Showing papers on "Goethite published in 2015"

Heteroaggregation of graphene oxide with minerals in aqueous phase.

Abstract: Upon release into waters, sediments, and soils, graphene oxide (GO) may interact with fine mineral particles. We investigated the heteroaggregation of GO with different minerals, including montmorillonite, kaolinite, and goethite, in aqueous phase. GO significantly enhanced the dispersion of positively charged goethite (>50%) via heteroaggregation, while there was no interaction between GO and negatively charged montmorillonite or kaolinite. Electrostatic attraction was the dominant force in the GO–goethite heteroaggregation (pH 4.0–8.5), and the dissolved Fe ions (<0.16 mg/L) from goethite were unable to destabilize GO suspension. The GO–goethite heteroaggregation was further quantitatively investigated through GO adsorption study. All adsorption isotherms of GO at different solution pH (4.0 and 6.5) followed the Linear model. The apparent intercept (1.0–6.9 mg/g) was observed for all the adsorption isotherms, indicating that this fraction of adsorbed GO was difficult to desorb from goethite (defined her...

Influence of Coprecipitated Organic Matter on Fe2+(aq)-Catalyzed Transformation of Ferrihydrite: Implications for Carbon Dynamics.

Abstract: Aqueous Fe(II) is known to catalyze the abiotic transformation of ferrihydrite to more stable Fe minerals. However, little is known about the impacts of coprecipitated OM on Fe(II)-catalyzed ferrihydrite transformation and its consequences for C dynamics. Accordingly, we investigated the extent and pathway of Fe(II)-induced transformation of OM-ferrihydrite coprecipitates as a function of C/Fe ratios and aqueous Fe(II) concentrations, and its implications for subsequent C dynamics. The coprecipitated OM resulted in a linear decrease in ferrihydrite transformation with increasing C/Fe ratios. The secondary mineral profiles upon Fe(II) reaction with OM-ferrihydrite coprecipitates depend on Fe(II) concentrations At 0.2 mM Fe(II), OM completely inhibited goethite formation and stimulated lepidocrocite formation. At 2 mM Fe(II), whereas goethite was formed in the presence of OM, OM reduced the amount of goethite and magnetite formation and increased the formation of lepidocrocite. The solid-phase C content rem...

Stable isotopes and iron oxide mineral products as markers of chemodenitrification.

Abstract: When oxygen is limiting in soils and sediments, microorganisms utilize nitrate (NO3-) in respiration--through the process of denitrification--leading to the production of dinitrogen (N2) gas and trace amounts of nitrous (N2O) and nitric (NO) oxides. A chemical pathway involving reaction of ferrous iron (Fe2+) with nitrite (NO2-), an intermediate in the denitrification pathway, can also result in production of N2O. We examine the chemical reduction of NO2- by Fe(II)--chemodenitrification--in anoxic batch incubations at neutral pH. Aqueous Fe2+ and NO2- reacted rapidly, producing N2O and generating Fe(III) (hydr)oxide mineral products. Lepidocrotite and goethite, identified by synchrotron X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) spectroscopy, were produced from initially aqueous reactants, with two-line ferrihydrite increasing in abundance later in the reaction sequence. Based on the similarity of apparent rate constants with different mineral catalysts, we propose that the chemodenitrification rate is insensitive to the type of Fe(III) (hydr)oxide. With stable isotope measurements, we reveal a narrow range of isotopic fractionation during NO2- reduction to N2O. The location of N isotopes in the linear N2O molecule, known as site preference, was also constrained to a signature range. The coexistence of Fe(III) (hydr)oxide, characteristic 15N and 18O fractionation, and N2O site preference may be used in combination to qualitatively distinguish between abiotic and biogenically emitted N2O--a finding important for determining N2O sources in natural systems.

Synergistic effect of reductive and ligand-promoted dissolution of goethite.

Abstract: Ligand-promoted dissolution and reductive dissolution of iron (hydr)oxide minerals control the bioavailability of iron in many environmental systems and have been recognized as biological iron acquisition strategies. This study investigated the potential synergism between ligands (desferrioxamine B (DFOB) or N,N'-Di(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid (HBED)) and a reductant (ascorbate) in goethite dissolution. Batch experiments were performed at pH 6 with ligand or reductant alone and in combination, and under both oxic and anoxic conditions. Goethite dissolution in the presence of reductant or ligand alone followed classic surface-controlled dissolution kinetics. Ascorbate alone does not promote goethite dissolution under oxic conditions due to rapid reoxidation of Fe(II). The rate coefficients for goethite dissolution by ligands are closely correlated with the stability constants of the aqueous Fe(III)-ligand complexes. A synergistic effect of DFOB and ascorbate on the rate of goethite dissolution was observed (total rates greater than the sum of the individual rates), and this effect was most pronounced under oxic conditions. For HBED, macroscopically the synergistic effect was hidden due to the inhibitory effect of ascorbate on HBED adsorption. After accounting for the concentrations of adsorbed ascorbate and HBED, a synergistic effect could still be identified. The potential synergism between ligand and reductant for iron (hydr)oxide dissolution may have important implications for iron bioavailability in soil environments.

Laboratory synthesis of goethite and ferrihydrite of controlled particle sizes

Abstract: Iron oxyhydroxides, such as goethite and ferrihydrite, are highly abundant and ubiquitous minerals in geochemical environments. Because of their small particle sizes, their surface reactivity is high towards adsorption of anions and cations of environmental relevance. For this reason these minerals are extensively studied in environmental geochemistry, and also are very important for environmental and industrial applications. In the present work, we report the synthesis and characterization of goethite and ferrihydrite of controlled particle sizes. It has been shown that surface reactivity of these minerals is highly dependent on crystal sizes, even after normalizing by specific surface area. In order to investigate the reasons for this changing reactivity it is necessary to work with reproducible particle sizes of these minerals. We investigated here the experimental conditions to synthesize goethite samples of four different specific surface areas: ca. 40, 60, 80 and 100 m2 g-1, through the controlled speed of hydroxide addition during hydrolysis of acid Fe(III) solutions. In the case of 2-line ferrihydrite, samples with two different particle sizes were prepared by changing the aging time under the pH conditions of synthesis (pH = 7.5). The synthesized minerals were identified and characterized by: X-ray diffraction, N2 adsorption BET specific surface area, transmission electron microscopy, attenuated total reflectance Fourier transform infrared spectroscopy, and maximum Cr(VI) adsorption.

Surface loading effects on orthophosphate surface complexation at the goethite/water interface as examined by extended X-ray Absorption Fine Structure (EXAFS) spectroscopy.

Abstract: To investigate the effect of P surface loading on the structure of surface complexes formed at the goethite/water interface, goethite was reacted with orthophosphate at P concentrations of 0.1, 0.2, and 0.8 mmol L −1 at pH 4.5 for 5 days. The P concentrations were chosen to ensure that P loadings at the surface would allow one to follow the transition between adsorption and surface precipitation. Extended X-ray Absorption Fine Structure (EXAFS) spectra were collected in fluorescence mode at the P K-edge at 2150 eV. The structural parameters were obtained through the fits of the sorption data to single and multiple scattering paths using Artemis. EXAFS analysis revealed a continuum among the different surface complexes, with bidentate mononuclear ( 2 E), bidentate binuclear ( 2 C) and monodentate mononuclear ( 1 V) surface complexes forming at the goethite/water interface under the studied conditions. The distances for P–O (1.51–1.53 A) and P–Fe (3.2–3.3 A for bidentate binuclear and around 3.6 A for mononuclear surface complexes) shells observed in our study were consistent with distances obtained via other spectroscopic techniques. The shortest P–Fe distance of 2.83–2.87 A was indicative of a bidentate mononuclear bonding configuration. The coexistence of different surface complexes or the predominance of one sorption mechanism over others was directly related to surface loading.

Ab initio modeling of Fe(II) adsorption and interfacial electron transfer at goethite (α-FeOOH) surfaces

Abstract: Goethite (α-FeOOH) surfaces represent one of the most ubiquitous redox-active interfaces in the environment, playing an important role in biogeochemical metal cycling and contaminant residence in the subsurface. Fe(II)-catalyzed recrystallization of goethite is a fundamental process in this context, but the proposed Fe(II)aq–Fe(III)goethite electron and iron atom exchange mechanism of recrystallization remains poorly understood at the atomic level. We examine the adsorption of aqueous Fe(II) and subsequent interfacial electron transfer (ET) between adsorbed Fe(II) and structural Fe(III) at the (110) and (021) goethite surfaces using density functional theory calculations including Hubbard U corrections (DFT + U) aided by ab initio molecular dynamics simulations. We investigate various surface sites for the adsorption of Fe2+(H2O)6 in different coordination environments. Calculated energies for adsorbed complexes at both surfaces favor monodentate complexes with reduced 4- and 5-fold coordination over higher-dentate structures and 6-fold coordination. The hydrolysis of H2O ligands is observed for some pre-ET adsorbed Fe(II) configurations. ET from the adsorbed Fe(II) into the goethite lattice is calculated to be energetically uphill always, but simultaneous proton transfer from H2O ligands of the adsorbed complexes to the surface oxygen species stabilizes post-ET states. We find that surface defects such as oxygen vacancies near the adsorption site also can stabilize post-ET states, enabling the Fe(II)aq–Fe(III)goethite interfacial electron transfer reaction implied from experiments to proceed.

Non-thermal plasma synthesis of sea-urchin like alpha-FeOOH for the catalytic oxidation of Orange II in aqueous solution

Abstract: In this study, a template-free synthesis of iron oxyhydroxide nanostructures by gliding arc plasma at atmospheric pressure was evaluated. The results showed that exposure of a Mohr’s salt solution to the plasma discharge induces a rapid oxidation–precipitation of iron(II) into a non-porous and amorphous iron(III) (hydr) oxide. After ageing in temporal post-discharge for three hours, the amorphous iron (hydr) oxide was transformed into crystalline goethite (α-FeOOH). The presence of goethite was confirmed by FTIR, Raman spectroscopy and thermogravimetric analysis. Textural analyses showed that the material is mesoporous with a BET surface area of 134 m2 g−1. SEM pictures revealed that the plasma-synthesized goethite particles consist of sea-urchin like hollow spheres. The catalytic activity of such goethite in the Fenton degradation of Orange II (organic dye) showed that this material can be used as heterogeneous catalyst for effective removal of organic pollutants from wastewater. This study establishes that the plasma discharge of gliding arc type can be used as a green and cheap efficient route for the synthesis of porous metal oxide nanostructures.

Technetium Incorporation into Goethite (α-FeOOH): An Atomic-Scale Investigation

Abstract: During the processing of low-activity radioactive waste to generate solid waste forms (e.g., glass), technetium-99 (Tc) is of concern because of its volatility. A variety of materials are under consideration to capture Tc from waste streams, including the iron oxyhydroxide, goethite (α-FeOOH), which was experimentally shown to sequester Tc(IV). This material could ultimately be incorporated into glass or alternative low-temperature waste form matrices. However, questions remain regarding the incorporation mechanism for Tc(IV) in goethite, which has implications for predicting the long-term stability of Tc in waste forms under changing conditions. Here, quantum-mechanical calculations were used to evaluate the energy of five different charge-compensated Tc(IV) incorporation scenarios in goethite. The two most stable incorporation mechanisms involve direct substitution of Tc(IV) onto Fe(III) lattice sites and charge balancing either by removing one nearby H(+) (i.e., within 5 A) or by creating an Fe(III) vacancy when substituting 3 Tc(IV) for 4 Fe(III), with the former being preferred over the latter relative to gas-phase ions. When corrections for hydrated references phases are applied, the Fe(III)-vacancy mechanism becomes more energetically competitive. Calculated incorporation energies and optimized bond lengths are presented. Proton movement is observed to satisfy undercoordinated bonds surrounding Fe(III)-vacancies in the goethite structure.

In situ Imaging of Interfacial Precipitation of Phosphate on Goethite

Abstract: Adsorption and subsequent immobilization of orthophosphate on iron oxides is of considerable importance in soil fertility and eutrophication studies. Here, in situ atomic force microscopy (AFM) has been used to probe the interaction of phosphate-bearing solutions with goethite, α-FeOOH, (010) cleavage surfaces. During the dissolution of goethite we observed simultaneous nucleation of nanoparticles (1.0–3.0 nm in height) of iron phosphate (Fe–P) phases at the earliest nucleation stages, subsequent aggregation to form secondary particles (about 6.0 nm in height) and layered precipitates under various pH values and ionic strengths relevant to acid soil solution conditions. The heterogeneous nucleation rates of Fe–P precipitates at phosphate concentrations ranging from 5.0 to 50.0 mM were quantitatively defined. Enhanced goethite dissolution in the presence of high concentration NaCl or AlCl3 leads to a rapid increase in Fe–P nucleation rates, whereas low concentration MgCl2 inhibits goethite dissolution, thi...

Effects of metal cations and fulvic acid on the adsorption of ciprofloxacin onto goethite

Abstract: Ciprofloxacin (CIP) can be strongly adsorbed by ferric oxides, but some influencing factors, such as multivalent cations and soil organic matter, have not been evaluated extensively. In this study, the interaction between CIP and four divalent metals (Ca, Cd, Cu, and Pb) was investigated using potentiometric titration and the results indicated that CIP can bind to the divalent metals in the following affinity order: Cu(II) > Pb(II) > Cd(II) > Ca(II). The effects of metals and fulvic acid (FA) on the adsorption behavior of CIP onto goethite surfaces were also examined using batch experiments. It was found that metal cations enhanced the CIP retention on goethite surfaces in the same order as the affinity order with CIP, indicating that metals likely increased CIP retention through cation bridging. FA was found to promote CIP sorption rather than compete with it, and the coexistence of FA and Cu(II) in the system exhibited an addictive effect with CIP sorption, indicating that they might influence the sorption separately under the studied loading condition. Taken together, our results suggested that the coexistence of divalent cations or soil organic matter will enhance CIP sorption on goethite surfaces, hence reducing its mobility and bioavailability in the environment.

Impact of environmental conditions on aggregation kinetics of hematite and goethite nanoparticles

Abstract: Hematite and goethite nanoparticles were used as model minerals to investigate their aggregation kinetics under soil environmental conditions in the present study. The hydrodynamic diameters of hematite and goethite nanoparticles were 34.4 and 66.3 nm, respectively. The positive surface charges and zeta potential values for goethite were higher than for hematite. The effective diameter for goethite was much larger than for hematite due to anisotropic sticking of needle-shaped goethite during aggregation. Moreover, the critical coagulation concentration (CCC) values of nanoparticles in solutions of NaNO3, NaCl, NaF, and Na2SO4 were 79.2, 75.0, 7.8, and 0.5 mM for hematite and they were 54.7, 62.6, 5.5, and 0.2 mM for goethite, respectively. The disparity of anions in inducing hematite or goethite aggregation lay in the differences in interfacial interactions. NO3 − and Cl− could decrease the zeta potential and enhance aggregation mainly through increasing ionic strength and compressing electric double layers of hematite and goethite nanoparticles. F− and SO4 2− highly destabilized the suspensions of nanoparticles mainly through specific adsorption and then neutralizing the positive surface charges of nanoparticles. Specific adsorption of cations could increase positive surface charges and stabilize hematite and goethite nanoparticles. The Hamaker constants of hematite and goethite nanoparticles were calculated to be 2.87 × 10−20 and 2.29 × 10−20 J−1, respectively. The predicted CCC values based on DLVO theory were consistent well with the experimentally determined CCC values in NaNO3, NaCl, NaF, and Na2SO4 systems, which demonstrated that DLVO theory could successfully predict the aggregation kinetics even when specific adsorption of ions occurred.