Showing papers on "Goethite published in 2008"

Reductive processes controlling arsenic retention: revealing the relative importance of iron and arsenic reduction.

Abstract: The fate and transport of arsenic is regulated, in part, by its strong affinity for iron (hydr)oxides. A transition from aerobic to anaerobic conditions resulting in concomitant reduction of both As(V) and iron (hydr)oxides can thus have a pronounced influence on As partitioning. However, it is presently unclear whether As desorption under anaerobic conditions results predominantly from a transformation from As(V) to As(III) or from mineralogical changes as a consequence of iron and manganese reduction. Here, we examine desorption of both As(III) and As(V) from ferrihydrite-, goethite-, and hematite-coated sand under hydrodynamic conditions. Furthermore, to resolve the relative role of Fe(III) and/or As(V) reduction in regulating dissolved As concentrations, we also examined As desorption from ferrihydrite- and goethite-coated sands presorbed with As(V) using wild type or mutants of Shewanella sp. ANA-3, capable of Fe(III)- and/or As(V)-reduction. We reveal substantial differences in As(III) and As(V) desorption from ferrihydrite, goethite, and hematite. Despite being adsorbed to a greater extent than As(V), As(III) is desorbed more rapidly and extensively from all oxides, suggesting weaker binding of As(III) than As(V). When As(V) and Fe(III) reduction are decoupled, As(V) reduction appears to be the dominant process controlling As release. Our results also suggest the importance of appreciating physical properties of specific Fe (hydr)oxides when predicting the potential for As desorption.

Minerals in the clay fraction of Brazilian Latosols (Oxisols): a review

Abstract: This review focuses on the clay mineralogy of the most important Brazilian soils: the Latosols, which cover >60% of the country by area, and occur in association with other soils. They are typically deep, highly-weathered soils, dominated by low-activity 1:1 clay minerals and Fe and Al oxyhydroxides, with varying proportions of these minerals, depending on parent material and weathering intensity. They are usually of low fertility, although eutric types also occur. Latosols are generally correlated with Oxisols (American soil taxonomy) and Ferralsols (WRB system). Clay mineralogy is typically monotonous: kaolinite, gibbsite, hematite, goethite, maghemite and Ti minerals (mainly ilmenite and anatase) are the prominent mineral phases in the clay fraction. Some Latosols developing on basalt from southern Brazil contain significant amounts of hydroxyl-interlayed vermiculite. Among the pedogenic oxides the most frequent are goethite (α-FeOOH), indicated by yellowish colours (2.5Y–10YR; in the absence of hematite), and hematite (α-Fe2O3), which imbues reddish colors (2.5YR–5R), even when present in very minor amounts. Maghemite (γ-Fe2O3) is less frequent; it imparts a reddish-brown colour (5YR–2.5YR) and magnetic properties. Both goethite and hematite show Al-substitution, with a greater relative proportion in soil goethites. Hence, in similar drainage conditions, goethite is less prone to dissolution than hematite. Most reddish Latosols also contain maghemite, due to partial or complete oxidation of magnetite, which generally occurs naturally or is fire-induced. Magnetite and/or maghemite are associated with trace elements which are important in plant nutrition, such as Cu, Zn and Co. The contents of gibbsite in Latosols are extremely variable, from a complete absence in brown Latosols, to 54% in red Latosols from mafic rocks. Relatively large amounts of gibbsite are found in the clay fraction of these soils and this mineral is important in P sorption in deeply weathered Latosols in association with goethite and hematite. Even though most Latosols are dystrophic, some are eutrophic, revealing an unusually large base saturation in areas under ustic regimes where the parent material is particularly rich in bases, such as basalts. This eutrophic nature is attributed to the protecting role of micro-aggregates in ferric red Latosols, which retard base-leaching from the inner aggregate. At the other extreme, some Brazilian Latosols are acric and positively-charged in sub-surface horizons, as revealed by the relationship pH KCl > pH H2O. These acric Latosols are the result of long-term weathering and intensive leaching, during which pH tends to increase to values close to the zero point charge of Fe and Al oxides (between 6 and 7), greatly increasing P adsorption, which is mainly attributed to gibbsite, goethite and hematite. Soil kaolinites in Brazilian Latosols are mostly of low crystallinity, with Hughes and Brown indexes of between 6 and 15. In this review we have discussed the role of these clay-fraction minerals in soil genesis and fertility, highlighting the marked role of inheritance from deeply-weathered parent material. Latosols typically retain large amounts of Fe oxides, some of which are magnetic, with spontaneous magnetization >1 J T−1 kg−1. In this regard, reddish Latosols developed from mafic rocks are the most representative magnetic soils, and cover as much as 3.9% of Brazil. An overview of magnetic soils on four representative examples of mafic lithologies is presented, together with some aspects of their Fe-oxide mineralogy and related field and laboratory technqiues.

Humic nanoparticles at the oxide-water interface: interactions with phosphate ion adsorption.

Abstract: In this work, data for the interactions between humic acid (HA) or fulvic acid (FA) with phosphate ions at the surface of goethite (alpha-FeOOH) are presented. The results show very clear differences between HA and FA in their interactions with phosphate at goethite surface. HA is strongly bound to goethite but surprisingly does not strongly affect the phosphate binding, whereas FA is less strongly bound, but these molecules have a very large effect on the phosphate adsorption, and vice versa. Phosphate adsorption to goethite in the presence of adsorbed HA or FA can be well predicted with the LCD model (ligand and charge distribution). According to the model calculations, the nature of the interactions between HA or FA with phosphate at goethite surface is mainly electrostatic. The stronger effects of FA on phosphate adsorption are caused by its spatial location which is closer to the oxide surface, and as a consequence, the electrostatic interactions between adsorbed FA particles and phosphate ions are much stronger than for HA particles. This is the first time that effects of natural organic matter (NOM) on an anion adsorption are predicted successfully using an integrated ion-binding model for oxides and for humics that accounts for chemical heterogeneity of NOM.

Humic acid fractionation upon sequential adsorption onto goethite.

Abstract: Mineral-humic complexes are commonly distributed in natural environments and are important in regulating the transport and retention of hydrophobic organic contaminants in soils and sediments. This study investigated the structural and conformational changes of humic acid (HA) and mineral-HA complexes after sequential HA adsorption by goethite, using UV-visible spectroscopy, high performance size exclusion chromatography (HPSEC), Fourier transform infrared (FT-IR) spectroscopy, and solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. The HA remaining in the solution after adsorption showed low polarity index values ((N+O)/C), which indicates that polar functional moieties are likely to adsorb on the goethite surface. In addition, we observed decreased E4/E6 and E2/E3 ratios of unbound HA with increasing number of coatings, implying that aliphatic rich HA fractions with polar functional moieties readily adsorb to the goethite surface. According to IR spectra, carbohydrate carbon would be the important fractions associated with goethite. NMR spectra provided evidence for HA fractionation during adsorption onto the mineral surface; that is, aliphatic fractions were preferentially adsorbed by goethite while aromatic fractions were left in solution. Relatively small molecular weight (MW) HA fractions had a greater affinity for the goethite surface based on analyses of the HPSEC chromatograms, which differs from the results reported in the literature. Finally, our results suggest that the polar aliphatic fractions of HA were mainly adsorbed to goethite via electrostatic attraction and/or ligand exchange reactions.

Removal of arsenic from water streams: an overview of available techniques

Abstract: Arsenic poisoning has become one of the major environmental worries worldwide, as millions of people, which have been exposed to high arsenic concentrations (through contaminated drinking water), developed severe health problems. The high toxicity of this element made necessary the enforcement of stringent maximum allowable limits in drinking water. So, the development of novel techniques for its removal from aqueous streams is a very important issue. This paper offers an overview of geochemistry, distribution, sources, toxicity, regulations and applications of selected techniques for arsenic removal. The contribution briefly summarizes adsorption processes and mechanism of arsenic species removal from water streams by means of iron oxide/oxyhydroxide based materials. Sorption capacities of various sorbents (e.g. akaganeite, goethite, hydrous ferric oxide, iron oxide coated sand, Fe(III) loaded resin, granular ferric hydroxide, Ce(IV) doped iron oxide, natural iron ores, iron oxide coated cement, magnetically modified zeolite, Fe-hydroxide coated alumina) have been compared.

Photoinduced degradation of orange II on different iron (hydr)oxides in aqueous suspension: rate enhancement on addition of hydrogen peroxide, silver nitrate, and sodium fluoride.

Abstract: Photoinduced organic oxidation with iron (hydr)oxides in aqueous suspension has been argued with respect to two principal mechanisms: (a) photoinduced ligand-to-metal charge transfer within a surface complex and (b) semiconductor photocatalysis. In this work, the photodegradation of azo dye orange II with UV light (λ ≥ 320 nm) in the aerated aqueous suspensions of haematite, maghemite, magnetite, goethite, lepidocrocite, and feroxyhite at an initial pH of 6.5 has been examined. The results showed that (1) all of the catalysts were effective at initiating dye photodegradation but the iron oxides appeared to be more active than the iron hydroxides; (2) the photodissolution of different iron phases and the dye photolysis in the dissolved iron solutions were very slow; (3) the initial rate of dye loss was proportional to the initial amount of adsorption, implying dye photodegradation on the catalyst surface; and (4) upon addition of H2O2, AgNO3, and NaF to the suspension, the rate of dye photodegradation was...

Oxidation of FeS by oxygen-bearing acidic solutions.

Abstract: Oxidation of FeS in oxygen-bearing acidic solutions was investigated at different temperatures (25 to 45 °C) and pH (2.75 to 3.45). The rate of the oxidative dissolution of FeS is strongly dependent on pH. The reaction order with respect to hydrogen ions has been found to be 1.03 ± 0.02 at 25 °C, and the apparent activation energy ( E a ) is 41.6 ± 10.7 kJ mol−1 at initial pH 3.00, suggesting that the FeS oxidative dissolution is controlled by the diffusion of oxidant species across a sulfur-rich layer (SRL) that undergoes chemical transformations leading to an increase in the mean number of sulfur atoms in polysulfide chains and the rearrangement of these chains. Fourier transform infrared spectroscopy and X-ray diffraction results obtained for the FeS samples reacted for 72 h at 25 °C and pH between 2.75 and 3.45 indicate the formation of goethite, of lepidocrocite, and of poorly ordered solid phases (assigned as SRL) on initial surfaces. The experimental data suggest a mechanism based on the protonation of FeS surfaces followed by oxidation of FeS by dissolved oxygen to produce Fe2+, S0, and S2−n. Fe2+ is unstable under oxidative conditions and transforms into Fe(OH)3(s), goethite and lepidocrocite.

Comparison of catalytic decomposition of hydrogen peroxide and catalytic degradation of phenol by immobilized iron oxides

Abstract: Immobilized iron oxides on silica matrixes in fluidized bed reactors, including SiG1, SiG2, C1, and the commercial catalyst FeOOH, were used in the catalytic decomposition of H2O2 and the catalytic degradation of phenol. They were characterized using XRD, SEM, N2-sorption, and elucidation of the kinetics of dissolved iron by oxalic acid in dark surroundings. XRD patterns reveal that SiG1, SiG2, and C1 exhibit amorphous structures, and FeOOH exhibits the poor crystallinity of goethite. The SEM images reveal that the surfaces of all the iron oxides are smooth and that the iron oxides are aggregated by the iron oxide floc. The N2-sorption isotherm indicates that SiG1 and SiG2 are non-porous materials, and that C1 and FeOOH are typical type II and typical type IV materials, respectively. A kinetic model for iron dissolved by oxalic acid is established. The order of apparent first-order dissolution rate constants (kc) is SiG1 > SiG2 > FeOOH ∼ C1. The immobilized iron oxides, SiG1 and SiG2, are weakly bonded to the support (silica sand) in the presence of oxalic acid. The decomposition of H2O2 follows pseudo-first-order kinetics. The number of active sites for the decomposition of H2O2 is similar among all iron oxides at a particular kapp (1.8 × 10−3 min−1). There are no interactions between phenol and iron oxides in the absence of hydrogen peroxide at pH 4. SiG1 and SiG2 exhibit much higher catalytic activities in phenol degradation than either C1 or FeOOH. The reactivity of iron oxides in catalyzing the phenol degradation by H2O2 relates to the tendency of iron to be dissolved by oxalic acid. The intermediates of phenol degradation, such as catechol and oxalic acid, promote the dissolution of iron from SiG1 and SiG2 by reductive and non-reductive pathways and lower the pH values. The catalyses of SiG1 and SiG2 involve heterogeneous and homogeneous reactions.

The kinetics and mechanisms of schwertmannite transformation to goethite and hematite under alkaline conditions

Abstract: The transformation of schwertmannite to goethite and/or hematite in high pH solutions was studied between 60 and 240 °C using synchrotron-based, in-situ energy-dispersive X-ray diffraction (EDXRD). Powder diffraction and electron microscopy indicate that the crystallization of hematite and goethite occurred via intermediate ferrihydrite. At temperatures ≤80 °C goethite was the only crystallization product, while at temperatures >80 °C goethite and hematite crystallized almost simultaneously. At temperatures ≥150 °C a secondary crystallization stage was observed in which goethite transformed to hematite. The activation energies of nucleation for goethite and hematite are 27 ± 1 and 25 ± 1 kJ/mol, respectively, while the activation energies of crystallization are 33 ± 1 and 28 ± 1 kJ/mol. Most of the sulfate was released from the schwertmannite during the early stages of crystallization with <5% of the sulfate remaining associated with the solid phase after crystallization was complete. Sulfate from the initial schwertmannite retarded the dissolution of ferrihydrite, which inhibited the nucleation and the early stages of goethite formation, but did not significantly affect the later stages of goethite crystallization. At high temperatures the presence of sulfate favored the crystallization of hematite over goethite. The activation energy of crystallization for the secondary transformation of goethite to hematite is 103 ± 3 kJ/mol.

Catalytic properties of goethite prepared in the presence of Nb on oxidation reactions in water: Computational and experimental studies

Abstract: Nb-substituted goethites have been prepared and characterized by Mossbauer spectroscopy, XRD, FTIR and BET surface area measurements. The doublet formation in Mossbauer spectra and the decreasing of the crystallinity shown in XRD analyses indicated that the Fe domain size is small, which may be the result of either Fe3+ substitution for Nb5+ in the goethite structure or simply the formation of small particle-size goethite when Nb is present. FTIR analyses showed shifts and broadening of the bands as result of the incorporation of Nb5+ ions into the α-FeOOH structure. The insertion of Nb in the goethite structure caused a significant increase in the BET surface area of the material. The prepared materials were investigated for the H2O2 decomposition and the Fenton reaction in the oxidation of methylene blue dye. It was observed that the introduction of Nb during the synthesis of goethite produced a strong increase in the activity for the dye contaminant oxidation by H2O2. Theoretical quantum DFT calculations were carried out in order to understand the degradation mechanism for methylene blue with goethites.

Spectroscopic evidence for Ni(II) surface speciation at the iron oxyhydroxides-water interface.

Abstract: Understanding in situ metal surface speciation on mineral surfaces is critical to predicting the natural attenuation of metals in the subsurface environment. In this study, we have demonstrated the novel Ni K-edge X-ray absorption spectroscopy (XAS) measurements needed to understand Ni(ll) surface speciation in three synthetic iron oxyhydroxides (ferrihydrite, goethite, and hematite). The adsorption of Ni gradually increases with increasing pH from 5 to 8, and the adsorption edge appears at near the point of zero salt effect (PZSE) of the solids. The results of XAS analysis indicate four different Ni inner-sphere surface species are present. While total Ni surface species in hematite at pH 6.85 surfaces consist of approximately 63% face-sharing (interatomic distance of Ni-Fe (R(Ni-Fe)) approximately 2.9 A) and approximately 37% corner-sharing (R(Ni-Fe) approximately 4.0 A) surface species on iron octahedra, a combination of two different edge-sharing (between NiO6 and FeO6 octahedra, in chains or in rows) and corner-sharing surface species are observed in goethite and ferrihydrite at pH 5.09-6.89. In ferrihydrite, approximately 70% of surface species are edge-sharing surface species (in chains) (R(Ni-Fe) approximately 3.0 A), followed by approximately 30% of edge-sharing species (in rows) (R(Ni-Fe) approximately 3.2 A) and approximately 3-5% of corner-sharing surface species (R(Ni-Fe) approximately 4.0 A). Goethite contains approximately 54% edge-sharing (R(Ni-Fe) approximately 3.0 A), approximately 26% edge-sharing (R(Ni-Fe) approximately 3.2 A), and 20% corner-sharing surface species. These findings indicate that the reactivity and surface speciation of Ni are sensitive to the crystallinity of iron oxyhydroxides. The spectroscopic evidence for multi-Ni surface speciation should be factored into predictions of the transport of Ni in soil-water environments.

Enhancement of the reductive transformation of pentachlorophenol by polycarboxylic acids at the iron oxide-water interface.

Abstract: The enhancement effect of polycarboxylic acids on reductive dechlorination transformation of pentachlorophenol (PCP) reacting with iron oxides was studied in anoxic suspension. Batch experiments were performed with three species of iron oxides (goethite, lepidocrocite and hematite) and four species of polycarboxylic acids (oxalate, citrate, succinate, and tartrate) through anoxic abiotic reactors. The chemical analyses and morphological observation from scanning and transmission electron microscopy showed that different combinations between polycarboxylic acids and iron oxides produced distinct contents of Fe(II)-polycarboxylic ligand complexes, which significantly enhanced PCP transformation. Generation of the surface-bound Fe(II) depended on concentration of polycarboxylic acids. The optimal concentration for the enhancement was 2.0 mM oxalic acid. The dechlorination mechanism was further demonstrated by generation of chloride ions. The results suggest that surface-bound Fe(II) formed on the iron oxides surface appears to be a key factor in enhancing PCP transformation, and the mole ratio of oxalate to surface-bound Fe(II) (oxalate/Fe(II)) acted as an indicator of the enhancement effect. The enhancement mechanism attributes to strong nucleophilic ability and low reductive potential of the equivalent Fe(II)-polycarboxylate complexes. Therefore, the enhancement effects might be helpful for understanding the natural attenuation of reducible organic pollutants at the interface of contaminated soil in anoxic condition.

Periodic density functional theory calculations of bulk and the (010) surface of goethite

Abstract: Goethite is a common and reactive mineral in the environment. The transport of contaminants and anaerobic respiration of microbes are significantly affected by adsorption and reduction reactions involving goethite. An understanding of the mineral-water interface of goethite is critical for determining the molecular-scale mechanisms of adsorption and reduction reactions. In this study, periodic density functional theory (DFT) calculations were performed on the mineral goethite and its (010) surface, using the Vienna Ab Initio Simulation Package (VASP). Calculations of the bulk mineral structure accurately reproduced the observed crystal structure and vibrational frequencies, suggesting that this computational methodology was suitable for modeling the goethite-water interface. Energy-minimized structures of bare, hydrated (one H2O layer) and solvated (three H2O layers) (010) surfaces were calculated for 1 × 1 and 3 × 3 unit cell slabs. A good correlation between the calculated and observed vibrational frequencies was found for the 1 × 1 solvated surface. However, differences between the 1 × 1 and 3 × 3 slab calculations indicated that larger models may be necessary to simulate the relaxation of water at the interface. Comparison of two hydrated surfaces with molecularly and dissociatively adsorbed H2O showed a significantly lower potential energy for the former. Surface Fe-O and (Fe)O-H bond lengths are reported that may be useful in surface complexation models (SCM) of the goethite (010) surface. These bond lengths were found to change significantly as a function of solvation (i.e., addition of two extra H2O layers above the surface), indicating that this parameter should be carefully considered in future SCM studies of metal oxide-water interfaces.