goethite

244 citations


Journal ArticleDOI
TL;DR: Raman spectroscopy can be used for the rapid identification of a wide variety of minerals ranging from common iron oxy(hydroxides), such as ferrihydrite, to rare minerals, such as adelite.

220 citations


Journal ArticleDOI
Yanping Zhao1, Jinju Geng1, Xiaorong Wang1, Xueyuan Gu1, Shixiang Gao1 
01 Sep 2011
TL;DR: Results indicated that heavy metal cations and soil organic matters have great effects on the tetracycline mobility in the soil environment and eventually affect its exposure concentration and toxicity to organisms.
Abstract: Adsorption of tetracycline, one of the most widely used antibiotics, onto goethite was studied as a function of pH, metal cations, and humic acid (HA) over a pH range 3-10. Five background electrolyte cations (Li(+), Na(+), K(+), Ca(2+), and Mg(2+)) with a concentration of 0.01 M showed little effect on the tetracycline adsorption at the studied pH range. While the divalent heavy metal cation, Cu(2+), could significantly enhance the adsorption and higher concentration of Cu(2+), stronger adsorption was found. The results indicated that different adsorption mechanisms might be involved for the two types of cations. Background electrolyte cations hardly interfere with the interaction between tetracycline and goethite surfaces because they only form weak outer-sphere surface complexes. On the contrary, Cu(2+) could enhance the adsorption via acting as a bridge ion to form goethite-Cu(2+)-tetracycline surface complex because Cu(2+) could form strong and specific inner-sphere surface complexes. HA showed different effect on the tetracycline sorption under different pH condition. The presence of HA increased tetracycline sorption dramatically under acidic condition. Results indicated that heavy metal cations and soil organic matters have great effects on the tetracycline mobility in the soil environment and eventually affect its exposure concentration and toxicity to organisms.

206 citations


Journal ArticleDOI
TL;DR: In this article, a static spin-echo mapping NMR experiment was conducted to determine how the phosphate anion binds to common soil minerals, including goethite, akaganeite, and lepidocrocite.
Abstract: Phosphate adsorption on the surfaces of the iron oxyhydroxide polymorphs goethite, akaganeite, and lepidocrocite were studied by using 31P static spin-echo mapping NMR experiments to determine how this environmentally-important anion binds to common soil minerals. The large 31P hyperfine shifts confirm the formation of inner-sphere complexes between the phosphate anion and the iron oxyhydroxide surface, the large shifts indicating the presence of Fe3+–O–P covalent bonds. Binding was explored as a function of pH and phosphate concentrations, the phosphate ion binding via two oxygen ions to the oxyhydroxide surface under all conditions and for all the surfaces. To support our analysis of the NMR spectra, adsorption of dimethyl phosphinic acid (DPA) on iron oxyhydroxides was also investigated, since this ion can only bond via one Fe–O–P interaction to the surface. The 31P hyperfine shifts observed for this anion were 50% of those seen for the phosphate anions, confirming that the phosphate ions bind to the surface via two P–O–Fe linkages.

187 citations


Journal ArticleDOI
TL;DR: The results suggest that proteinaceous constituents were adsorbed preferentially on montmorillonite and kaolinite, and phosphorylated macromolecules were absorbed preferenially on goethite, suggesting the importance of hydrogen bonding in EPS adsorption.

160 citations


Journal ArticleDOI
TL;DR: In this paper, the specific effects of microbial sulfidogenesis on Fe mineralogy and associated As mobility in mildly acidic (pH 6) and mildly basic (PH 8) advective-flow environments were investigated.

139 citations


Journal ArticleDOI
TL;DR: In this paper, the authors examined the possibility of using bacteria that can bring about the reductive dissolution of ferric iron minerals and thereby facilitate the extraction of nickel from a lateritic ore at relatively low.

126 citations


Journal ArticleDOI
TL;DR: Experiments demonstrate that Fe(II) with goethite efficiently catalyzes the reduction of technetium in deionized water and complex solutions that mimic the chemical composition of caustic waste scrubber media and provides significant advantages for limiting reoxidation and curtailing release of Tc disposed in nuclear waste repositories.
Abstract: During the nuclear waste vitrification process volatilized (99)Tc will be trapped by melter off-gas scrubbers and then washed out into caustic solutions, and plans are currently being contemplated for the disposal of such secondary waste. Solutions containing pertechnetate [(99)Tc(VII)O(4)(-)] were mixed with precipitating goethite and dissolved Fe(II) to determine if an iron (oxy)hydroxide-based waste form can reduce Tc(VII) and isolate Tc(IV) from oxygen. The results of these experiments demonstrate that Fe(II) with goethite efficiently catalyzes the reduction of technetium in deionized water and complex solutions that mimic the chemical composition of caustic waste scrubber media. Identification of the phases, goethite + magnetite, was performed using XRD, SEM and TEM methods. Analyses of the Tc-bearing solid products by XAFS indicate that all of the Tc(VII) was reduced to Tc(IV) and that the latter is incorporated into goethite or magnetite as octahedral Tc(IV). Batch dissolution experiments, conducted under ambient oxidizing conditions for more than 180 days, demonstrated a very limited release of Tc to solution (2-7 μg Tc/g solid). Incorporation of Tc(IV) into the goethite lattice thus provides significant advantages for limiting reoxidation and curtailing release of Tc disposed in nuclear waste repositories.

121 citations


Journal ArticleDOI
TL;DR: In this article, a tuneable dye laser was used to enhance the Raman spectra for the detection of iron oxide and iron oxyhydroxide compounds using an excitation wavelength of 636.4 nm.
Abstract: Raman spectroscopy, in principle, is an excellent technique for the study of molecular species developed on metal surfaces during electrochemical investigations. However, the use of the more common laser wavelengths such as the 514.5-nm line results in spectra of less than optimal intensity, particularly for iron oxide compounds. In the present work, near-resonance enhancement of the Raman spectra was investigated for the iron oxide and iron oxyhydroxide compounds previously reported to be present in the passive film on iron, using a tuneable dye laser producing excitation wavelengths between 560 and 637 nm. These compounds were hematite (α-Fe2O3), maghemite (γ-Fe2O3), magnetite (Fe3O4), goethite (α-FeOOH), akaganeite (β-FeOOH), lepidocrocite (γ-FeOOH) and feroxyhyte (δ-FeOOH). Optimum enhancement, when compared to that with the 514.5-nm line, was obtained for all the iron oxide and oxyhydroxide standard samples in the low wavenumber region (<1000 cm−1) using an excitation wavelength of 636.4 nm. Particularly significant enhancement was obtained for lepidocrocite, hematite and goethite. Copyright © 2010 John Wiley & Sons, Ltd.

119 citations


Journal ArticleDOI
TL;DR: In this article, the relationship between size, shape, and thermodynamic stability of unpassivated hematite (α-Fe2O3) and goethite nanoparticles, using a robust thermodynamic morphology model with input parameters from reliable first-principles calculations and thermochemical data, was investigated.
Abstract: Iron oxide and oxyhydroxide nanoparticles are among the most important mobile and catalytic agents in a variety of biogeochemical environments, and are being increasingly synthesized for energy, electronic, catalyst, environmental and medical applications. The morphologies at nanoscale are relevant to the control of shapes and sizes, surface chemistry, and performance of these nanoparticles, as well as our understanding of naturally occurring processes. Therefore, we have begun to develop this understanding by studying the relationship between size, shape, and thermodynamic stability of unpassivated hematite (α-Fe2O3) and goethite (α-FeOOH) nanoparticles, using a robust thermodynamic morphology model with input parameters from reliable first-principles calculations and thermochemical data. The results revealed the thermodynamic stable shapes of hematite and goethite nanoparticles, and demonstrated that the phase transformation from goethite to hematite is highly dependent on the particle size and temperature. Goethite nanoparticles are thermodynamically stable with small sizes, compared to hematite, but the equilibrium transformation temperature increases rapidly with decreasing particle size. The morphology sensitive phase transformation predicted by our model is a step further towards a nanophase diagram of iron oxides and oxyhydroxides.

Journal ArticleDOI
TL;DR: In this article, the effect of oxalate on dust iron solubility in simulated rainwater was investigated and it was shown that oxalates contributes to the dissolution of pure iron-bearing minerals usually present in dust particles.

Journal ArticleDOI
TL;DR: Results suggest that when the Fe(II)-catalyzed transformation of ferrihydrite-like iron oxyhydroxides is inhibited, at least under conditions similar to those used in these experiments, uranium reduction will not occur.
Abstract: It has recently been reported that the Fe(II)-catalyzed crystallization of 2-line ferrihydrite to goethite and magnetite can result in the immobilization of uranium. Although it might be expected that interference of the crystallization process (for example, by the presence of silicate) would prevent uranium immobilization, this has not yet been demonstrated. Here we present results of an X-ray absorption spectroscopy study on the fate of hexavalent uranium (U(VI)) during the Fe(II)-catalyzed transformations of 2-line ferrihydrite and ferrihydrite coprecipitated with silicate (silicate-ferrihydrite). Two-line ferrihydrite transformed monotonically to goethite, whereas silicate-ferrihydrite transformed into a form similar to ferrihydrite synthesized in the absence of silicate. Modeling of U L(III)-edge EXAFS data indicated that both coprecipitated and adsorbed U(VI) were initially associated with ferrihydrite and silicate-ferrihydrite as a mononuclear bidentate surface complex. During the Fe(II)-catalyzed transformation process, U(VI) associated with 2-line ferrihydrite was reduced and partially incorporated into the newly formed goethite mineral structure, most likely as U(V), whereas U(VI) associated with silicate-ferrihydrite was not reduced and remained in a form similar to its initially adsorbed state. Uranium(VI) that was initially adsorbed to silicate-ferrihydrite did, however, become more resistant to reductive dissolution indicating at least a partial reduction in mobility. These results suggest that when the Fe(II)-catalyzed transformation of ferrihydrite-like iron oxyhydroxides is inhibited, at least under conditions similar to those used in these experiments, uranium reduction will not occur.

Journal ArticleDOI
TL;DR: In this paper, the authors explored the extent, rates, and pathways of Fe(II)-induced secondary mineralization of Al-ferrihydrites by reacting aqueous Fe(III) (0.2 and 2.0 mM) with 2-line ferrihydrite containing a range of Al levels substituted within (6−24 ǫ% Al) or adsorbed on the surface.

Journal ArticleDOI
01 Nov 2011-Geology
TL;DR: In this article, the authors demonstrate that Ni is cycled through the minerals goethite and hematite during redox-driven recrystallization, and they conclude that the redistribution of Ni among the mineral bulk, mineral surface and aqueous solution appears to be thermodynamically controlled and catalyzed by Fe(II).
Abstract: Microbially driven iron redox cycling in soil and sedimentary systems, including during diagenesis and fluid migration, may activate secondary abiotic reactions between aqueous Fe(II) and solid Fe(III) oxides. These reactions catalyze dynamic recrystallization of iron oxide minerals through localized and simultaneous oxidative adsorption of Fe(II) and reductive dissolution of Fe(III). Redox-active trace elements undergo speciation changes during this process, but the impact redox-driven recrystallization has on redox-inactive trace elements associated with iron oxides is uncertain. Here we demonstrate that Ni is cycled through the minerals goethite and hematite during redox-driven recrystallization. X-ray absorption spectroscopy demonstrates that during this process adsorbed Ni becomes progressively incorporated into the minerals. Kinetic studies using batch reactors containing aqueous Fe(II) and Ni preincorporated into iron oxides display substantial release of Ni to solution. We conclude that iron oxide recrystallization activated by aqueous Fe(II) induces cycling of Ni through the mineral structure, with adsorbed Ni overgrown in regions of Fe(II) oxidative adsorption and incorporated Ni released in regions of reductive dissolution of structural Fe(III). The redistribution of Ni among the mineral bulk, mineral surface, and aqueous solution appears to be thermodynamically controlled and catalyzed by Fe(II). Our work suggests that important proxies for ocean composition on the early Earth may be invalid, identifies new processes controlling micronutrient availability in soil, sedimentary, and aquatic ecosystems, and points toward a mechanism for trace element mobilization during diagenesis and enrichment in geologic fluids.

Journal ArticleDOI
TL;DR: It is reported that intrinsic Pu nanocolloids generated in the absence of goethite or quartz were 2-5 nm in diameter, and both electron diffraction analysis and HRTEM confirm the expected Fm3m space group with the fcc, PuO2 structure.
Abstract: The subsurface migration of Pu may be enhanced by the presence of colloidal forms of Pu. Therefore, complete evaluation of the risk posed by subsurface Pu contamination needs to include a detailed physical/chemical understanding of Pu colloid formation and interactions of Pu colloids with environmentally relevant solid phases. Transmission electron microscopy (TEM) was used to characterize Pu nanocolloids and interactions of Pu nanocolloids with goethite and quartz. We report that intrinsic Pu nanocolloids generated in the absence of goethite or quartz were 2-5 nm in diameter, and both electron diffraction analysis and HRTEM confirm the expected Fm3m space group with the fcc, PuO2 structure. Plutonium nanocolloids formed on goethite have undergone a lattice distortion relative to the ideal fluorite-type structure, fcc, PuO2, resulting in the formation of a bcc, Pu4O7 structure. This structural distortion results from an epitaxial growth of the plutonium colloid on goethite, leading to stronger binding of plutonium to goethite compared with other minerals such as quartz, where the distortion was not observed. This finding provides new insight for understanding how molecular-scale behavior at the mineral-water interface may facilitate transport of plutonium at the field scale.

Journal ArticleDOI
TL;DR: 2-Line ferrihydrite, a form of iron in uranium mine tailings, is a dominant adsorbent for elements of concern (EOC), such as arsenic, and arsenic was found to retard ferriHydrite dissolution and transformation as well as goethite formation.
Abstract: 2-Line ferrihydrite, a form of iron in uranium mine tailings, is a dominant adsorbent for elements of concern (EOC), such as arsenic. As ferrihydrite is unstable under oxic conditions and can undergo dissolution and subsequent transformation to hematite and goethite over time, the impact of transformation on the long-term stability of EOC within tailings is of importance from an environmental standpoint. Here, studies were undertaken to assess the rate of 2-line ferrihydrite transformation at varying As/Fe ratios (0.500-0.010) to simulate tailings conditions at the Deilmann Tailings Management Facility of Cameco Corporation, Canada. Kinetics were evaluated under relevant physical (~1 °C) and chemical conditions (pH ~10). As the As/Fe ratio increased from 0.010 to 0.018, the rate of ferrihydrite transformation decreased by 2 orders of magnitude. No transformation of ferrihydrite was observed at higher As/Fe ratios (0.050, 0.100, and 0.500). Arsenic was found to retard ferrihydrite dissolution and transformation as well as goethite formation.

Journal ArticleDOI
TL;DR: In this article, the authors compared the sorption behavior of several dissolved organic phosphorus (DOP) compounds and phosphate onto three commonly occurring iron oxides (Fe ox): ferrihydrite, goethite, and hematite.

Journal ArticleDOI
TL;DR: In this article, a detailed mineralogical, geochemical, and microbiological investigation of two tailing impoundments near the town of Pezinok, Slovakia is presented. But the primary objective of this study was the mineralogy that formed in the impoundment after the deposition of the tailings (so-called tertiary minerals), which are present as grains and as rims on primary ore minerals.
Abstract: The mineralogical composition of mining wastes deposited in voluminous tailing impoundments around the world is the key factor that controls retention and release of pollutants. Here we report a detailed mineralogical, geochemical, and microbiological investigation of two tailing impoundments near the town of Pezinok, Slovakia. The primary objective of this study was the mineralogy that formed in the impoundment after the deposition of the tailings (so-called tertiary minerals). Tertiary minerals include oxyhydroxides of Fe, Sb, As, Ca and are present as grains and as rims on primary ore minerals. X-ray microdiffraction data show that the iron oxyhydroxides with abundant As are X-ray amorphous. The limiting (lowest) Fe/As (wt/wt%) ratio in this material is 1.5; beyond this ratio, the hydrous ferric oxide does not retain arsenic. The grains with less As and little to moderate amounts of Sb are goethite; the grains where Sb dominates over Fe are poorly crystalline tripuhyite (FeSbO4). Even the most heavily contaminated samples (up to 29 wt% As2O5) are populated with diverse communities of microorganisms including typical arsenic-resistant heterotrophic species as well as iron reducers and sulfur oxidizers. Several recovered clones cluster within phylogenetic groups that are solely based on environmental sequences and do not contain a single cultivated species, thus calling for more work on such extreme environments.

Journal ArticleDOI
TL;DR: In this paper, Boehmite and goethite were synthesized and characterized to compare their adsorptive properties for Cd(II) from aqueous solutions, and the influences of different parameters, such as contact time, initial cadmium concentration, pH and temperature, on the adsorption processes were investigated.

Journal ArticleDOI
TL;DR: In this article, the authors compared biological mineralization of mineral-bound organic matter (OM) to its resistance to chemical oxidation by 6 mass% NaOCl and showed that chemically oxidizable OM does not represent the portion of sorbed OM available to biological consumption.
Abstract: Understanding the turnover of organic matter (OM) in soils necessitates information on biological stability and ecological functions. For easy characterization of slowly cycling OM, treatments using oxidants such as sodium hypochlorite (NaOCl) have been applied. The rationale for that approach is, however, questionable and concerns exist to which extent abiotic oxidation can mimic biological mineralization. Here we compare biological mineralization of mineral-bound OM to its resistance to chemical oxidation by 6 mass% NaOCl. Water-extractable OM, sorbed to goethite, vermiculite, and pyrophyllite at pH 4.0 and in different background electrolytes (CaCl 2 , NaCl, NaCl–NaH 2 PO 4 ) to favor or exclude certain binding mechanisms, was subsequently subjected to NaOCl treatment (pH 7, either for 18 or 6 × 6 h). Irrespective of mineral surface properties and mechanisms involved in OM sorption, NaOCl removed a constant portion of the sorbed OC. More OC survived when bound to goethite than to vermiculite, thus confirming previous results on the increase of oxidation-resistant OC with increasing Fe and Al (hydr)oxide contents in different soils. Mineralizable OC (within 90 days) was much smaller than the NaOCl-removable OC and both fractions were negatively correlated ( r 2 = 0.90 for the 18 h treatment; r 2 = 0.86 for the 6 × 6 h treatment), suggesting that chemically oxidizable OM does not represent the portion of sorbed OM available to biological consumption.

Journal ArticleDOI
TL;DR: The observed trends of the reactivity and analysis of the corresponding surface structure and particle morphology suggest an intimate relation between the surface chemistry of exposed crystal facets on the iron minerals.
Abstract: Adsorption of trimethyl phosphate (TMP) on well-characterized hematite, maghemite and goethite nanopartides was studied by in situ DRIFT spectroscopy as a model system for adsorption of organophosphorous (OP) compounds on iron minerals. The iron minerals were characterized by X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), specific surface area, and pore size distribution. The minerals were found to consist of stoichimetrically and morphologically well-defined maghemite, hematite, and goethite nanoparticles. Analysis of in situ diffuse reflectance Fourier transform (DRIFT) spectroscopy shows that TMP bonds mainly to Lewis acid Fe sites through the O phosphoryl atom (-P=O-Fe) on hematite and maghemite. On goethite most TMP molecules bond to Bronstedt acid surface OH groups and form hydrogen bonded surface complexes. The vibrational mode analysis and uptake kinetics suggest two main reasons for the observed trend of reactivity toward TMP (hematite > maghemite > goethite): (i) larger number of accessible Lewis acid adsorption sites on hematite; (ii) stronger interaction between the Lewis acid Fe sites and the phosphoryl O atom on TAP for hematite and maghemite compared to goethite with concomitant formation of surface coordinated TMP and dimethyl phosphate intermediates. As a result, on the oxides a surface oxidation pathway dominates during the initial adsorption, which results in the formation of surface methoxy and formate. In contrast, on goethite a slower hydrolysis pathway is identified, which eventually yields phosphoric acid. The observed trends of the reactivity and analysis of the corresponding surface structure and particle morphology suggest an intimate relation between the surface chemistry of exposed crystal facets on the iron minerals. These results are important to understand OP surface chemistry on iron minerals.

Journal ArticleDOI
TL;DR: It is demonstrated that the sorption of species incompatible with iron oxide structure is not substantially affected by Fe(II) but that such species may potentially interfere with Fe( II)-iron oxide reactions via competitive adsorption.
Abstract: Biogeochemical iron cycling often generates systems where aqueous Fe(II) and solid Fe(III) oxides coexist. Reactions between these species result in iron oxide surface and phase transformations, iron isotope fractionation, and redox transformations of many contaminant species. Fe(II)-induced recrystallization of goethite and hematite has recently been shown to cause the repartitioning of Ni(II) at the mineral-water interface, with adsorbed Ni incorporating into the iron oxide structure and preincorporated Ni released back into aqueous solution. However, the effect of Fe(II) on the fate and speciation of redox inactive species incompatible with iron oxide structures is unclear. Arsenate sorption to hematite and goethite in the presence of aqueous Fe(II) was studied to determine whether Fe(II) causes substantial changes in the sorption mechanisms of such incompatible species. Sorption isotherms reveal that Fe(II) minimally alters macroscopic arsenate sorption behavior except at circumneutral pH in the presence of elevated concentrations (10⁻³ M) of Fe(II) and at high arsenate loadings, where a clear signature of precipitation is observed. Powder X-ray diffraction demonstrates that the ferrous arsenate mineral symplesite precipitates under such conditions. Extended X-ray absorption fine structure spectroscopy shows that outside this precipitation regime arsenate surface complexation mechanisms are unaffected by Fe(II). In addition, arsenate was found to suppress Fe(II) sorption through competitive adsorption processes before the onset of symplesite precipitation. This study demonstrates that the sorption of species incompatible with iron oxide structure is not substantially affected by Fe(II) but that such species may potentially interfere with Fe(II)-iron oxide reactions via competitive adsorption.

Journal ArticleDOI
TL;DR: High binding efficiency of Fe(III) species in Fe-M are more efficient in binding arsenate than in ferrihydrite or goethite, indicating that Fe( III) species are well spread on montmorillonite, forming small oligomeric species or surface clusters containing just a few iron atoms.

Journal ArticleDOI
TL;DR: The relationship between the crystal structure of iron(III) oxyhydroxides and the mechanism of metal removal is discussed, as well as the linear relationship observed between the rate constant and the surface area of precipitates.
Abstract: The reaction of potassium ferrate(VI), K(2)FeO(4), with weak-acid dissociable cyanides--namely, K(2)[Zn(CN)(4)], K(2)[Cd(CN)(4)], K(2)[Ni(CN)(4)], and K(3)[Cu(CN)(4)]--results in the formation of iron(III) oxyhydroxide nanoparticles that differ in size, crystal structure, and surface area. During cyanide oxidation and the simultaneous reduction of iron(VI), zinc(II), copper(II), and cadmium(II), metallic ions are almost completely removed from solution due to their coprecipitation with the iron(III) oxyhydroxides including 2-line ferrihydrite, 7-line ferrihydrite, and/or goethite. Based on the results of XRD, Mossbauer and IR spectroscopies, as well as TEM, X-ray photoelectron emission spectroscopy, and Brunauer-Emmett-Teller measurements, we suggest three scavenging mechanisms for the removal of metals including their incorporation into the ferrihydrite crystal structure, the formation of a separate phase, and their adsorption onto the precipitate surface. Zn and Cu are preferentially and almost completely incorporated into the crystal structure of the iron(III) oxyhydroxides; the formation of the Cd-bearing, X-ray amorphous phase, together with Cd carbonate is the principal mechanism of Cd removal. Interestingly, Ni remains predominantly in solution due to the key role of nickel(II) carbonate, which exhibits a solubility product constant several orders of magnitude higher than the carbonates of the other metals. Traces of Ni, identified in the iron(III) precipitate, are exclusively adsorbed onto the large surface area of nanoparticles. We discuss the relationship between the crystal structure of iron(III) oxyhydroxides and the mechanism of metal removal, as well as the linear relationship observed between the rate constant and the surface area of precipitates.

Journal ArticleDOI
TL;DR: The geochemistry, mineralogy and microbiology of bacteriogenic iron oxides (BIOS) deposited at a circumneutral groundwater seep were examined to evaluate the biogeochemical controls on the redox cycle of iron in such environments.

Journal ArticleDOI
TL;DR: The results show that fuel cell technologies can not only be used for simultaneous AMD treatment and power generation, but that they can generate useful products such as iron oxide particles having sizes appropriate for used as pigments and other applications.

Journal ArticleDOI
TL;DR: The interplay between As(V) sorption to mineral surfaces and bacterially induced desorption may be critical in controlling the kinetics of As reduction and release in reducing soils and sediments.
Abstract: The kinetics of As(V) reduction by Shewanella putrefaciens strain CN-32 was investigated in suspensions of 0.2, 2, or 20 g L(-1) ferrihydrite, goethite, or boehmite at low As (10 μM) and lactate (25 μM) concentrations. Experimental data were compared with model predictions based on independently determined sorption isotherms and rates of As(V) desorption, As(III) adsorption, and microbial reduction of dissolved As(V), respectively. The low lactate concentration was chosen to prevent significant Fe(III) reduction, but still allowing complete As(V) reduction. Reduction of dissolved As(V) followed first-order kinetics with a 3 h half-life of As(V). Addition of mineral sorbents resulted in pronounced decreases in reduction rates (32-1540 h As(V) half-life). The magnitude of this effect increased with increasing sorbent concentration and sorption capacity (goethite < boehmite < ferrihydrite). The model consistently underestimated the concentrations of dissolved As(V) and the rates of microbial As(V) reduction after addition of S. putrefaciens (∼5 × 10(9) cells mL(-1)), suggesting that attachment of S. putrefaciens cells to oxide mineral surfaces promoted As(V) desorption and thereby facilitated As(V) reduction. The interplay between As(V) sorption to mineral surfaces and bacterially induced desorption may thus be critical in controlling the kinetics of As reduction and release in reducing soils and sediments.

Journal ArticleDOI
TL;DR: The low solubility of scorodite, the relatively low content of AFA and the formation of compounds of variable charge, mostly of amorphous nature, with high capacity to adsorb As attenuate importantly the dispersion of this element into the environment from these arsenopyrite-bearing wastes.

Journal ArticleDOI
TL;DR: This study has investigated the preservation of filamentous iron oxidising bacteria and organics through optical microscopy, scanning electron microscopy (SEM) and Fourier transform infra-red (FTIR) spectroscopy, from laboratory cultures of natural samples to contemporary natural materials to million-year old river terraces.
Abstract: One of the keys to understanding and identifying life on other planets is to study the preservation of organic compounds and their precursor micro-organisms on Earth. Rio Tinto in southwestern Spain is a well documented site of microbial preservation within iron sulphates and iron oxides over a period of 2.1 Ma. This study has investigated the preservation of filamentous iron oxidising bacteria and organics through optical microscopy, scanning electron microscopy (SEM) and Fourier transform infra-red (FTIR) spectroscopy, from laboratory cultures of natural samples to contemporary natural materials to million-year old river terraces. Up to 40% elemental carbon and >7% nitrogen has been identified within microbial filaments and cell clusters in all samples through SEM EDS analyses. FTIR spectroscopy identified C-H(x) absorption bands between 2960 and 2800 cm(-1), Amide I and II absorption bands at 1656 and 1535 cm(-1), respectively and functional group vibrations from within nucleic acids at 917, 1016 and 1124 cm(-1). Absorption bands tracing the diagenetic transformation of jarosite to goethite to hematite through the samples are also identified. This combination of mineralogy, microbial morphology and biomolecular evidence allows us to further understand how organic fossils are created and preserved in iron-rich environments, and ultimately will aid in the search for the earliest life on Earth and potential organics on Mars.