Showing papers on "Goethite published in 2018"

Impact of Organic Matter on Iron(II)-Catalyzed Mineral Transformations in Ferrihydrite-Organic Matter Coprecipitates

Abstract: Poorly crystalline Fe(III) (oxyhydr)oxides like ferrihydrite are abundant in soils and sediments and are often associated with organic matter (OM) in the form of mineral-organic aggregates. Under anoxic conditions, interactions between aqueous Fe(II) and ferrihydrite lead to the formation of crystalline secondary minerals, like lepidocrocite, goethite, or magnetite. However, the extent to which Fe(II)-catalyzed mineral transformations are influenced by ferrihydrite-associated OM is not well understood. We therefore reacted ferrihydrite-PGA coprecipitates (PGA = polygalacturonic acid, C:Fe molar ratios = 0–2.5) and natural Fe-rich organic flocs (C:Fe molar ratio = 2.2) with 0.5–5.0 mM isotopically labeled 57Fe(II) at pH 7 for 5 weeks. Relying on the combination of stable Fe isotope tracers, a novel application of the PONKCS method to Rietveld fitting of X-ray diffraction (XRD) patterns, and 57Fe Mossbauer spectroscopy, we sought to follow the temporal evolution in Fe mineralogy and elucidate the fate of ad...

Multiple exchange processes on mineral surfaces control the transport of dissolved organic matter through soil profiles

Abstract: Organic topsoil layers are important sources of dissolved organic matter (DOM) transported to deeper soil layers. During passage through the mineral soil, both organic matter (OM) quality and quantity change markedly. Whether these alterations are due to sorption processes alone or to additional stepwise exchange processes of OM on mineral surfaces (“cascade model”) is not fully understood. To test the “cascade model”, we conducted a laboratory flow cascade experiment with undisturbed soil columns from three depths of two different soil profiles (Dystric and Eutric Cambisol) using carbon (C) isotope labelling. Each of the connected topsoil and subsoil columns contained a goethite (α-FeOOH) layer either with or without sorbed 13C-labelled OM to assess the importance of OM immobilization/mobilization reactions with reactive soil minerals. By using a multiple method approach including 13C analysis in the solid and solution phases, nanometer scale secondary ion mass spectrometry (NanoSIMS), and quantitative polymerase chain reaction (qPCR), we quantified organic carbon (OC) adsorption and desorption and net OC exchange at goethite surfaces as well as the associated microbial community patterns at every depth step of the column experiment. The gross OC exchange between OM-coated goethite and the soil solution was in the range of 15–32%. This indicates that a considerable proportion of the mineral associated OM was mobilized and replaced by percolating DOM. We showed that specific groups of bacteria play an important role in processing organic carbon compounds in the mineral micro-environment. Whereas bulk soils were dominated by oligotrophic bacteria such as Acidobacteria, the goethite layers were specifically enriched with copiotrophic bacteria such as Betaproteobacteria. This group of microorganisms made use of labile carbon derived either from direct DOM transport or from OM exchange processes at goethite surfaces. Specific microorganisms appear to contribute to the cascade process of OM transport within soils. Our study confirms the validity of the postulated “cascade model”, featuring the stepwise transport of OM within the soil profile.

Ferrous Iron Oxidation under Varying pO2 Levels: The Effect of Fe(III)/Al(III) Oxide Minerals and Organic Matter

Abstract: Abiotic Fe(II) oxidation by O2 commonly occurs in the presence of mineral sorbents and organic matter (OM) in soils and sediments; however, this tertiary system has rarely been studied. Therefore, we examined the impacts of mineral surfaces (goethite and γ-Al2O3) and organic matter [Suwannee River fulvic acid (SRFA)] on Fe(II) oxidation rates and the resulting Fe(III) (oxyhydr)oxides under 21 and 1% pO2 at pH 6. We tracked Fe dynamics by adding 57Fe(II) to 56Fe-labeled goethite and γ-Al2O3 and characterized the resulting solids using 57Fe Mossbauer spectroscopy. We found Fe(II) oxidation was slower at low pO2 and resulted in higher-crystallinity Fe(III) phases. Relative to oxidation of Fe(II)(aq) alone, both goethite and γ-Al2O3 surfaces increased Fe(II) oxidation rates regardless of pO2 levels, with goethite being the stronger catalyst. Goethite surfaces promoted the formation of crystalline goethite, while γ-Al2O3 favored nano/small particle or disordered goethite and some lepidocrocite; oxidation of Fe...

Structural Incorporation of Manganese into Goethite and Its Enhancement of Pb(II) Adsorption.

Abstract: Natural goethite (α-FeOOH) commonly accommodates various metal elements by substituting for Fe, which greatly alters the surface reactivity of goethite. This study discloses the enhancement of Mn-substitution for the Pb2+adsorption capacity of goethite. The incorporated Mn in the synthesized goethite presents as Mn(III) and causes a slight decrease in the a and c of the unit cell parameters and an observable increase in the b direction due to the Jahn–Teller effect of the Mn(III)O6 octahedra. With the Mn content increasing, the particle size decreases gradually, and the surface clearly becomes roughened. The Pb2+ adsorption capacity of goethite is observably enhanced by Mn substitution due to the modified surface complexes. And the increased surface-area-normalized adsorption capacity for Mn-substituted goethite indicated that the enhancement of Pb adsorption is not only attributed to the increase of surface area but also to the change of binding complexes. Extended X-ray absorption fine structure (EXAFS)...

The Role of Defects in Fe(II)–Goethite Electron Transfer

Abstract: Despite substantial experimental evidence for Fe(II)–Fe(III) oxide electron transfer, computational chemistry calculations suggest that oxidation of sorbed Fe(II) by goethite is kinetically inhibited on structurally perfect surfaces We used a combination of 57Fe Mossbauer spectroscopy, synchrotron X-ray absorption and magnetic circular dichroism (XAS/XMCD) spectroscopies to investigate whether Fe(II)–goethite electron transfer is influenced by defects Specifically, Fe L-edge and O K-edge XAS indicates that the outermost few Angstroms of goethite synthesized by low temperature Fe(III) hydrolysis is iron deficient relative to oxygen, suggesting the presence of defects from Fe vacancies This nonstoichiometric goethite undergoes facile Fe(II)–Fe(III) oxide electron transfer, depositing additional goethite consistent with experimental precedent Hydrothermal treatment of this goethite, however, appears to remove defects, decrease the amount of Fe(II) oxidation, and change the composition of the oxidation pr

Mineralogical characteristics of sediments and heavy metal mobilization along a river watershed affected by acid mine drainage

Abstract: Trace-element concentrations in acid mine drainage (AMD) are primarily controlled by the mineralogy at the sediment-water interface. Results are presented for a combined geochemical and mineralogical survey of Dabaoshan Mine, South China. Developed sequential extraction experiments with the analysis of the main mineralogical phases by semi-quantitative XRD, differential X-ray diffraction (DXRD) and scanning electron microscopy (SEM) were conducted to identify the quantitative relationship between iron minerals and heavy metals. Results showed that schwertmannite, jarosite, goethite and ferrihydrite were the dominant Fe-oxyhydroxide minerals which were detected alternately in the surface sediment with the increasing pH from 2.50 to 6.93 along the Hengshi River. Decreasing contents of schwertmannite ranging from 35 wt % to 6.5 wt % were detected along the Hengshi River, which was corresponding to the decreasing metal contents. The easily reducible fractions exert higher affinity of metals while compared with reducible and relatively stable minerals. A qualitative analysis of heavy metals extracted from the sediments indicated that the retention ability varied: Pb > Mn > Zn > As ≈ Cu > Cr > Cd ≈ Ni. Results in this study are avail for understanding the fate and transport of heavy metals associated with iron minerals and establishing the remediation strategies of AMD systems.

Impacts of hydrous manganese oxide on the retention and lability of dissolved organic matter.

Abstract: Minerals constitute a primary ecosystem control on organic C decomposition in soils, and therefore on greenhouse gas fluxes to the atmosphere. Secondary minerals, in particular, Fe and Al (oxyhydr)oxides—collectively referred to as “oxides” hereafter—are prominent protectors of organic C against microbial decomposition through sorption and complexation reactions. However, the impacts of Mn oxides on organic C retention and lability in soils are poorly understood. Here we show that hydrous Mn oxide (HMO), a poorly crystalline δ-MnO2, has a greater maximum sorption capacity for dissolved organic matter (DOM) derived from a deciduous forest composite Oi, Oe, and Oa horizon leachate (“O horizon leachate” hereafter) than does goethite under acidic (pH 5) conditions. Nonetheless, goethite has a stronger sorption capacity for DOM at low initial C:(Mn or Fe) molar ratios compared to HMO, probably due to ligand exchange with carboxylate groups as revealed by attenuated total reflectance-Fourier transform infrared spectroscopy. X-ray photoelectron spectroscopy and scanning transmission X-ray microscopy–near-edge X-ray absorption fine structure spectroscopy coupled with Mn mass balance calculations reveal that DOM sorption onto HMO induces partial Mn reductive dissolution and Mn reduction of the residual HMO. X-ray photoelectron spectroscopy further shows increasing Mn(II) concentrations are correlated with increasing oxidized C (C=O) content (r = 0.78, P < 0.0006) on the DOM–HMO complexes. We posit that DOM is the more probable reductant of HMO, as Mn(II)-induced HMO dissolution does not alter the Mn speciation of the residual HMO at pH 5. At a lower C loading (2 × 102 μg C m−2), DOM desorption—assessed by 0.1 M NaH2PO4 extraction—is lower for HMO than for goethite, whereas the extent of desorption is the same at a higher C loading (4 × 102 μg C m−2). No significant differences are observed in the impacts of HMO and goethite on the biodegradability of the DOM remaining in solution after DOM sorption reaches steady state. Overall, HMO shows a relatively strong capacity to sorb DOM and resist phosphate-induced desorption, but DOM–HMO complexes may be more vulnerable to reductive dissolution than DOM–goethite complexes.

Iron in Glacial Systems: Speciation, Reactivity, Freezing Behavior, and Alteration During Transport

Abstract: A more insightful view of iron in glacial systems requires consideration of iron speciation and mineralogy, the potential for iron minerals to undergo weathering in ice-water environments, the impact of freezing on concentration and speciation, and potential for glacial delivery to undergo alteration during transport into the ocean. A size fractionation approach improves recognition of iron speciation by separating dissolved Fe (0.1 wt. %) which represent samples in which the on-going transformation of ferrihydrite to goethite/hematite is incomplete. Numerical models of freezing in subglacial systems show that the nanomolar levels of soluble Fe in icebergs cannot be achieved solely by freezing, and must indicate the presence of nanoparticulate Fe and/or iron desorbed from ice or sediments during melting. Models of freezing effects in sea ice show that nanomolar levels of Fe are achievable because high concentrations of hydroxide and chloride ions maintain dissolved iron as soluble complexes. Delivery of iron through fjords is temporally and spatially variable due to circulation patterns, mixing of different sources and aggregation through salinity gradients.

Effect of Soil Fulvic and Humic Acids on Pb Binding to the Goethite/Solution Interface: Ligand Charge Distribution Modeling and Speciation Distribution of Pb.

Abstract: The effect of adsorbed soil fulvic (JGFA) and humic acid (JGHA) on Pb binding to goethite was studied with the ligand charge distribution (LCD) model and X-ray absorption fine structure (XAFS) spectroscopy analysis. In the LCD model, the adsorbed small JGFA particles were evenly located in the Stern layer, but the large JGHA particles were distributed over the Stern layer and the diffuse layer, which mainly depended on the JGHA diameter and concentrations. Specific interactions of humic substances (HS) with goethite were modeled by inner-sphere complexes between the −FeOH20.5+ of goethite and the −COO– of HS and by Pb bridges between surface sites and COO– groups of HS. At low Pb levels, nearly 100% of Pb was bound as Pb bridges for both JGFA and JGHA. At high Pb levels and low HS loading, Pb–goethite almost dominated over the entire studied pH range, but at high HS loading, the primary species was goethite–HS–Pb at acidic pH and goethite–Pb at alkaline pH. Compared with JGFA, there was a constant contrib...

Sulfidation mechanisms of Fe(III)-(oxyhydr)oxide nanoparticles: a spectroscopic study

Abstract: We used synchrotron-based X-ray absorption spectroscopy, transmission electron microscopy, and wet chemical analyses to study the sulfidation mechanism(s) and sulfur oxidation products from the reaction of ferrihydrite, goethite, and hematite nanoparticles with dissolved sulfide at different S/Fe molar ratios under anaerobic condition. Our results suggest that surface area alone does not explain the differences in reactivity of Fe(III)-(oxyhydr)oxide nanoparticles with dissolved sulfides; differences in atomic-level surface structure are also likely to play an important role. The higher reactivity of ferrihydrite leads to a faster sulfidation rate compared to that of goethite and hematite. We found that polysulfides as well as elemental sulfur are the major reaction products in the sulfidation of all three Fe(III)-(oxyhydr)oxide nanoparticles studied. We also found that thiosulfate and sulfate formed during the sulfidation of goethite and hematite but did not form in the case of ferrihydrite, suggesting that the slower reaction kinetics of goethite and hematite favors the formation of solid-phase thiosulfates and elemental sulfur in our experiments. In addition, our results revealed that the S/Fe ratio is a critical variable in the sulfidation reaction. Iron dissolution rates for ferrihydrite, goethite, and hematite nanoparticles were found to increase up to a S/Fe ratio of ≤0.5 and decline above this ratio, suggesting formation of FeS species. Similarly, Fe dissolution rates increased with increasing S/Fe ratios and remained an order of magnitude higher for ferrihydrite than for goethite and three times higher for ferrihydrite than for hematite. Sulfur-K-edge X-ray absorption near edge structure (XANES) spectroscopy revealed for the first time the mass distribution of these solid-phase sulfur oxidation products. In addition, we used Fe-K-edge XANES and extended X-ray absorption fine structure (EXAFS) spectroscopic analysis to follow the kinetics of FeS formation for the three types of Fe(III)-(oxyhydr)oxide nanoparticles, with varying S/Fe ratios. Ferrihydrite transformed completely to FeS in our experiments, but only 58% of the goethite and only 18% of the hematite transformed to FeS. These results have important environmental implications for Fe- and S-redox cycling and contaminant mobility and provide experimental evidence for the impact of S/Fe ratio on contaminant mobility in the systems studied, either by releasing surface-sorbed contaminants due to Fe(III)-reductive dissolution at lower S/Fe ratios or by trapping or co-precipitation of contaminants with FeS precipitation at higher S/Fe ratios.

Radium Sorption to Iron (Hydr)oxides, Pyrite, and Montmorillonite: Implications for Mobility

Abstract: Radium (Ra) is a radioactive element commonly found within soils, sediments, and natural waters. Elevated Ra activities arising through natural and anthropogenic processes pose a threat to groundwater resources and human health, and Ra isotope ratios are used to decipher groundwater movement, estimate submarine discharge flux, and fingerprint contamination associated with hydraulic fracturing operations. Although adsorption to metal (hydr)oxides and certain clay minerals is well established as a dominant mechanism controlling Ra transport and retention, the extent of Ra sorption to other minerals and under variable environmental conditions (e.g., pH and salinity) is limited. Accordingly, we present results of sorption studies and surface complexation modeling (SCM) of Ra to ferrihydrite, goethite, montmorillonite, and pyrite, for a range of pH values and common background cations. Ra sorption to all substrates is observed under geochemical conditions considered, but varies according to mineral, solution p...

Integrated study of Red Mediterranean soils from Southern Italy

Abstract: Terra Rossa is a typical Mediterranean soil characterized by an association of the Mediterranean climate, high internal drainage (due to the karstic nature of the underlying hard limestone) and neutral pH conditions. The genesis of this soil is a controversial subject in terms of the origin of the parent material, from the residual underlying (carbonate/dolomite) bedrock and/or from external (aeolian dust) contributions. We apply an integrated approach (chemical, physical, mineralogical and geochemical) to nine soil profiles of terra rossa from Apulia region (southern Italy), in order to investigate the main soil properties relating to soil weathering and pedogenetic processes, as well as to acquire knowledge on soil-bedrock relationships and their origin. Results showed that these terra rossa were generally clayey, had colors (moist) ranging from 2.5YR to 7.5YR Munsell hues and a mineralogical composition of mainly kaolinite, illite/mica and Fe-oxides (hematite and goethite). The pedogenetic indices (Feo/Fed, Fed/Fet) exhibited a generally high degree of crystallinity of iron forms and soil weathering. The correlation between illite/kaolinite ratio and pedogenetic indices, as well as that of kaolinite and hematite with the Feo/Fed ratio indicated that weathering processes in the studied environments promoted the formation of both kaolinite and hematite from illite/mica minerals. Since the hematite/goethite ratio was generally higher than 1, rubification processes also occurred in these soils. The comparison of the geochemical composition of terra rossa with that of insoluble residues (obtained from the underlying limestone and dolomite rocks) indicated that a group of elements (such as Ti, Mn, Th) was more concentrated in terra rossa than in the insoluble residues, whereas another group (made up of Fe, K, Ca, Cr, Cu, Zr, Zn, Rb, Ni, As, Sr and Pb) was more concentrated in the insoluble residues than in terra rossa. The two groups of elements were considered to be different as a result of their having different sources, the first being allochtonous and the second mainly authoctonous. The additional correlation of Ti, Mn and Th with terra rossa clay content seemed to support the hypothesis of wind-blown long distance transport for these elements.

Unravelling the nature of glyphosate binding to goethite surfaces by ab initio molecular dynamics simulations

Abstract: Investigation of the interaction between glyphosate (GLP) and soil minerals is essential for understanding GLP's fate in the environment. Whereas GLP-goethite binding has been discussed extensively, the impact of water as well as of different goethite surface planes has not been studied yet. In this contribution, periodic density functional theory-based molecular dynamics simulations are applied to explore possible binding mechanisms for GLP with three goethite surface planes (010, 001, and 100) in the presence of water. The investigation included several binding motifs of monodentate (M) and bidentate (B) type. It was found that the binding stability increases in the order M@001 < M@010 < (2O + 2Fe) B@100 < M@100 < (1O + 2Fe) B@001 < (2O + 1Fe) B@010. This behavior has been traced to the presence of intramolecular H-bonds (HBs) in GLP as well as intermolecular HBs between GLP and water, GLP and goethite, and water and goethite. These interactions are accompanied by proton transfer from GLP to water and to goethite, and from water to goethite as well as water dissociation at the goethite surface. Further, it was observed that the OH- species can replace the adsorbed GLP at the goethite surface, which could explain the well-known drastic drop in GLP adsorption at high pH. The present results highlight the role of water in the GLP-goethite interaction and provide a molecular level perspective on available experimental data.