Showing papers on "Goethite published in 2003"

Comparison of arsenic(V) and arsenic(III) sorption onto iron oxide minerals: implications for arsenic mobility.

Abstract: Arsenic derived from natural sources occurs in groundwater in many countries, affecting the health of millions of people. The combined effects of As(V) reduction and diagenesis of iron oxide minerals on arsenic mobility are investigated in this study by comparing As(V) and As(III) sorption onto amorphous iron oxide (HFO), goethite, and magnetite at varying solution compositions. Experimental data are modeled with a diffuse double layer surface complexation model, and the extracted model parameters are used to examine the consistency of our results with those previously reported. Sorption of As(V) onto HFO and goethite is more favorable than that of As(III) below pH 5−6, whereas, above pH 7−8, As(III) has a higher affinity for the solids. The pH at which As(V) and As(III) are equally sorbed depends on the solid-to-solution ratio and type and specific surface area of the minerals and is shifted to lower pH values in the presence of phosphate, which competes for sorption sites. The sorption data indicate tha...

Nanogoethite is the dominant reactive oxyhydroxide phase in lake and marine sediments

Abstract: Iron oxides affect many elemental cycles in aquatic sediments via numerous redox reactions and their large sorption capacities for phosphate and trace elements. The reactive ferric oxides and oxyhydroxides are usually quantified by operationally defined selective chemical extractions that are not mineral specific. We have used cryogenic 57Fe Mossbauer spectroscopy to show that the reactive iron oxyhydroxide phase in a large variety of lacustrine and marine environments is nanophase goethite (α-FeOOH), rather than the assumed surface-complex–stabilized, two-line ferrihydrite and accompanying mixture of clay and oxyhydroxide Fe-bearing phases. This result implies that the kinetic and stability parameters of the type of nanogoethite that we observe to be present in sediments should be first determined and then used in models of early diagenesis. The identity and characteristics of the reactive phase will also set constraints on the mechanisms of its authigenesis.

Evidence for surface precipitation of phosphate on goethite.

Abstract: Recent studies have suggested that the interaction between phosphate and goethite includes ternary adsorption/surface precipitation as well as surface complex formation The ternary adsorption/surface precipitation process envisioned involves the dissolution of the goethite crystal and subsequent adsorption of iron on the surface-bound phosphate Further evidence to support the suggested process is needed The process was investigated using two approaches First, the sorption of iron spiked into a slurry of phosphated goethite and the effect of the iron sorption on phosphate uptake kinetics were investigated to determine whether iron would be adsorbed on the phosphated surface and whether it would enhance phosphate adsorption Lead was also spiked into solution for comparison Second, changes in the ζ-potential of phosphated goethite were monitored with time Adsorption of iron on the surface of phosphated goethite should increase the ζ-potential of the goethite Iron spiked into a phosphated goethite slu

Modeling the adsorption of citric acid onto Muloorina illite and related clay minerals

Abstract: The adsorption of citric acid onto goethite, kaolinite, and illite was measured as a function of pH (adsorption edges) and concentration (adsorption isotherms) at 25 degrees C. The greatest adsorption was onto goethite and the least onto illite. Adsorption onto goethite was at a maximum below pH 5 and decreased as the pH was increased to pH 9. For kaolinite, maximum adsorption occurred between pH 4.5 and pH 7, decreasing below and above this pH region, while for illite maximum adsorption occurred between about pH 5 and pH 7, decreasing at both lower and higher pH. ATR-FTIR spectra of citrate adsorbed to goethite at pH 4.6, pH 7.0, and pH 8.8 were compared with those of citrate solutions between pH 3.5 and pH 9.1. While the spectra of adsorbed citrate resembled those of the fully deprotonated solution species, there were significant differences. In particular the C[bond]O symmetric stretching band of the adsorbed species at pH 4.6 and 7.0 changed shape and was shifted to higher wave number. Further spectral analysis suggested that citrate adsorbed as an inner-sphere complex at pH 4.6 and pH 7.0 with coordination to the surface most probably via one or more carboxyl groups. At pH 8.8 the intensity of the adsorbed bands was much smaller but their shape was similar to those from the deprotonated citrate solution species, suggesting outer-sphere adsorption. Insufficient citric acid adsorbed onto illite or kaolinite to provide spectroscopic information about the mode of adsorption onto these minerals. Data from adsorption experiments, and from potentiometric titrations of suspensions of the minerals in the presence of citric acid, were fitted by extended constant-capacitance surface complexation models. On the goethite surface a monodentate inner-sphere complex dominated adsorption below pH 7.9, with a bidentate outer-sphere complex required at higher pH values. On kaolinite, citric acid adsorption was modeled with a bidentate outer-sphere complex at low pH and a monodentate outer-sphere complex at higher pH. There is evidence of dissolution of kaolinite in the presence of citric acid. For illite two bidentate outer-sphere complexes provided a good fit to all data.

Thermodynamics of Fe oxides: Part II. Enthalpies of formation and relative stability of goethite (α-FeOOH), lepidocrocite (γ-FeOOH), and maghemite (γ-Fe2O3)

Abstract: The enthalpy of formation from the elements at 298.15 K of lepidocrocite ( gamma-FeOOH) and maghemite ( gamma-Fe 2 O 3 has been measured by acid-solution calorimetry as -549.4 ± 1.4 and -808.1 ± 2.9 kJ/mol, respectively. The enthalpy of formation of goethite ( alpha-FeOOH) was measured by high-temperature transposed temperature drop and acid-solution calorimetry as -559.5 ± 1.1 and 560.7 ± 1.2 kJ/mol, respectively. Mathematical programming analysis (MAP) was used to generate an internally consistent data set for goethite and hematite, using the thermodynamic data presented in this study for goethite, and additional thermodynamic data for hematite and synthesis experiments of Baneyeva and Bendeliani (1973) (BB) and Voigt and Will (1981) (VW). Using BB brackets, the thermodynamic values for goethite were refined to the enthalpy of formation = -561.9 kJ/mol and entropy at standard pressure and temperature (S ) = 59.2 J/K mol; using VW brackets, we arrived at the enthalpy of formation = 561.4 kJ/mol and S = 59.5 J(K.mol). However, MAP failed to include the magnetic transition in goethite, and the derived data should be used with caution. Combined with the entropies for the studied phases, the Gibbs free energies of formation from the elements at 298.15 K are -489.8 ± 1.2, -480.1 ± 1.4, and -727.9 ± 2.0 kJ/mol, for goethite, lepidocrocite, and maghemite, respectively. Only hematite ( alpha-Fe 2 O 3 ) and goethite have a stability field in the Fe 2 O 3 -H 2 O system at low to moderate pressures; maghemite and lepidocrocite are metastable at all pressures and temperatures. Goethite is 1.0 ± 1.4 kJ/mol metastable in G with respect to hematite and liquid water, and 2.0 ± 1.4 kJ/mol metastable with respect to hematite and water vapor at 298 K and 50% relative humidity.

Microbial Reduction of Structural Fe(III) in Illite and Goethite

Abstract: Microbial reduction of Fe(III) in illite was studied to evaluate the possibility of microbial utilization of Fe(III) in sedimentary clays and to determine the effects of bioreduction on clay compos...

From Nanodots to Nanorods: Oriented aggregation and magnetic evolution of nanocrystalline goethite

Abstract: [1] Goethite is a common iron oxyhydroxide and an important mineral in the biogeochemical cycle of iron at the Earth's surface. However, environmental controls on its formation and alteration have been difficult to quantify. Perhaps this is because past studies have traditionally used needle-shaped goethite particles that are substantially larger than the goethite nanoparticles commonly observed in nature. High-resolution transmission electron microscopy and low-temperature magnetometry of synthetic goethite nanocrystals show that when aqueous suspensions are aged at 90°C, the nanocrystals grow almost exclusively by oriented aggregation of 3–4 nm primary nanocrystals. These primary particles are superparamagnetic above about 35 K, as shown by variations of magnetic susceptibility with temperature. At low temperature (<300 K), both remanent and induced magnetizations of primary nanoparticles are about an order of magnitude larger than for micron-sized goethite and can act as magnetic signatures of nanophase in controlled environments.

Chemical and Biological Interactions during Nitrate and Goethite Reduction by Shewanella putrefaciens 200

Abstract: Although previous research has demonstrated that NO3− inhibits microbial Fe(III) reduction in laboratory cultures and natural sediments, the mechanisms of this inhibition have not been fully studied in an environmentally relevant medium that utilizes solid-phase, iron oxide minerals as a Fe(III) source. To study the dynamics of Fe and NO3− biogeochemistry when ferric (hydr)oxides are used as the Fe(III) source, Shewanella putrefaciens 200 was incubated under anoxic conditions in a low-ionic-strength, artificial groundwater medium with various amounts of NO3− and synthetic, high-surface-area goethite. Results showed that the presence of NO3− inhibited microbial goethite reduction more severely than it inhibited microbial reduction of the aqueous or microcrystalline sources of Fe(III) used in other studies. More interestingly, the presence of goethite also resulted in a twofold decrease in the rate of NO3− reduction, a 10-fold decrease in the rate of NO2− reduction, and a 20-fold increase in the amounts of N2O produced. Nitrogen stable isotope experiments that utilized δ15N values of N2O to distinguish between chemical and biological reduction of NO2− revealed that the N2O produced during NO2− or NO3− reduction in the presence of goethite was primarily of abiotic origin. These results indicate that concomitant microbial Fe(III) and NO3− reduction produces NO2− and Fe(II), which then abiotically react to reduce NO2− to N2O with the subsequent oxidation of Fe(II) to Fe(III).

Geochemical distribution of arsenic in waters, sediments and weathered gold mineralized rocks from Iron Quadrangle, Brazil

Abstract: The Iron Quadrangle has been the scenery of the most important gold production in Brazil. It is estimated that during the three centuries of gold mining in the Iron Quadrangle, at least 390,000 t of arsenic was discharged into the drainage system. This study presents geochemical data for the three river basins in the region, with focus on surface water and stream sediment monitoring. Samples of primary and oxidized sulfide ores as well as of tailings and groundwater from the major gold mines were also studied. The highest As concentrations in water and stream sediments occur in the vicinity of mining areas. In surface water, up to 300 g As/l were found whereas the As contents in stream sediments were in the range of 20 to 4,000 mg/kg. The As3+/As5+ concentration ratios obtained for some water samples range from 1.10−1 to 4.10−2. The As mobility associated with ore-deposit weathering could be traced in some closed gold mines by observation of in-situ pyrite and arsenopyrite oxidation, precipitation of scorodite and gippsite, As adsorption onto goethite, and final liberation of As into underground and surface waters. This process is likely to produce large volumes of mine effluents containing total As and trivalent As up to 1,960 and 60 g/l, respectively. River sediments and tailings pile samples were submitted to a leaching procedure showing maximal arsenic release from 1 to 4% of the original total As in the samples. There are potential risks for As hazards in some areas induced by, for instance, the dispersion of old tailings by flooding, occupation of poisoned soils for settlements, and occasional consumption of contaminated surface and groundwater.

Incorporation of Ni into natural goethite: An investigation by X-ray absorption spectroscopy

Abstract: Goethite (α-FeOOH) is abundant at the Earth’s surface and has the unusual capacity to adsorb and fix ions from migrating solutions. Understanding the mechanisms by which foreign elements are incorporated into natural goethite has implications for environmental and mining problems. X-ray absorption spectroscopy (XAS) was used to obtain structural information on the local environment around Ni in natural Ni-containing goethite (1.8–4.1 mol% Ni) from Vermelho lateritic deposit of Serra dos Carajas (Brazil) and in synthetic analogues. The data were collected at the LNLS XAS beam line at the Ni and Fe K -edges, at room temperature, and at the Ni K -edge at 8 K. Nickel was found in essentially the same environment in all natural and synthetic samples, with negligible thermal disorder. The coordination polyhedron is a tetragonal dipyramid of oxygen atoms showing that Ni preserves its usual local symmetry. This finding is compatible with a model in which substitution of Ni for Fe is accompanied by a proton capture resulting in NiO2(OH)4 octahedra. The polyhedral linkages are similar to that of pure a-FeOOH, consisting of four shared edges at about the same metal-metal distances, as in the pure mineral. The third and longest metal-metal distance is about 6% larger than the expected corner-sharing distance in the α-FeOOH structure, showing that incorporation of Ni locally distorts and opens the structure.

Temperature Dependence of Goethite Dissolution Promoted by Trihydroxamate Siderophores

Abstract: OAK-B135 Results of laboratory experiments are presented on the dissolution behavior of the mineral, goethite, in the presence of siderophores as affected by temperature changes between 25 and 55 Celsius. Data also are presented on the relationship between the parameters in the Arrhenius equation describing the temperature effects.

Sorption of uranium(VI) onto ferric oxides in sulfate-rich acid waters.

Abstract: The mechanisms of the uranium(VI) sorption on schwertmannite and goethite in acid sulfate-rich solutions were studied by Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. The samples were prepared under N2 atmosphere and initial uranium(VI) concentrations of 1 x 10(-5) (pH 6.5) to 5 x 10(-5) M (pH 4.2). The ionic strength was adjusted using 0.01 M Na2SO4 or 0.01 M NaClO4, respectively. The EXAFS structural parameters for uranium(VI) sorbed on goethite in sulfate-rich, acid and near-neutral solutions indicate that uranium(VI) forms an inner-sphere, mononuclear, bidentate surface complex. This complex is characterized by a uranium-ferric-iron distance of approximately 3.45 A. Uranium(VI) sorbed onto schwertmannite in acid and sulfate-rich solution is coordinated to one or two sulfate molecules with a uranium-sulfur distance of 3.67 A. The EXAFS results indicate formation of binuclear, bidentate surface complexes and partly of mononuclear, monodentate surface complexes coordinated to the structural sulfate of schwertmannite. The formation of ternary uranium(VI)-sulfate surface complexes could not be excluded because of the uncertainty in assigning the sulfate either to the bulk structure or to adsorption reactions. The uranium(VI) adsorption onto schwertmannite in perchlorate solution occurs predominantly as a mononuclear, bidentate complexation with ferric iron due to the release of sulfate from the substrate.

Green rust and iron oxide formation influences metolachlor dechlorination during zerovalent iron treatment

Abstract: Electron transfer from zerovalent iron (Fe0) to targeted contaminants is affected by initial Fe0 composition, the oxides formed during corrosion, and surrounding electrolytes. We previously observed enhanced metolachlor destruction by Fe0 when iron or aluminum salts were present in the aqueous matrix and Eh/pH conditions favored formation of green rusts. To understand these enhanced destruction rates, we characterized changes in Fe0 composition during treatment of metolachlor with and without iron and aluminum salts. Raman microspectroscopy and X-ray diffraction (XRD) indicated that the iron source was initially coated with a thin layer of magnetite (Fe3O4), maghemite (gamma-Fe2O3), and wustite (FeO). Time-resolved analysis indicated that akaganeite (beta-FeOOH) was the dominant oxide formed during Fe0 treatment of metolachlor. Goethite (alpha-FeOOH) and some lepidocrocite (gamma-FeOOH) formed when Al2(SO4)3 was present, while goethite and magnetite (Fe3O4) were identified in Fe0 treatments containing FeSO4. Although conditions favoring formation of sulfate green rust (GR(II); Fe6(OH)12SO4) facilitated Fe0-mediated dechlorination of metolachlor, only adsorption was observed when GR(II) was synthesized (without Fe0) in the presence of metolachlor and Eh/pH changed to favor Fe(III)oxyhydroxide or magnetite formation. In contrast, dechlorination occurred when magnetite or natural goethite was amended with Fe(II) (as FeSO4) at pH 8 and continued as long as additional Fe(II) was provided. While metolachlor was not dechlorinated by GR(II) itself during a 48-h incubation, the GR(II) provided a source of Fe(II) and produced magnetite (and other oxide surfaces) that coordinated Fe(II), which then facilitated dechlorination.

Speciation of Pb(II) sorbed by Burkholderia cepacia/goethite composites.

Abstract: Bacterial-mineral composites are important in the retention of heavy metals such as Pb due to their large sorption capacity under a wide range of environmental conditions. However, the partitioning of heavy metals between components in such composites is not probed directly. Using Burkholderia cepacia biofilms coated with goethite (α-FeOOH) particles, the partitioning of Pb(II) between the biological and iron-(oxyhydr)oxide surfaces has been measured using an X-ray spectroscopic approach. EXAFS spectra were fit to quantitatively determine the fraction of Pb(II) associated with each component as a function of pH and [Pb]. At pH 70% Pb/goethite) above pH 6. Direct comparison can be made between the amount of Pb(II) bound to each component in the composite vs separate binary systems (i.e., Pb/biofilm or Pb/goethite). At high pH, Pb(II) uptake on the ...