Showing papers on "Goethite published in 2004"

Reactivity of Fe(II)-bearing minerals toward reductive transformation of organic contaminants.

Abstract: Fe(II) present at surfaces of iron-containing minerals can play a significant role in the overall attenuation of reducible contaminants in the subsurface. As the chemical environment, i.e., the type and arrangement of ligands, strongly affects the redox potential of Fe(II), the presence of various mineral sorbents is expected to modulate the reactivity of surficial Fe(II)-species in aqueous systems. In a comparative study we evaluated the reactivity of ferrous iron in aqueous suspensions of siderite (FeCO3), nontronite (ferruginous smectite SWa-1), hematite (α-Fe2O3), lepidocrocite (γ-FeOOH), goethite (α-FeOOH), magnetite (Fe3O4), sulfate green rust (FeII4FeIII2(OH)12SO4·4H2O), pyrite (FeS2), and mackinawite (FeS) under similar conditions (pH 7.2, 25 m2 mineral/L, 1 mM Fe(II)aq, O2 (aq) < 0.1 g/L). Surface-area-normalized pseudo first-order rate constants are reported for the reduction of hexachloroethane and 4-chloronitrobenzene representing two classes of environmentally relevant transformation reaction...

Iron isotope fractionation during microbial reduction of iron: The importance of adsorption

Abstract: In experiments investigating the causes of Fe isotope fractionation, the d 56/54 Fe value of Fe(II) remaining in solution (Fe(II)(aq)) after reduction of Fe(III) (goethite) by Shewanella putrefaciens is ;21.2‰ relative to the goethite, in agreement with previous research. The addition of an electron shuttle did not affect fractionation, suggesting that Fe isotope fractionation may not be related to the kinetics of the electron transfer. Furthermore, in abiotic, anaerobic FeCl2(aq) experiments in which approximately one-third of Fe(II)(aq) is lost from solution due to adsorption of Fe(II) onto goethite, the d 56/54 Fe value of Fe(II)(aq) remaining in solution is shifted by 20.8‰ relative to FeCl 2. This finding demonstrates that anaerobic nonbiological interaction between Fe(II) and goethite can generate signif- icant Fe isotope fractionation. Acid extraction of sorbed Fe(II) from goethite in experi- ments reveals that heavy Fe preferentially sorbs to goethite. Simple mass-balance modeling indicates that the isotopic composition of the sorbed Fe(II) pool is ;11.5‰ to 12.5‰ heavier than Fe in the goethite (;2.7‰-3.7‰ heavier than aqueous Fe(II)). Mass balance is also consistent with a pool of heavy Fe that is not released to solution during acid extraction.

EXAFS study of mercury(II) sorption to Fe- and Al-(hydr)oxides. I. Effects of pH.

Abstract: The study of mercury sorption products in model systems using appropriate in situ molecular-scale probes can provide detailed information on the modes of sorption at mineral/water interfaces. Such studies are essential for assessing the influence of sorption processes on the transport of Hg in contaminated natural systems. Macroscopic uptake of Hg(II) on goethite ( α -FeOOH), γ -alumina ( γ -Al 2 O 3 ), and bayerite ( β -Al(OH) 3 ) as a function of pH has been combined with Hg L III -edge EXAFS spectroscopy, FTIR spectroscopy, and bond valence analysis of possible sorption products to provide this type of information. Macroscopic uptake measurements show that Hg(II) sorbs strongly to fine-grained powders of synthetic goethite (Hg sorption density Γ =0.39–0.42 μmol/m 2 ) and bayerite ( Γ =0.39–0.44 μmol/m 2 ), while sorbing more weakly to γ -alumina ( Γ =0.04–0.13 μmol/m 2 ). EXAFS spectroscopy on the sorption samples shows that the dominant mode of Hg sorption on these phases is as monodentate and bidentate inner-sphere complexes. The mode of Hg(II) sorption to goethite was similar over the pH range 4.3–7.4, as were those of Hg(II) sorption to bayerite over the pH range 5.1–7.9. Conversion of the γ -Al 2 O 3 sorbent to a bayerite-like phase in addition to the apparent reduction of Hg(II) to Hg(I), possibly by photoreduction during EXAFS data collection, resulted in enhanced Hg uptake from pH 5.2–7.8 and changes in the modes of sorption that correlate with the formation of the bayerite-like phase. Bond valence calculations are consistent with the sorption modes proposed from EXAFS analysis. EXAFS analysis of Hg(II) sorption products on a natural Fe oxyhydroxide precipitate and Al/Si-bearing flocculent material showed sorption products and modes of surface attachment similar to those for the model substrates, indicating that the model substrates are useful surrogates for the natural sediments.

Effects of phosphate on uranium(VI) adsorption to goethite-coated sand

Abstract: U(VI)-phosphate interactions are important in governing the subsurface mobility of U(VI) in both natural and contaminated environments. We studied U(VI) adsorption on goethite-coated sand (to mimic natural Fe-coated subsurface materials) as a function of pH in systems closed to the atmosphere, in both the presence and the absence of phosphate. Our results indicate that phosphate strongly affects U(VI) adsorption. The effect of phosphate on U(VI) adsorption was dependent on solution pH. At low pH, the adsorption of U(VI) increased in the presence of phosphate, and higher phosphate concentration caused a larger extent of increase in U(VI) adsorption. Phosphate was strongly bound by the goethite surface in the low pH range, and the increased adsorption of U(VI) at low pH was attributed to the formation of ternary surface complexes involving both U(VI) and phosphate. In the high pH range, the adsorption of U(VI) decreased in the presence of phosphate at low total Fe concentration, and higher phosphate concentration caused a larger extent of decrease in U(VI) adsorption. This decrease in U(VI) adsorption was attributed to the formation of soluble uranium-phosphate complexes. A surface complexation model (SCM) was proposed to describe the effect of phosphate on U(VI) adsorption to goethite. This proposed model was based on previous models that predict U(VI) adsorption to iron oxides in the absence of phosphate and previous models developed to predict phosphate adsorption on goethite. A postulated ternary surface complex of the form of (>FePO4UO2) was included in our model to account for the interactions between U(VI) and phosphate. The model we established can successfully predict U(VI) adsorption in the presence of phosphate under a range of conditions (i.e., pH, total phosphate concentration, and total Fe concentration).

Long-term in vitro transformation of 2-line ferrihydrite to goethite/hematite at 4, 10, 15 and 25°C

Abstract: 2-line ferrihydrite stored in water at ambient temperatures from 4 to 25°C and at ten different pH values between 2.5 and 12 for up to 10–12 y transformed to both goethite and hematite at all temperatures and pH values except at pH 12 where only goethite was formed. The rate and degree of transformation (20–100%) increased with increasing pH and temperature. The hematite/(hematite+goethite) ratio varied between 0 and ∼0.8, increased with increasing temperature and showed a strong maximum at pH 7–8 which increased from 0.1–0.2 at 4°C to 0.7–0.8 at 25°C. The maximum coincides with the zero point of charge of ferrihydrite where its solubility and, thus, its via-solution transformation rate to goethite are minimal. We assume, therefore, that in this pH-range the (slower) via-solution transformation to hematite can more efficiently compete with that to goethite.

Adsorption of humic acid on goethite: isotherms, charge adjustments, and potential profiles.

Abstract: The adsorption of natural organic matter (NOM) on mineral (hydr)oxide plays an important role in the evaluation of the speciation of toxic metal ions in the environment. Because both NOM and mineral oxide have variable charges that adjust upon adsorption, a good understanding of proton binding is required before the binding of metal ions can be understood. In this study, the adsorption of purified Aldrich humic acid (PAHA) on goethite was examined as a function of the environmental conditions (pH, salt concentration, and free concentration of PAHA) together with the proton adsorption to PAHA, goethite, and their mixtures. The induced charges on both components were separated on the basis of the difference between the charge/pH curves of the mixture and those of the single components. The electrostatic potential profile across the adsorbed layer was obtained as a numerical solution of the Poisson-Boltzmann equation using the charge density of the adsorbed PAHA and the goethite surface. From the quantitative evaluation of the induced charge on both components, it is revealed that the degree of the charge adjustment is related to the electrostatic affinity between the PAHA segments and the goethite surface, the electrostatic repulsion between the PAHA segments, and the electrostatic shielding by salt ions. Considering the charge distribution of the adsorbed PAHA at the goethite surface, it is concluded that the change of the charge adjustment is sensitive to that of the conformation of the adsorbed PAHA. From the detailed inspection of the assumptions made and the comparison with the reported theoretical calculations, the obtained potential profiles are considered to broadly reflect the true potential profiles. Because a charge adjustment is not frequently considered in detail in relation to the NOM adsorption on metal (hydr)oxides, the obtained results can form the basis for the further development of modeling of the adsorption of NOM on (hydr)oxide surfaces.

Formation of metal-arsenate precipitates at the goethite-water interface.

Abstract: Little information is available concerning cosorbing oxyanion and metal contaminants in the environment, yet in most metal-contaminated areas, cocontamination by arsenate [AsO4, As(V)] is common. This study investigated the cosorption of As(V) and Zn on goethite at pH 4 and 7 as a function of final solution concentration. Complimentary extended X-ray absorption fine structure (EXAFS) spectroscopic data were collected at the As and Zn K-edges in order to glean information about the coordination environment of As and Zn at the goethite−water interface. Macroscopic sorption studies revealed that As(V) and Zn sorption on goethite increased in cosorption experiments beyond that suggested by single sorption isotherms. At pH 4 and 7, As(V) surface saturation was 3.2 and 2.2 μmol m-2, respectively, and Zn surface saturation was absent at pH 4 and ∼ 1.0 μmol m-2 at pH 7. Arsenate sorption on goethite increased in the presence of Zn by 29% and by more than 500% at pH 4 and 7, respectively. In the presence of As(V),...

Mechanisms and products of surface-mediated reductive dehalogenation of carbon tetrachloride by Fe(II) on goethite.

Abstract: Natural attenuation processes of chlorinated solvents in soils and groundwaters are increasingly considered as options to manage contaminated sites. Under anoxic conditions, reactions with ferrous iron sorbed at iron(hyro)xides may dominate the overall transformation of carbon tetrachloride (CCl4) and other chlorinated aliphatic hydrocarbons. We investigated mechanisms and product formation of CCl4 reduction by Fe(II) sorbed to goethite, which may lead to completely dehalogenated products or to chloroform (CHCl3), a toxic product which is fairly persistent under anoxic conditions. A simultaneous transfer of two electrons and cleavage of two C−Cl bonds of CCl4 would completely circumvent chloroform production. To distinguish between initial one- or two-bond cleavage, 13C-isotope fractionation of CCl4 was studied for reactions with Fe(II)/goethite (isotopic enrichment factor e = −26.5‰) and with model systems for one C−Cl bond cleavage and either single-electron transfer (Fe(II) porphyrin, e = −26.1‰) or pa...

Weathering Geochronology by (U-Th)/He Dating of Geothite

Abstract: Ten samples of supergene goethite (FeOOH) from Brazil and Australia were selected to test the suitability of this mineral for (U-Th)/He dating. Measured He ages ranged from 8 to 61 Ma, and were reproducible to better than a few percent despite very large variations in [U] and [Th]. In all samples with internal stratigraphy or independent age constraints, the He ages honored the expected relationships. These data demonstrate that internally consistent He ages can be obtained on goethite, but do not prove quantitative 4He retention. To assess possible diffusive He loss, stepped-heating experiments were performed on two goethite samples that were subjected to proton irradiation to produce a homogeneous distribution of spallogenic 3He. The 3He release pattern indicates the presence of at least two diffusion domains, one with high helium retentivity and the other with very low retentivity at Earth surface conditions. The low retentivity domain, which accounts for ~ 5% of 3He, contains no natural 4He, and may represent poorly crystalline or intergranular material which has lost all radiogenic 4He by diffusion in nature. Diffusive loss of 3He from the high retentivity domain is independent of the macroscopic dimensions of the analyzed polycrystalline aggregate, so probably represents diffusion from individual micrometer-size goethite crystals. The 4He/3He evolution during the step heating experiments shows that the high retentivity domain has retained 90-95% of its radiogenic helium. This degree of retentivity is in excellent agreement with that independently predicted from the helium diffusion coefficients extrapolated to Earth surface temperature and held for the appropriate duration. These data indicate that one of the samples retained 90% of its radiogenic 4He over 46.8 Ma and the other retained 86% over 11.9 Ma. Thus while diffusive-loss corrections to supergene goethite He ages are required, these initial results indicate that the corrections are not extremely large and can be rigorously quantified using the proton-irradiation 4He/3He method.

Iron precipitate accumulations associated with waterways in drained coastal acid sulfate landscapes of eastern Australia

Abstract: Iron precipitate accumulations from surface environments surrounding waterways (such as the side of drains and soil surface horizons) in acid sulfate soil landscapes were analysed for their mineralogy, micromorphology and chemical properties. Schwertmannite (Fe8(OH)5.5(SO4)1.25) was the dominant mineral in these accumulations. Goethite (α-FeOOH) was the other iron precipitate mineral identified in these accumulations and the data indicate that this iron mineral was formed from schwertmannite, often as pseudomorphs after schwertmannite. The schwertmannite in these accumulations had similar morphology and chemical properties to schwertmannite reported for environments affected by acid mine drainage. The activity of Fe3+ in the drainage waters in these landscapes appears to be controlled by schwertmannite during both low flow (dry season) and flood conditions. Iron precipitate accumulations contained appreciable amounts of stored acidity (i.e. titratable actual acidity of between 164 and 443 mol (H+) t–1, and 1900 to 2580 mol (H+) t–1 of schwertmannite upon complete conversion to goethite) that tends to buffer these waters to very acidic conditions (i.e. pHs ~3.0–3.5). The relationship between water quality (i.e. pH and sulfate concentration) and type of iron precipitate mineral formed should enable the mineralogy of the iron precipitates in these surface environments to be used to help identify the degree of severity of degradation in these acid sulfate soil landscapes and to monitor the effectiveness of remediation programmes.

Abiotic Degradation of Pentachloronitrobenzene by Fe(II): Reactions on Goethite and Iron Oxide Nanoparticles

Abstract: Pentachloronitrobenzene is a fungicide that is degraded in anoxic soils and sediments through unknown processes that are often thought to be biologically mediated. The present research describes the kinetics for the abiotic reduction of this compound in aqueous Fe(II)/goethite systems at near-neutral pH values. The results provide evidence for a rate-affecting surface-association process rather than a direct (i.e., kinetically second-order) reaction with an adsorbed Fe(II) species. It is therefore likely that the iron oxide surface participates directly in the reaction. Furthermore, reduction is observed in the apparent presence of trace amounts of suspended iron oxide nanoparticles, formed in situ by the oxidation of Fe(II). Given that Fe(III) colloids and other nanoscale phases may occur in natural sediments, such abiotic reactions could significantly influence the environmental fate of nitroaromatic compounds.

Influence of electrostatics on the oxidation rates of organic compounds in heterogeneous Fenton systems.

Abstract: Electrostatic effects influence the oxidation rates of charged dissolved organic compounds in systems where the hydroxyl radical (*OH) is produced by the iron oxide-catalyzed decomposition of hydrogen peroxide (H2O2). Experiments were performed using goethite and the *OH probes 14C-labeled formic acid, 2-chlorophenol (2-CP), and nitrobenzene. At pH 4 and an ionic strength of 0.01 M, formic acid (pKa = 3.745) detected a steady-state concentration of *OH ([*OH]ss, calculated as a solution average) approximately 50 times higher than the two neutral probes did in the same systems, indicating significant enrichment of formate at the surface of the positively charged iron oxide where the *OH is being produced. Increasing the pH and ionic strength decreased formic acid oxidation rates by factors consistent with predicted decreases in electrostatic effects. In the presence of high 2-CP concentrations, the [*OH]ss measured by formic acid decreased with time, and goethite coagulation increased, due to loss of positive charge on the oxide surface as the oxidation products of 2-CP complexed surface Fe species. The [*OH]ss detected by 2-CP did not change significantly, indicating that neither goethite coagulation nor surface complexation of 2-CP oxidation products interfered with the rate of *OH generation; however, such an effect could have occurred in experiments using dissolved Fe instead of goethite. Model predictions of organic compound oxidation rates in mineral-catalyzed Fenton-like systems were improved by taking electrostatic effects into account.

Morphology of synthetic goethite particles.

Abstract: The specific surface area of synthetic goethite depends on the preparation: the Fe(III):OH ratio, the rate of base titration of Fe salt, and the temperature and time of crystallization. The crystals also have different morphologies as determined by SEM or TEM. Carbon coating is used to improve the quality of SEM images of nonconducting specimens. We show here that needle-like goethite particles become substantially thicker in the course of standard carbon coating, and the length-to-width ratio obtained for carbon-coated particles is lower than that for the original goethite particles. The morphology of the goethite particles was also studied by tapping mode AFM.