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Cobalt (Co) and nickel (Ni) are critical metals for modern renewable energy technologies as well as essential micronutrients for terrestrial plant health and marine primary production. Both metals are commonly surface-adsorbed onto and/or structurally-incorporated into iron (oxyhydr)oxide minerals, such as goethite (α-FeOOH), that are ubiquitously present in soils and sediments at the Earth's surface. In sub- and anoxic environments, aqueous ferrous iron (Fe(II)) generated from dissimilatory Fe(III) reduction can induce the recrystallization of goethite and subsequently influences the speciation and mobilization of associated metals, e.g., Co(III) being reduced to Co(II). While it is generally considered that divalent Co and Ni behave similarly at goethite-water interfaces, there lacks a direct comparison of their cycling through goethite in response to Fe(II)-catalyzed recrystallization. Here, under circumneutral anoxic conditions with and without addition of aqueous Fe(II), we performed batch reaction experiments on Co(II)-substituted goethite and Co(II) and Ni(II) sorption experiments on pure goethite. The redox state and coordination environment of Co associated with goethite were determined using high energy resolution fluorescence detected X-ray absorption spectroscopy at the Co K-edge, and the distribution of solid-bound Co and Ni in goethite following sorption was revealed by sequential dissolution. Our results show that substitution of Co(II) for Fe(III) in goethite has less negative feedback on Fe(II)-catalyzed recrystallization than Ni(II), which may be related to their differing structural distortions as evidenced by EXAFS. In the absence of Fe(II), aqueous Co(II) is more favourably adsorbed onto and incorporated deeper into goethite than Ni(II), suggesting that Co(II) is more structurally compatible with goethite. The presence of Fe(II) markedly enhances the structural incorporation of both Co(II) and Ni(II) as a result of goethite recrystallization, which in turn can be inhibited by the accumulation of metals at the mineral surface. Furthermore, structurally-incorporated Co(II) is more difficult to be released back into solution (i.e. sum of aqueous and extract fractions) than Ni(II) during Fe(II)-catalyzed goethite recrystallization. Overall, our work highlights the significant differences between Co(II) and Ni(II) in their cycling at goethite-water interfaces and intricate interplay with Fe(II)-catalyzed recrystallization. This improves our understanding of their mobilization and distribution in anoxic goethite-rich systems and can provide useful insights for their enrichment and extraction from natural and artificial laterites generated from the enhanced weathering of ultramafic mine tailings. [ABSTRACT FROM AUTHOR]

Jarosite, a prominent mineral in oxidised acid sulfate soil, is known to sorb and incorporate a variety of elements, including Al. However, to understand the role that jarosite plays in regulating element cycles, it is crucial to understand the stability and transformation pathways of jarosite in an acid sulfate soil under dynamic biogeochemical conditions. In this study, we observed the transformation of unsubstituted jarosite and Al-substituted jarosite, collectively referred to as 'jarosite', in an acid-sulfate rice paddy topsoil and subsoil from Thailand. Jarosite was incubated in flooded paddy topsoils and subsoils for up to sixteen weeks, both in laboratory mesocosms and in the field, using bags made of polyethylene terephthalate mesh. One set of mesh bags contained jarosite that was not mixed with any other minerals, and referred to as 'pure mineral' incubations. Mineral transformations occurred under the influence of the soil porewater only and were primarily followed by X-ray diffraction analysis. A parallel set of mesh bags contained soil with 57Fe-labelled jarosite enrichment (Fe enriched in soil by a factor of 1.3 but 57Fe enrichment factor of 12.5–13.6), which allowed jarosite transformation to occur in close association with the soil matrix. Mineral transformations in 57Fe-jarosite-enriched soil were followed using 57Fe Mössbauer spectroscopy. In laboratory mesocosms and in the field, jarosite transformed most quickly in topsoil, whereas jarosite underwent limited transformation in subsoils, especially in laboratory mesocosms where Fe reduction was slow. The chemical environment around the jarosite affected the outcome of the transformation processes. Crystalline Fe oxyhydroxides, such as goethite, dominated the products in mesh bags where jarosite was not mixed with soil, whereas short-range-ordered or non-mineral Fe phases, such as Fe(II) sorbed to mineral surfaces or complexed with organic ligands, were dominant transformation products of jarosite when mixed in soil. Furthermore, Al substitution in jarosite caused contrasting effects in mesh bags containing pure minerals or mineral-enriched soil. Aluminium substitution slowed the transformation of jarosite in pure mineral mesh bags, but Al-substituted and unsubstituted jarosite showed similar transformation rates and pathways when incubated as a mixture with soil. The contrasting rate of transformation in topsoil and subsoil, the contrasting products of transformation in pure mineral mesh bags and 57Fe-jarosite-enriched soil, and the contrasting effect of Al substitution in pure mesh bags or jarosite-enriched soil, all demonstrate that the rate and products of jarosite transformation are defined by a balance between competitive transformation pathways that affect the transforming minerals. [ABSTRACT FROM AUTHOR]

Deep-sea mud shows tremendous resource potential for rare earth elements (REEs) and its formation is closely associated with sea-floor hydrothermal activities. Iron (oxyhydr)oxides link the sources and sinks of REEs in sea-floor hydrothermal systems. However, the complexation mechanisms of REEs on iron (oxyhydr)oxides have not been well understood yet. In this study, by using the first principles molecular dynamics technique, we first calculated the pK a 's of surface groups on goethite (1 1 0) surface at elevated temperatures relevant to sea-floor hydrothermal systems and then evaluated the complexation structures and free energies of REEs on goethite (1 1 0) and (0 1 0) surfaces using the method of constraint by taking Sc3+, Y3+, and La3+ as model REE cations. The results show that REE complexation occurs in mildly acidic to neutral conditions. The most thermodynamically stable complexes of REEs are bidentate complexes on two neighboring FeOH sites on goethite (1 1 0) surface and tridentate complexes on two neighboring FeOH sites plus one Fe 2 OH site on goethite (0 1 0) surface. Sc3+ complexes match the goethite lattice and can be incorporated into the lattice. The stabilities of REE complexes increase with the distance from hydrothermal vents. Complexation of Y3+ is less favored on goethite compared to other REEs whereas Sc3+ prefers complexation on goethite (0 1 0) surface and La3+ exhibits similar stabilities on both (0 1 0) and (1 1 0) surfaces. The derived atomic level complexation mechanisms would be helpful for the interpretation of experimental data and the prediction of REEs' behavior in the sea-floor. The findings presented here provide valuable insights into REEs fractionation and enrichment in deep-sea muds. [ABSTRACT FROM AUTHOR]

The occurrence of manganese (Mn) oxides on Mars is believed to be an indicator of an O 2 -rich paleoenvironment of Mars because Mn oxides often form through the oxidation of Mn(II) by O 2 on the surface of Earth. An alternative formation pathway was recently proposed, in which Mn(II) is oxidized by bromate (BrO 3 −), a common oxidant in contemporary Martian regolith. However, the oxidation of Mn(II) by bromate in solution is kinetically controlled and slow unless using very high concentrations (100 mM) of reactants that may be irrelevant to the conditions of Mars. We conducted laboratory simulations to determine whether iron (Fe) oxides (hematite and goethite) and a phyllosilicate (montmorillonite), abundant minerals on the surface of Mars, could catalyze the oxidation of Mn(II) by bromate. Hematite and goethite, but not montmorillonite, dramatically accelerated the oxidation with a low concentration (1 mM) of Mn(II) and bromate under various solution conditions. The reaction system was autocatalytic with Fe oxides initiating the oxidation of Mn(II) at the early stage and the subsequent catalysis mainly provided by the Mn oxide products. In contrast to producing Mn(IV)O 2 only during the homogeneous oxidation of Mn(II) by bromate in solutions, the heterogeneous mineral-surface catalyzed oxidation resulted in a mixture of Mn(III)OOH and Mn(IV)O 2 phases. Mn(III)OOH was an intermediate product and can be further oxidized by bromate to Mn(IV)O 2. The occurrence and accumulation of the intermediate product MnOOH can be attributed to its rapid formation due to surface-enhanced nucleation and growth on Fe oxide surfaces and to its higher resistance to oxidation by bromate than Mn(III) ions or clusters. Overall, mineral-surface catalyzed oxidation of Mn(II) by bromate is favorable from both thermodynamic and kinetic perspectives, and can be a major pathway for the occurrence of Mn oxides on Mars where microorganisms are lacking to catalyze the reaction. Our study further improves our understanding of the thermodynamic and kinetic controls on Mn(II) oxidation. [ABSTRACT FROM AUTHOR]

Geogenic arsenic has become a globally-distributed groundwater contaminant, liberated from the weathering of arsenic-bearing sulfide minerals and often transported to aquifer sediments adsorbed to iron oxides. Among the iron oxides, goethite (α-FeOOH) is uniquely important for the fate of arsenic because of its widespread abundance, stability, and high affinity for binding arsenic. Goethite is ubiquitous in soils and sediments and often contains substituted elements, including manganese. Structural manganese may affect the surface reactivity and redox capacity of goethite and alter the mechanisms of recrystallization catalyzed by dissolved Fe(II), potentially affecting arsenic adsorption. This study examined the fate of As(V) during the interactions between dissolved Fe(II) and Mn-substituted goethites at pH 4 and 7 as well as associated changes in arsenic speciation. At pH 7, the addition of dissolved Fe(II) initially increases the adsorption of As(V) onto Mn-bearing and Mn-free goethites. For the Mn-substituted goethites, the adsorbed As(V) slowly releases to solution at longer aging times. Fe(II) addition at pH 4 slightly increases As(V) uptake by Mn-substituted goethites, with differences in total sorption correlating with the Mn content in goethite. The addition of Fe(II) releases substantial dissolved manganese but the amount solubilized is higher at pH 4 compared to 7, suggesting that the presence of adsorbed As(V) may substantially promote the Mn release at pH 4. X-ray absorption fine structure spectroscopy shows that arsenic is stabilized as As(V) in all the samples and adsorbed on goethite via a bidentate binuclear mechanism. Fitting results show that the binding distance and coordination numbers are stable in Mn-free goethite and Mn-substituted goethite samples; the effect of substituted Mn on the surface complex structure is minor. High resolution transmission electron microscopy and X-ray diffraction confirm that no secondary ferrous arsenate minerals precipitate under both pH conditions. This study improves our understanding of the Fe(II)-As(V) interactions on iron oxides, and demonstrates that the substituted cations such as manganese may quantitatively alter the geochemical fate of arsenic during the reaction of dissolved Fe(II) with Fe(III) oxides. [ABSTRACT FROM AUTHOR]

We have determined the proton, electrolyte (NaNO 3) and arsenate affinity constants on the corresponding surface sites of goethite. An empirical optimization approach was applied using the Charge Distribution Multisite Complexation (CD-MUSIC) model, initially, by simulating an extensive proton adsorption data set obtained from four goethites of specific surface areas (SSAs) spanning from 43 to 89 m2/g. Each goethite showed different crystal face compositions, which were measured previously from independent high resolution electron microscopy observations. Only the capacitance value was left as an additional optimizing parameter. For arsenate adsorption, with the above optimized values fixed, the contributing surface arsenate complexes and their respective affinity constants and charge distributions (CD) were also optimized. A unified set of affinity and CD parameters was obtained, where the only resulting variables among goethites were the capacitance 1, the specific surface area and the crystal face contributions (and thus their reactive surface site densities). It was found that the site density parameter is decisive when data show adsorption maxima, such as in the arsenate adsorption isotherms. The self-consistent modeling approach yielded pKa values of singly-coordinated sites of 8.82, and of triply-coordinated sites of 9.65. Three surface arsenate complexes bound only to singly-coordinated sites were found to describe all experimental data, although only two of them were predominant across the pH and As(V) concentration ranges investigated: a bidentate non protonated (BD) complex, and a protonated monodentate (HMD) one. Charge distribution of surface arsenate complexes was found to significantly influence the optimizations, but increased values of optimized capacitance 1 were found to compensate for previously underestimated surface site density values, to yield almost identical surface affinity and CD parameters. Finally, correlations found between surface site density and capacitance-1 parameters with SSA expanded the applicability of the modeling approach presented, to other goethites with different SSAs than the ones investigated here. [ABSTRACT FROM AUTHOR]

Goethite and pyrite are common iron minerals in oxic or anoxic environments, respectively, both minerals being major reservoirs for Nickel, a bio-essential element. Mineral transformation between goethite and pyrite is frequent owing to the alternation of oxic and anoxic conditions in sulfate-rich environments. This mineral transformation has been amply studied, but the effect of Ni on this transformation and its fate along it remain poorly understood. Sulfidation of Ni-free and Ni-containing (through adsorption or isomorphic substitution) goethites was thus studied experimentally by reacting goethite with dissolved S(-II) (molar Fe:S≈1:1). X-ray diffraction and associated Rietveld refinement, thermogravimetric analysis, scanning/transmission electron microscopy, X-ray absorption spectroscopy, and wet chemistry were used to monitor mineralogical evolutions and unravel Ni association with reaction products. After 44 days of sulfidation, about half of initial goethite converted to iron sulfides: thermodynamically stable pyrite (67%–93%) with minor contents of mackinawite (2%–15%) and greigite (5%–25%). Although the overall content of iron sulfides formed was essentially independent of Ni presence, Ni hampered the conversion from metastable iron sulfides (i.e., mackinawite and greigite) to pyrite (67%–78% vs. 93%, in the presence and absence of Ni, respectively). Pyrite formation from metastable sulfide precursors yielded a uniform Ni distribution in newly formed pyrite, regardless of the initial Ni association with goethite. Although no Ni was released to solution during pyrite formation, Ni incorporation to pyrite results in an increased risk of release to the environment as iron sulfides will be oxidized when exposed to air and water in supergene environments, leading to highly acidic conditions favoring Ni solubility and mobility. [ABSTRACT FROM AUTHOR]

Formed in plant tissues as fine silica particles, phytoliths are deposited within plant debris in soils where they can dissolve and feed silicon (Si) fluxes to the biosphere and hydrosphere. Yet, soil phytoliths can be protected from dissolution by entrapment in aggregates, and thus be withdrawn from the global silica cycle. Among clay-sized minerals interacting in stable aggregates, goethite and kaolinite are ubiquitous in soils. We analyzed the impact of goethite-mediated aggregation on the release of aqueous Si from phytoliths entrapped in microaggregates containing organic matter and kaolinite, with quartz and goethite at variable concentrations, simulating a soil sequence with increasing contents of clay and iron oxide, as it can commonly occur in terrestrial ecosystems. The microaggregates stored sizable amount of organic carbon, the release of which decreased with increasing goethite concentration. Aqueous Si was assessed through a kinetic extraction with dilute CaCl 2 , while pH, aluminum (Al) and germanium (Ge) concentrations were measured in the CaCl 2 extracts. Our experimental data showed that phytoliths were the source of aqueous Si. They also showed that the process of phytolith dissolution prevailed over Si adsorption on goethite. As mediated by goethite, aggregation protected phytoliths from dissolution at goethite concentrations above 20 g kg−1. Increasing goethite concentration enhanced aggregation on the one hand, but increased pH from 5.5 to 7.5 on the other. Thus, while aggregation significantly reduced the release of aqueous Si by 1.7- to 3-fold at a given pH, the increase in pH enhanced it. Overall, at common soil solution pH (5–6), aggregation reduced Si release by 2–3 times. Thus, preservation of phytoliths in aggregates can be widespread in well-aerated soils and more effective than Si adsorption on secondary oxides in retaining Si. [ABSTRACT FROM AUTHOR]

For goethites synthesized at low (∼1–2) and high (∼13–14) extremes of pH, the values of 1000ln18α gt-w at ca. 25 °C are, respectively, +6.2 (±0.6) and + 0.9 (±0.6). Note that 18α gt-w = (18O/16O) gt /(18O/16O) w and gt = goethite (α-FeOOH); w = liquid water. A steady-state, flux-balance model indicates that this pH-related difference in values of 1000ln18α gt-w arises because of an effectively irreversible oxygen flux associated with aqueous Fe(III) hydroxide adsorption on, and incorporation in, goethite during growth at crystal surfaces. The model predicts that the transition from a low-pH to a high-pH value of 1000ln18α gt-w is relatively abrupt. At 22 to 25 °C, extant data indicate that the transition occurs in the interval of pH from about 6 to 8. Consequently, uncertainty about the pH of ancient waters could be a factor in interpretations of goethite δ 18O values. However, an experimentally determined equation for the temperature dependence of 1000ln18α (LpH) has been applied with apparent success to natural goethites that formed in the presence of meteoric waters (18α (LpH) = low-pH 18α gt-w). This suggests that those ancient waters may have been acidic (pH < 6) in the immediate environments of goethite crystallization. Published values of D/H fractionation between synthetic goethite and water (Dα gt-w) show no systematic effect of either pH or temperature (T) over a range of pH from 1 to 14 and a range of T from 22 °C to 62 °C. Within these ranges, the average value of Dα gt-w is 0.905 (±0.005) – a value which seems to characterize the D/H fractionation observed in natural goethites. If hydrogen in transitional, chemisorbed Fe(III) hydroxides – represented here as Fe(OH) 3 A – rapidly exchanges D/H with ambient water during crystal growth, there is a model-based expectation that Dα gt-w will not be affected by pH. This postulated D/H exchange would cease when Fe(OH) 3 A irreversibly transitions to FeOOH during crystallization – i.e., when Fe, O, and H are incorporated in the structure of the growing crystal. Thus, the flux balance model suggests that the observed dichotomy in the effects of pH on 18α gt-w and Dα gt-w is a result of distinctly different exchangeabilities of 18O/16O and D/H in transitional Fe(III) hydroxides that are chemisorbed on growing surfaces of goethite crystals. Observed values of 18α gt-w and Dα gt-w may represent steady-state – but not necessarily thermodynamic equilibrium – distributions of isotopes between H 2 O and the oxygen or hydrogen in the interiors of crystallizing goethites. Nevertheless, these steady-state values of Dα gt-w and 18α gt-w are generally reproducible and systematically relate δ 18O and δ D values of goethite to environmental variables. [ABSTRACT FROM AUTHOR]

Iron oxides and oxyhydroxides (referred to as "iron oxides") have been proposed as geochemical proxy archives for the reconstruction of paleoenvironmental conditions. Interpreting their isotopic and elemental compositions is potentially complicated by Fe2+-catalyzed recrystallization, a process by which iron oxides undergo substantial post-formational changes in their isotopic compositions in the presence of Fe2+ without exhibiting overt mineralogical or morphological changes. One major challenge in accounting for the effect of this process on iron oxide compositions is the ambiguity associated with quantifying recrystallization rates from isotopic data collected in laboratory experiments. Specifically, quantifying recrystallization rates has required an assumption regarding the further dissolution and reprecipitation that the recrystallized solid undergoes (referred to as "back-reaction"). Assumption of the fraction of back-reacting recrystallized solid may substantially affect the rates and extents of recrystallization calculated from bulk isotopic data. Recent experimental evidence indicates that back-reaction between recrystallized iron oxides and aqueous Fe2+ is gradual and partial. Here, we developed a model based on these recent experimental insights that simulated isotope dynamics during Fe2+-catalyzed recrystallization of goethite to quantify the rate of recrystallization. We estimated rate parameters using isotopic data collected by Joshi et al. (2017) and Frierdich et al. (2015a). We then simulated isotope dynamics using the estimated rate parameters and compared the simulations to published datasets from Frierdich et al. (2015a), Handler et al. (2009), Frierdich et al. (2014b), Joshi and Gorski (2016), Frierdich et al. (2019a), which were collected under similar experimental conditions of pH 7.5 and high solid Fe:fluid Fe molar ratios (20.2–22.0). We observed that a model that included partial back-reaction described all the datasets investigated here with a narrow range of rates: initial rates of 2.65–4.67 μ mol*m−2*d−1 and final rates of 4.72*10−3 - 0.178 μ mol*m−2*d−1. The resulting extents of goethite recrystallization were 14.1–19.8% over 28–60 days, substantially lower than previous estimates. The low rates and extents quantified in this work indicate that Fe2+-catalyzed recrystallization is likely less extensive than previously reported, and that this process has a limited impact on proxy archives in the rock record. The results of our work also suggest that back-reaction may have a major effect on isotopic fractionation factors interpreted from laboratory experiments and should be considered in future studies. [ABSTRACT FROM AUTHOR]

As consequence of the dual demands for pollution control and carbon (C) fixation in soils, Fe(II)-catalyzed mineral transformation may be a promising method to simultaneously immobilize heavy metals or organic matter (OM), but the underlying mechanisms remain unclear. Here, the synchronous sequestration mechanism of cadmium (Cd) and fulvic acid (FA) during Fe(II)-catalyzed the transformation ferrihydrite with C/Fe molar ratio of 0.21 were examined. Mineral phase analysis revealed that increasing the Fe(II) concentration (1–5 mM) favored the transformation of lepidocrocite and goethite to magnetite, and ferrihydrite transformation rate increased with increasing Fe(II) concentration. Color overlays and line profiles of elements depicted that Cd was dominantly adsorbed on the lepidocrocite and goethite surfaces. A positive correlation between the quantity of nonextractable Cd and magnetite further indicated that Cd may be sequestered by magnetite. Meanwhile, FA molecules were adsorbed on goethite surfaces and magnetite aggregates, and incomplete structure of lepidocrocite provide spaces for immobilizing C. Newly formed iron (Fe) (oxyhydr)oxides may immobilize Cd through surface binding, structural substitution, and physical encapsulation. The OM bound to the newly formed Fe (oxyhydr)oxides was rich in aromatic and carboxyl functional groups, which was beneficial for binding Cd, whereas the presence of Cd promoted the generation of nano pore spaces or defects and consequently enhanced FA sequestration. Therefore, Cd immobilization and FA sequestration can be synchronously achieved during the phase transformation. The findings provide a profound insight into various nanoscale mechanisms accounting for the fate of Cd and FA coupled with mineral transformation. The findings also are very helpful for developing strategies for simultaneously immobilizing heavy metals and C in soils. [ABSTRACT FROM AUTHOR]

The reaction mechanism of weathering of chlorite, an important rock-forming phyllosilicate, is not well understood in natural settings. In this work we investigated the weathering of Fe-rich chlorite from deep protolith to saprock to soil across a small shale-underlain watershed in the Appalachian Mountains, USA (Shale Hills). We found that oxidation of Fe(II) in chlorite always occurs prior to dissolution of the interlayers of the mineral. The oxidation of pyrite and chlorite commence near the water table across narrow depth intervals under the upper-catchment ridges, but well below the water table across wide depth intervals under the valley. We hypothesize that these patterns can be explained by hydrological and geochemical differences between the ridge and the valley: oxygenated water descends sub-vertically (1D flow) under the ridge, while under the valley, oxygen-depleted water moves upward to the stream and laterally out of the watershed in the subsurface (3D flow). Geochemical and mineralogical characterization indicates that the transformation of Fe-rich chlorite at Shale Hills is initiated by the oxidation of Fe(II). Next, the interlayer hydroxide sheet dissolves to form hydroxy-interlayered vermiculite and then vermiculite. During the transformation, Mg and Fe are released into solution and Fe is reprecipitated as goethite in pore space. Delivery of oxygen to the deep subsurface by infiltration of meteoric water is thought to control the initial transformation of chlorite at Shale Hills. It is possible that weathering of many Fe(II)-rich minerals is initiated by oxidation as mediated by rates of subsurface oxygen delivery. [ABSTRACT FROM AUTHOR]

Banded Iron Formations (BIFs) are ancient marine chemical sediments that contain various Fe-bearing minerals such as hematite (Fe 2 O 3), magnetite (Fe 3 O 4), siderite (FeCO 3) and a variety of FeII - /FeIII-silicates. The prevailing opinion is that primary Fe(III) (oxyhydr)oxides, such as ferrihydrite (simplified formula of Fe(OH) 3), were precipitated from the ocean's photic zone by marine plankton, and a fraction of these minerals was subsequently transformed into secondary magnetite and siderite by dissimilatory Fe(III)-reducing bacteria (DIRB). However, aside from broad estimates, it is currently unknown what fraction of the primary Fe(III) minerals was sedimented to the seafloor where it was eventually lithified, and what fraction was reduced by DIRB in the water column, thus forming a microbial Fe cycle in the water column. To test this, we conducted Fe cycling experiments with marine phototrophic Fe(II)-oxidizing bacteria and DIRB under conditions mimicking the Precambrian ocean water column with elevated Fe(II) and Si concentrations. We followed secondary mineral formation over three consecutive redox cycles (oxidation followed by reduction) over a time interval of up to 58 days to determine which mineral phases would ultimately have settled as BIF forming sediments. We used wet geochemical methods to follow Fe speciation, measured dissolved silica and volatile fatty acid (VFA) concentrations, determined cell-mineral associations using fluorescence and electron microscopy, and characterized the mineralogy of the precipitates using 57Fe-Moessbauer spectroscopy and X-ray diffraction (XRD). Our results showed that both the absence of silica and an increasing number of Fe cycles favored the formation of more crystalline minerals, such as goethite (α-FeOOH). However, in the presence of high concentrations of monomeric silica, as suggested for ancient oceans (2.2 mM), only short-range ordered (SRO) Fe(III) minerals such as ferrihydrite were observed. These did not transform into the more thermodynamically stable goethite during repeated Fe cycling. Interestingly, no magnetite formed in any of the setups. Instead, increasing Si concentrations favored the formation of increasing quantities of Fe(II) minerals. Microscopy revealed a tight association between microbial biomass and minerals formed. Dissolved silica analysis showed the removal of Si from solution congruent with Fe(II) oxidation and a release of Si during Fe(III) reduction. Together, these results suggest an important role of co-precipitated biomass as well as silica for secondary mineral formation by either constraining crystal growth and/or inhibiting Fe(II)-induced mineral transformation. Overall, our results imply that microbial Fe cycling during settling of primary ferrihydrite through the photic zone in a Precambrian ocean would have resulted in the partial transformation of ferrihydrite into secondary Fe(II) mineral phases in the water column. This would have resulted in the accumulation of mixtures of a ferrihydrite-silica composite and Fe(II) minerals in the initial BIF forming sediments. [ABSTRACT FROM AUTHOR]

We examined iron biogeochemistry in continental margin sediments along the western side of the Antarctic Peninsula (WAP) to explore the connections between iron redox cycling and other sediment biogeochemical processes, and to specifically examine the role of sediments as a source of iron to support Southern Ocean primary productivity. Total iron (Fe T) in WAP sediments ranged from ∼4 to 6 wt% Fe and showed no consistent depth variations. Total iron oxides (Fe Ox) represented ∼20–30% of Fe T in WAP surface sediments and was comprised of two types of materials: Fe ox1 , which is thought to contain amorphous, highly reactive, and poorly crystalline iron oxides such as ferrihydrite and lepidocrocite, and Fe ox2 , which is thought to contain magnetite and less reactive, more crystalline iron oxides such as goethite and hematite. Absolute and relative concentrations of Fe Ox declined with sediment depth, presumably due to reductive dissolution, and there was also a major depth change in the speciation of Fe Ox. Near the sediment surface ∼30% of Fe Ox was Fe ox1 , while below ∼30 cm Fe ox1 was almost completely consumed and therefore here virtually all Fe Ox was Fe ox2. Consistent with these observations, a simple reaction-transport model applied to the depth distributions of Fe ox1 and Fe ox2 iron in WAP shelf sediments suggested a ∼20-fold difference in the relative reactivity of these different oxides towards reductive dissolution (Fe ox1 > Fe ox2). At several stations profiles of pore water dissolved iron and solid phase Fe ox1 can be explained by steady state iron redox cycling. In contrast, profiles at other stations showed evidence of non steady-state iron redox cycling. Seasonal changes in the sediment organic carbon rain rate at these sites may explain this latter behavior. Differences in the behavior of iron at different sites may be related to the interplay between changes in sediment redox conditions and their impact on bioturbation and iron redox cycling. Sediment iron sources to the water column include dissolved iron (∼Fe2+) benthic fluxes as well as sediment resuspension processes that mix iron oxides (i.e., Fe ox1) found in surface sediments into the bottom waters. The impact these benthic iron sources will have on surface water iron concentrations (and eventually primary production) will depend on transport processes that move this iron from deeper waters to surface waters. They will also depend on chemical transformations in the water column that affect iron bioavailability. While sediment processes (in general) appear to be an important source of iron to Southern Ocean surface waters, there is large uncertainty in their magnitude. However, the results presented here demonstrate that the suspended sediment flux of amorphous iron oxides needs to be considered when discussing sediment iron sources to Southern Ocean surface waters. [ABSTRACT FROM AUTHOR]

The dynamics of tropical weathering through time with the formation and long-term evolution of laterite associated with climatic and geodynamic forcing is still a poorly explored issue. To better access this, we focused on lateritic-bauxitic duricrusts from the well-explored, 300 m high Kaw mountain in northeastern French Guiana. Macroscopically homogeneous Fe (oxyhydr)oxides-rich subsamples were separated from 10 bulk samples. Bulk- and subsamples were investigated by mineralogical and geochemical analyses and (U-Th)/He geochronology. The samples show a large heterogeneity on the macro- and microscopic scale reflecting different stages of duricrust formation and evolution through processes of dissolution and (re)precipitation of Fe (oxyhydr)oxides. The 284 (U-Th)/He ages obtained for goethite α-(Fe, Al)OOH and hematite α-Fe 2 O 3 range from 30.5 ± 3.1 to < 0.8 Ma and show large variability within a sample. The oldest hematite and Al-poor goethite subsamples precipitated since 30 Ma and formed while kaolinite was stable. Precipitation of Fe-minerals increased since ∼ 14–12 Ma but still happened under ferruginous lateritic, non-bauxitic conditions. The dissolution and (re)precipitation of Fe minerals, Al-substitution in goethite, and the overall enrichment in Th, as well as gibbsite precipitation indicate an intensification of weathering and a shift towards bauxitic conditions since the end of the Miocene. The Th-, U-, and Al-rich Fe phases formed in this late episode of intense weathering partially replace the oldest, often Th- and U-poor phases leading to a considerable age spread. We claim that this episode of intensified weathering, which had its peak at ca. 6–2 Ma, corresponds to the bauxitization of the lateritic cover of Kaw mountain. Our proposed model of lateritization since at least 30 Ma and bauxitization since the late Miocene provides new constraints on the timescale and intensity of weathering at Kaw mountain. The onset of lateritization in French Guiana (Kaw region) is potentially older than ca. 30 Ma and was possibly synchronous with the development of bauxites in neighboring countries, and differences in the Paleogene weathering intensity might be due to different drainage capacities of the parental material. Late Neogene bauxitization suggests a regional increase in precipitations and drainage potentially linked to increased incision owing to local uplift. Finally, we confirm that a detailed combination of geochronological results coupled to mineralogical and geochemical analyses improves our understanding of tropical weathering processes and duricrust formation by placing mineralogical and geochemical processes into a temporal framework. [ABSTRACT FROM AUTHOR]

Iron (Fe) cycling exerts strong control on the mobility and bioavailability of the key nutrient phosphate (PO 4) in soils and sediments. Coprecipitation of PO 4 is known to alter the structure of Fe (oxyhydr)oxides (FeOx), however the environmental fate of PO 4 -bearing FeOx is not well-understood. Here, PO 4 -bearing FeOx with 9 mol% coprecipitated PO 4 were prepared by Fe(III) hydrolysis and Fe(II) oxidation in the presence of dissolved PO 4 , in addition to pure FeOx synthesized in PO 4 -free solutions. The pure and PO 4 -bearing FeOx were subsequently exposed to different concentrations of dissolved Fe(II) and sulfide (2 and 10 mmol L−1). Mineral transformations and the fate of PO 4 were tracked over 7–14 days with wet chemical techniques (including sequential Fe and S extraction) and synchrotron-based Fe K-edge X-ray absorption spectroscopy. Coprecipitation of PO 4 affected the rate and extent of FeOx transformation differently for Fe(II) and sulfide. Poorly-ordered PO 4 -bearing FeOx was preserved in the presence of dissolved Fe(II) while pure ferrihydrite was nearly completely transformed into goethite over 7 days. By contrast, coprecipitation of PO 4 rendered FeOx more reactive towards sulfide compared to pure FeOx. Reaction with dissolved sulfide resulted in the formation of non-sulfidized Fe(II) or Fe(II) sulfide under high and low Fe/sulfide ratio, respectively. Under low Fe/sulfide ratio, Fh and PO 4 -bearing, poorly-ordered FeOx were nearly completely sulfidized after 14 days. Sulfidation of FeOx led to efficient release of PO 4 into solution, and at low Fe/sulfide ratio more PO 4 was released than expected based on the extent of Fe sulfidation. The results suggest feedback mechanisms of environmental relevance: coprecipitation of strongly-sorbing species such as PO 4 disrupts FeOx structure, which affects FeOx reactivity and the overall nutrient or contaminant retention capacity of soils or sediments differently depending on the ambient redox conditions. Specifically, the switch from reducing to sulfidic conditions may be associated with the disproportionate release of nutrients and contaminants. [ABSTRACT FROM AUTHOR]

This study simulates the hydrothermal conditions that existed on carbonaceous chondrite planetesimals in the early solar system. Our experiments are relevant to alteration conditions that existed on the CV parent body and the late stage oxidizing alteration of the CM chondrites. We conducted 11 alteration experiments using chips of the CO3 chondrite Kainsaz. Water was added to each chip and sealed in separate Teflon reaction vessels for 175 days. Samples were altered at different initial water-to-rock ratios (W/R: 0.2–0.8) and temperatures (50 °C and 150 °C). Isotopically doped 17O-rich heavy water (δ17O: +64.5‰) was used in five runs. All samples experienced pronounced alteration under a partially open system environment where gases were able to escape the reaction vessels. The style of alteration (Fe-alkali metasomatism) is similar in all cases. The principal alteration minerals formed are Fe-oxyhydroxides (goethite) and Fe-oxides (magnetite), with smaller quantities of Fe-sulphides. Minor phases formed include fayalite, sulphates (gypsum and Fe-sulphate) and calcite. Nanophase, poorly crystalline phyllosilicates formed in the high-temperature samples but are absent from the low-temperature experiments. In all instances, Mg-rich chondrule silicates remained chemically unaltered although some grains suffered hydrothermal fracture. Chondrule mesostases remained largely unaffected. By contrast, kamacite readily dissolved, acting as a source of Fe and Ni for the fluid phase. A new generation of nanophase Fe-sulphides formed within the matrix, while pre-existing pyrrhotite group sulphides experienced Ni enrichment (<3 at%). In the high temperature samples these sulphides were also partially oxidized, lowering their (Fe + Ni)/S ratio. High-Ni sulphides (pyrrhotite with Ni > 10 at%) were formed in the 150 °C samples, most likely by sulphidation of taenite. Matrix alteration cemented grains together, reducing porosity. The fine-grained matrix shows highly variable degrees of alteration, with minimally altered matrix in direct contact with regions of heavily altered matrix. Chondrule fine-grained rims (FGRs) were preferentially altered. These textures imply that the unaltered matrix readily reacted with the fluid phase, resulting in an efficient depletion of dissolved ions (Fe2+ and S2-), limiting reactivity until further primary phases were dissolved. At larger length-scales the distribution of heavily altered matrix reveals the presence of large ∼100 µm wide channels that meander through the specimens. Their textures resemble features seen in some CM chondrites and the ungrouped CO-like chondrite MIL 07687. We suggest that alteration fronts developed by sustained rapid reaction of matrix with dissolved cations in solution. Our observations provide a mechanism for the establishment and maintenance of geochemical microenvironments on chondritic asteroids. The effects of open system loss notwithstanding, our experiments demonstrate that more advanced alteration is correlated with higher initial W/R ratios. The use of 17O-rich doped water allowed the isotopic effects of aqueous alteration to be observed. Bulk rock compositions evolved towards the initial water composition, reflecting the incorporation of heavy O into hydrated minerals. Additionally, altered samples shifted in δ18O space, reflecting the competing effects of water–mineral fractionation and mass fractionation due to the preferential escape of isotopically light water. [ABSTRACT FROM AUTHOR]

Sorption of Mo to goethite and related iron (hydr)oxides plays an important role in controlling the mobility of Mo in soil and aquatic environments. We first performed ab-initio molecular dynamics (MD) simulations of Mo complexation at the goethite {1 0 1}-water interface. We find that molybdenum adsorbed on goethite mainly exists as the inner-sphere tetrahedral bidentate and monodentate corner-sharing complex, instead of the previous argued bidentate edge-sharing or outer-sphere complex. Different from previous literature, we didn't find any distorted octahedral structure of Mo on goethite. The predicted Mo-Fe distances of bidentate and monodentate corner-sharing complex based on ab-initio MD is 3.53 and 3.38 Å, respectively, which are consistent with the fitted Mo-Fe distances: 3.40 ± 0.15 Å and 3.41 ± 0.1 Å from EXAFS. We measured the adsorption of Mo (VI) on goethite (α-FeOOH) at different initial concentration and pH from 3 to 11 under N 2 atmosphere and constructed a surface complexation model that is consistent with the molecular speciation based on ab-initio MD, XANES, EXAFS and reported in-situ ATR-IR analysis (Davantes and Lefevre, 2015, 2016). Application of SCM for Mo on goethite assuming iron oxides as the principal component of ferromanganese crust (containing average 276 mg/kg Mo) will have ∼0.3 μg/l Mo in seawater in equilibrium. The observed ∼10 μg/l Mo in seawater (c a. 400–800 yr) is between 0.3 (adsorption equilibrium by marine goethite) and 23 μg/l (adsorption equilibrium by marine birnessite, Kashiwabara et al., 2011), suggesting that molybdenum in seawater has reached equilibrium with ferromanganese crust, and goethite (57%) probably plays a more important role than birnessite (43%) in regulating molybdenum abundance in the ocean, which has not been fully recognized in past. Observed molybdenum isotopic fractionation between seawater and ferromanganese crust excesses the experimental molybdenum isotopic fractionation range during adsorption by birnessite and goethite (Goldberg et al., 2009). Based on reported experimental molybdenum isotopic fractionation values and our SCM prediction, the molybdenum isotopic fractionation δ98/95Mo value should vary between 1.6 and 2.3‰, which is lower than the observed range between seawater and ferromanganese crust: 2.7–3.2‰ about 1‰, suggesting the disequilibrium of molybdenum isotopic fractionation in ocean. To clarify the discrepancy, this study highlights the necessity of clarifying the molybdenum source in hydrogenic and hydrothermal ferromanganese crusts before understanding molybdenum isotopic fractionation between seawater and ferromanganese crust. [ABSTRACT FROM AUTHOR]

Iron minerals are the most important arsenic host in As-contaminated deltaic sediments. Arsenic release from Fe minerals to groundwater exposes millions of people worldwide to a severe health threat. To understand the coupling of Fe mineralogy with As (im)mobilization dynamics, we analyzed the geochemistry and mineralogy of a 46 m long sediment core drilled into the redox transition zone where a high As Holocene aquifer is juxtaposed to a low As Pleistocene aquifer in the Red River delta, Vietnam. We specifically concentrated on mm- to cm-scale redox interfaces within the sandy aquifer. Various Fe phases, such as Fe- and Mn- bearing carbonates, pyrite, magnetite, hematite and Fe-hydroxides (goethite, lepidocrocite) with distinct As concentrations were identified by a combination of high-resolution microscopic, magnetic and spectroscopic methods. The concentration of As and its redox species in the different Fe-minerals were quantified by microprobe analysis and synchrotron X-ray absorption. We developed a conceptual model integrating Fe-mineral transformations and related As (im)mobilization across the redox interfaces. Accordingly, As is first mobilized via the methanogenic dissolution of Fe(III) (oxyhydr)oxide mineral coatings on sand grains when reducing groundwater from the Holocene aquifer intruded into the Pleistocene sands. This stage is followed by the formation of secondary Fe(II)-containing precipitates (mainly Fe- and Mn-bearing carbonates with relatively low As < 70 μg/g), and minor pyrite (with high As up to 5800 μg/g). Due to small-scale changing redox conditions these Fe(II) minerals dissolve again and the oxidative behavior of residual Fe(III)-phases in contact with the reducing water leads to the formation of abundant Fe(III)/Fe(II) (oxyhydr)oxides especially at the studied redox interfaces. Microcrystalline coatings and cementations of goethite, magnetite and hematite have intermediate to high As sorption capacity (As up to 270 μg/g) creating a key sorbent responsible for As (im)mobilization at interfingering redox fronts. Our observations suggest a dynamic system at the redox interfaces with coupled redox reactions of abiotic and biotic origin on a mm to cm-scale. In a final stage, further reduction creates magnetite with low As sorption capacity as important secondary Fe-mineral remaining in reduced gray Pleistocene aquifer sands while considerable Fe and As is released into the groundwater. The presented redox-dependent sequence of Fe phases at redox interfaces provides new insights of their role in As (im)mobilization in reducing aquifers of south and southeast Asia. [ABSTRACT FROM AUTHOR]

Several recent studies have reported a strong association between Sc and goethite (α-FeOOH) in synthetic analogs and natural samples. However, the mechanism of Sc immobilization by goethite and controlling factors remain unclear. This study investigated the adsorption behavior and molecular-scale immobilization mechanisms of Sc at water/goethite interfaces through a combination of batch adsorption and desorption experiments, X-ray absorption fine structure (XAFS) analyses, and density functional theory (DFT) calculations. Results indicate that Sc is preferentially adsorbed on goethite with the formation of bidentate-binuclear inner-sphere complexes at the corner-sharing sites. Bulk Sc K-edge XAFS analyses suggest that Sc is incorporated into the goethite structure by substituting for Fe(III) within the crystal in synthetic Sc-substituted goethite, which is further confirmed in natural goethite particles in the laterite by using micro-focused XAFS (μ-XAFS). Furthermore, we demonstrate that the adsorbed Sc on the goethite surface can be structurally incorporated into the goethite lattice in the presence of aqueous Fe(II) possibly through goethite recrystallization induced by aqueous Fe(II). This process may affect the (re)partitioning of Sc between the goethite surface and the mineral bulk, which could be used to rationally explain disparate Sc speciation in laterites from different regions. Our study elucidates the molecular-scale mechanisms underlying Sc adsorption on and structural incorporation into goethite, providing critical insights into the understanding of geochemical behavior and environmental fates of Sc. [ABSTRACT FROM AUTHOR]

Fe(II) oxidation by O 2 is an important process generating Fe (oxyhydr)oxides, which play sorptive, structural and electron-transfer roles in soils. Here we explored how native minerals and organic matter (OM) affect the rate of Fe(II) oxidation and resulting de novo Fe(III) minerals in soil slurries. A topsoil was collected from the Luquillo Experimental Forest, and a topsoil and subsoil were collected from a cultivated site at the Calhoun Experimental Forest. We oxidized 57Fe(II) in these soils either untreated or with OM and/or Fe (oxyhydr)oxides removed. We measured Fe oxidation kinetics by tracking the loss of Fe(II) and characterized the de novo Fe(III) solids using 57Fe Mössbauer spectroscopy. We find that OM retarded Fe(II) oxidation, while pre-existing Fe (oxyhydr)oxides played a significant role in catalyzing Fe(II) oxidation. The non-extractable (residual) soil minerals (i.e. phyllosilicates and quartz) after removing Fe (oxyhydr)oxides, had only a minor effect on oxidation rates. In the topsoils, OM resulted in lower-crystallinity Fe(III) minerals, including nanogoethite and highly-disordered Fe phases, relative to soils with OM-removed. Goethite of varying crystallinity was promoted by the pre-existing Fe (oxyhydr)oxides in all soils, in contrast to homogenous oxidation treatments in which lepidocrocite was formed. Fe(II) oxidation in the Calhoun subsoil, which was enriched in native crystalline Fe phases and depleted in OM, resulted in large-particle goethite with the highest crystallinity of all treatments. Crystalline hematite was also formed in the Calhoun subsoil most likely due to a templating effect of pre-existing hematite. These findings suggest that the nature of de novo formed Fe minerals in soils and sediments may depend strongly on resident existing soil OM and Fe phases. This study extends similar results from previous model mineral and organic experiments to whole, complex soils and thus constitutes a significant step forward in understanding Fe transformation in natural environments. [ABSTRACT FROM AUTHOR]

Magnesium (Mg) isotopes fractionate during rock/mineral weathering and leaching, secondary mineral neoformation, adsorption/desorption, and plant-related Mg recycling, but the mechanisms and extent of fractionation are not well understood. Here, we report the fate of Mg and its isotopes during basalt weathering and soil development in the Hawaiian Islands by sampling soils of varying age (0.3, 20, 150, 1400, and 4100 ka) in undisturbed humid rainforests. Magnesium concentrations in bulk soils are variable with depth and age, ranging from 0.07 to 8.79 wt.%, and significant Mg depletions (up to 99%) relative to parent basalts are visible after 20 ka. Bulk soils display a large age-dependent range of δ26Mg values ranging from −0.60 to +0.26‰. A sequential leaching scheme showed that labile Mg is depleted whereas residual Mg is enriched in isotopically heavy Mg. The two youngest soils (0.3 ka) display δ26Mg value similar to basalt for both labile or residual Mg, indicating either that basalt weathering causes little Mg isotope fractionation or that δ26Mg value is overwhelmed by the primary minerals during 0.3 ka. However, in the older soils (≥20 ka), the δ26Mg values of both labile and residual Mg vary non-linearly as a function of time, with an increase in the difference between them. These variations are explained by both plant-related Mg recycling and progressive mineral transformations, evolving from short-range-order (SRO) minerals (allophane and ferrihydrite) to more crystalline products (goethite, gibbsite and kaolin minerals). Indeed, plant-related Mg recycling causes the enrichment of light Mg isotopes in the labile Mg, while secondary phases incorporate more and more heavy Mg isotopes with time. These results reconcile experimental and field studies and highlight a weathering control of Mg isotopes delivered to the oceans. [ABSTRACT FROM AUTHOR]

A key reaction underlying the charge transport in iron containing oxides, clays, micas is the Fe 2 + - Fe 3 + exchange reaction between edge-sharing iron octahedra. These reactions facilitate conduction in these minerals by the thermally-activated hopping of small polarons across the lattice. Depending on the mineral and local charge state the small polaron can either encase an electron or hole. The probability for conduction of small polarons depends strongly on the height and adiabicity of the reaction barrier, with larger and more diabatic barriers yielding slow conduction associated with either weak coupling or a large prerequisite rearrangement of the lattice during charge transport. To model these reactions, a first principle electron transfer (ET) method was developed to model the small polaron hopping between the edge-sharing octahedra sites in hematite ( e - polaron), goethite ( e - polaron), and annite ( h + polaron) bulk structures. The ET method is based on electronic structure methods (i.e., plane-wave Density Functional Theory) capable of performing calculations with periodic cells and large size systems efficiently while at the same time being accurate enough to be used in the estimation of the electron-transfer coupling matrix element, V AB , and the electron transfer transmission factor, κ el . The calculations confirmed the existence of small polarons in all three minerals, and the reactions were predicted to be strongly adiabatic. It was found that transfer of a hole in the octahedral layer of annite had an adiabatic barrier of 0.311 eV, and the transfer of an extra electron in hematite and goethite had adiabatic barriers of 0.242 eV and 0.232 eV respectively. The electronic coupling parameters, V AB , were found to be 0.188 eV, 0.196 eV, and 0.102 eV respectively for hematite, goethite, and annite. While similar bonding topologies pertain, the findings reveal the importance of subtle differences in local structure. [ABSTRACT FROM AUTHOR]

The alkaline-earth metal ion series comprises Be, Mg, Ca, Sr, Ba, and Ra. Calcium (Ca) and magnesium (Mg) are the most abundant alkaline-earth metal ions in nature and their interaction with the mineral surfaces of metal (hydr)oxides (e.g. ferrihydrite, Fh) affects the bioavailability, mobility, and geochemical cycling of many relevant ions. The adsorption of Ca2+ and Mg2+ ions to well-characterized freshly precipitated Fh has not been extensively measured yet in systems with a large variation in pH (5–10), ionic strength (0.01–1 M), and ion adsorption (0.002–2 μmol m−2). Nor have such adsorption data been interpreted with a surface complexation model that regards the structure of the adsorbed complexes and state-of-the-art insights into the surface structure of this nanomaterial. The primary adsorption data collected in this study (M2+/Fe) were scaled in a consistent manner to the surface area of Fh derived with a recently developed probe-ion methodology, before these data were interpreted with the charge distribution (CD) model, using MO/DFT/B3LYP/6-31+G** optimized hydrated geometries to obtain independently the CD coefficients. The pH-dependent adsorption behavior of Ca and Mg is rather similar. Both cations (M2+) form predominantly bidentate inner-sphere surface complexes ((FeOH) 2 Δz0MΔz1), most possibly as a binuclear double corner (2C) complex according to EXAFS. This binding mechanism explains the relatively high H+/Ca2+ exchange ratio and the related pH-dependency of the Ca2+ adsorption. Modeling of the adsorption data reveals and quantifies the surface site heterogeneity of Fh, distinguishing high and low affinity sites for binding M2+ ions. The surface structure of Fh has been evaluated to rationalize this phenomenon and identify possible surface configurations. The increase in the FeOH-M2+ bond strength may be due to a redistribution of charge within specific sets of Fe1 polyhedra at the Fh surface that have in the underlying solid a set of common oxygen ions with an insufficient charge neutralization. According to our surface structural analysis of 2.2–2.8 nm particles, the FeOH site density involved (∼0.3 ± 0.1 nm−2) aggress with the surface site density of high affinity sites found by Ca2+ ion adsorption modeling (0.30 ± 0.03 nm−2). Extending our data analysis to literature data, comprising the full series of alkaline-earth ions, an increase in adsorption affinity with increase in the ionic radius of these cations was found, i.e. Be2+ < Mg2+ < Ca2+ ≈ Sr2+ < Ba2+ < Ra2+, which is opposite to the order of the Hofmeister series observed for other Fe-(hydr)oxides (e.g. hematite, goethite). The affinity trends have been evaluated with a model for ion adsorption energy developed in this study. This analysis suggests that a difference in the order of affinity (log K) can be explained by a different energy and/or entropy contribution of interfacial water in the binding of the metal ions. This points to a relatively strong binding of physisorbed water by Fh in comparison to other Fe-(hydr)oxides where the energy of ligand exchange dominates. For Fh, interfacial water is more strongly bound by high affinity sites than by low affinity sites, according to our model. [ABSTRACT FROM AUTHOR]

This study examines the whole-rock geochemistry, Fe-oxide texture and crystal morphology, and Fe-oxide (U-Th)/He date variation of jasperoids, as well as the relationships between these characteristics, in order to evaluate jasperoids as an indicator for gold mineralization. Jasperoid samples with a range of textures, appearances, and expected gold concentrations were collected from two gold districts in Nevada: the northern Carlin trend (Gold Quarry Mine), and the Battle Mountain district (Marigold Mine; Battle Mountain prospect). In our jasperoid samples, whole-rock concentrations of Au are positively correlated with As, Ag, Pb, Sb, U, W, and Tl. The following Fe-oxide textures are associated with anomalous gold concentrations: disseminated, submicron crystals; feathery and acicular crystal morphologies; concentric zonation from hematite to goethite; and botryoidal textures. Calculated closure temperatures for the (U-Th)/He system in observed jasperoid Fe-oxide morphologies within our dataset range from 26 to 136 °C, indicating variable susceptibility to He diffusion at near-surface conditions. Fe-oxide (U-Th)/He dates range from 29.4 ± 0.5 Ma to 0.11 ± 0.01 Ma, displaying intra- and intersample variation. We attribute the date variation to multiple factors including He implantation, parent isotope exchange, and He loss through closure temperature sensitivity and alpha-ejection. The intra- and intersample variation within the Fe-oxide (U-Th)/He dates limits our ability to make geologic interpretations. Our case study identifies important limitations of the (U-Th)/He method in jasperoids and provides insight on how He date variation might be avoided in future studies. [ABSTRACT FROM AUTHOR]

Published (U-Th)/He ages indicate that an oolitic Miocene channel iron deposit (CID) on Mesa J in the Hamersley province of Western Australia (∼22 °S latitude) contains three predominant generations of Fe (III) oxides – two generations of older hematite and one of younger goethite. Selective dissolution and sequential atom balance calculations were combined with chemical and oxygen isotope analyses to determine the δ18O values of hematite, goethite, and quartz in eight samples from a core drilled in that CID. For the quartz (Q), δ18O Q = +21.7 (±0.9) ‰. For the younger hematite (Hm1), δ18O Hm1 ≥ +3.6 (±0.6) ‰, whereas for the older hematite (Hm2), δ18O Hm2 ≤ +2.1 (±0.8) ‰. The oolitic CID goethite (G) crystallized in the late Miocene [7 (±1) Ma] and is a solid solution represented as Fe (1−Y) Al Y (CO 3) X O (1− X) OH with values of δ18O G that range from −0.4‰ to +0.7‰. A mixing model for the solid solution expresses the value of δ18O G in terms of Y , X , relevant fractionation factors, and the δ18O of the endmember FeOOH (δ18O gt). Mixing model-derived values of δ18O gt range from −2.4‰ to −0.7‰. Paired values of δD gt and δ18O gt in seven of eight late Miocene oolitic goethites from Mesa J indicate crystallization from meteoric waters at an average temperature of 20 (±5) °C. In the late Miocene, Mesa J was in the subtropics at a paleolatitude of ∼29 °S, which invites comparison with the climate of the near-coastal community of Mingenew in Western Australia (presently at 29 °S latitude). The modern MAT at Mingenew is 20 °C – i.e., indistinguishable from the late Miocene Mesa J average of 20 °C. However, this similarity is not matched by the mean annual precipitation (MAP). The modern MAP at Mingenew is about 400 mm, but the lateritic weathering that produces abundant pedogenic Fe (III) oxides appears to require a seasonally contrasting climate with rainfall totals of at least 1300 mm/yr. In the late Miocene, southward-shifted summer season tropical cyclones might have delivered such large amounts of rain (with relatively low δD and δ18O values). If so, the δD gt and δ18O gt of the oolitic goethites of Mesa J support the idea of a rainfall-driven, possibly microbially mediated, summer season bias in the timing of crystallization. Thermal buffering in the regolith can reconcile summer-dominated goethite crystallization with a temperature that would be analytically indistinguishable from the MAT. Comparison of the δ18O gt values of the Mesa J goethites with published δ18O values of goethites of similar age from two other sites in the Hamersley province suggest a possible increase in δ18O of late Miocene rainfall with increasing distance from the coast. [ABSTRACT FROM AUTHOR]

Manganese and its compounds have been extensively studied because of their far-reaching roles in a wide range of biogeochemical processes in natural systems. The (ad)sorption behavior of Mn(II), however, is poorly understood despite its important role as the primary reaction step for surface-catalyzed Mn(II) oxidation that is the principal abiotic process forming various Mn (oxyhydr)oxides in nature. Here, we systematically examined Mn(II) (ad)sorption to one of the most common natural sorbents, goethite, in oxygen- and carbonate-free systems. Traditional sorption edge and isotherm experiments were conducted by varying sorbate-to-sorbent ratio (0.027–15 μmol∙m−2) and solution pH (pH 5.0–9.0). The effects of dissolved carbonates on Mn(II) sorption were also assessed in a range of naturally prevalent concentrations (0.5–10 mM NaHCO 3). The Mn(II) uptake on goethite followed a typical Langmuir isotherm in the absence of dissolved carbonates, with increasing maximum adsorption capacities (Γ max) from 0.19 at pH 6.5 to 3.4 μmol∙m−2 at pH 9.0. The presence of dissolved carbonates raised the extent of Mn(II) adsorption, which appeared to be directly correspondent to that of the adsorption of dissolved carbonates. Extended X-ray absorption fine structure (EXAFS) analysis indicated that Mn(II) predominantly formed inner-sphere binuclear bidentate surface complexes. Mn(II) uptake became deviated from the Langmuir model and showed a clear indication of surface precipitation when the Mn(II) sorption density (Γ) exceeded a threshold value in a given solution composition. This secondary Mn(II) phase was identified as rhodochrosite using X-ray diffraction (XRD) and transmission electron microscope (TEM). Additionally, it would be plausible that a minor fraction of adsorbed Mn(II) coexisted with the secondary rhodochrosite according to a linear combination fitting (LCF) of the X-ray absorption near edge structure (XANES) spectra of Mn reference and samples. These systematic investigations of the macroscopic and microscopic behaviors of Mn(II) (ad)sorption to goethite provide a critical avenue for disentangling surface-catalytic Mn(II) oxidation processes, which ultimately lead to the formation of diverse Mn (oxyhydr)oxides in the environment. [ABSTRACT FROM AUTHOR]

• The rapid consumption of reactive silicates suggests the immediate influence of geochemical alteration on reservoir transmissivity and structure. • Discrepancy between the average permeability change across the whole core and predicted by the reactive transport model may be attributed to swelling of clays and/or dislocation of particles. • Multi-resolution CT scans provide critical evaluation of scale and corresponding thresholding techniques for accurate porosity quantification. • Variation in the aqueous chemistry, RT simulations and CT-scans show alterations of the core occurring principally at the inlet. We report a series of acidified brine flow-through experiments designed to quantify the coupled alteration of geochemical, structural and fluid transport properties of a Mt. Simon sandstone core recovered at a depth of 2110.5 m as part of the Illinois Basin Decatur Project (IBDP). Flow-through experiments were completed at representative in-situ conditions to isolate the stages of initial CO 2 injection: first, a single-phase (CO 2 –saturated brine, Stage 1) followed by a second multi-phase (CO 2 –saturated brine and supercritical CO 2 , Stage 2) experiment. During both stages, effluent major and trace cation concentrations were tracked through time. Two imaging methods were employed to analyze the structural alterations of the rock core induced by the percolation of CO 2 -saturated brine and supercritical CO 2 : (1) scanning electron microscopy-petrography before Stage 1 and after Stage 2 and (2) computed tomography (CT) scans before and after Stage 2. The time series of Stage 1 effluent solutes were used to constrain a reactive transport simulation of the system. Modeling results suggest the evolution of the solute composition is a result of coupled dissolution of K-feldspar, calcite, illite and pyrite, and precipitation of montmorillonite, mesolite, alunite, diaspore, goethite and muscovite. The model predicted a net opening of pore space and associated increased permeability at the inlet. However, across the whole core, an overall decrease in permeability of approximately 23% ± 0.01 after Stage 1 was determined experimentally. CT analysis confirmed a corresponding decrease in porosity. A comparable permeability decrease was directly measured during Stage 2, concurrent with a decrease in the volume of macro-pores based on multiple CT-resolution methods. In total, this coupled approach demonstrates that geochemical alterations exert a first order control on the evolution of fluid transport properties through time at the earliest stages of in-situ CO 2 injection and suggest that chemical dynamics ultimately influence both the magnitude and timing of alterations to the physical integrity of Mt. Simon reservoir over these timescales. [ABSTRACT FROM AUTHOR]

Iron redox cycling in clay minerals plays important roles in nutrient cycling and contamination migration in soils and sediments. Studies have shown interfacial electron transfer (IET) between sorbed Fe(II) and structural Fe(III) in clays, but the impact of IET on biological redox reactions has not been investigated. Here we studied the impact of such IET process on an example redox reaction, i.e. coupled Fe(II) oxidation and nitrate reduction, in the presence of the nitrate-reducing bacterium Pseudogulbenkiania sp. strain 2002. Aqueous Fe2+ was sorbed to basal surface (pH 6) and edge sites (pH 8) of nontronite (NAu-2) and montmorillonite (SWy-2). The amount of Fe(II) sorption was lower at pH 6 than at pH 8. At pH 6, the extent of IET from basal Fe(II) to structural Fe(III) was higher in SWy-2 than in NAu-2, resulting in a higher proportion of structural Fe(II) in SWy-2. Because structural Fe(II) is more reactive than basal Fe(II), such IET resulted in a higher reactivity of SWy-2-associated Fe(II) than that of NAu-2-associated Fe(II) towards biologically-mediated nitrate reduction. At pH 8, extensive IET from highly reactive edge-Fe(II) to structural Fe(III) in NAu-2 resulted in formation of structural Fe(II) and Fe oxides, which lowered the reactivity of NAu-2-associated Fe(II). In contrast, due to limited IET in SWy-2 at pH 8, a large fraction of sorbed Fe(II) remained and was associated with SWy-2 and/or goethite/mixed Fe(II)-Fe(III) nanoparticles, which were highly reactive. As a result, SWy-2-associated Fe(II) is more reactive than NAu-2-associated Fe(II) at pH 8. The results of this study have important implications for understanding clay redox reactions in such environments where clay minerals and aqueous Fe2+ are in contact and IET occurs. [ABSTRACT FROM AUTHOR]

Abstract Sorption has been recognized as a predominant process for the mobility and transport of arsenic (As) in groundwater. However, the model-based description of the chemical and physical mechanisms controlling As interaction with mineral surfaces under natural hydrochemical conditions remains a formidable challenge. In this study we assess and compare the ability of existing surface complexation models (SCMs), the diffuse double layer model (DDL) and the charge distribution multisite complexation model (CD-MUSIC), to simulate As desorption from goethite in groundwater. We consider the outcomes of an in-situ experiment recently performed in an arsenic-contaminated aquifer of Northern China where As-loaded goethite-coated sand was deployed in 7 monitoring wells. Determination and measurements of As-surface species were carried out over a time period of 80 days in all monitoring wells. Simultaneous calibration of the models with the measurements in the 7 wells was performed to obtain single sets of surface complexation parameters for the DDL and the CD-MUSIC models, respectively. Although the general dynamic pattern of the As release at the site is captured by both models, the approach based on the CD-MUSIC agrees best with the field experimental data without modifications of the surface complexation database compiled from previous studies on goethite. Conversely, calibration of the DDL affinity constants led to substantial improvement in the agreement between model simulations and the considered field dataset. The model outcomes and the exploration of the sensitivity of the goethite surface composition to changes in hydrochemical conditions provide insights into the mechanisms controlling arsenic sorption and their different description in the DDL and the CD-MUSIC models. Both SCMs indicate that PO 4 3− acts as the main competitor for As(V) sorption sites, and that Fe(II) does not have a significant effect on the As(V) release despite its strong affinity for the goethite surface. Neither SCM suggests direct binding of As(III) to goethite. However, the CD-MUSIC model predicts significant formation of a goethite-Fe(II)-As(III) complex under the mildly alkaline conditions of the groundwater at the field site and that such complex is insensitive to phosphate competition. The CD-MUSIC implementation also allows capturing the non-linear charge effects of the major ions, including C a 2+ and M g 2+ , which appear to have important implication in the mechanisms of As sorption at the field site. [ABSTRACT FROM AUTHOR]

Abstract Antimony is an environmental contaminant, whose mobility in soils, sediments and groundwater systems is strongly influenced by interactions with Fe(III) oxide minerals. When exposed to reducing conditions, these minerals can undergo reductive dissolution via the activity of Fe(III)-reducing microorganisms, thereby potentially liberating previously retained Sb. In addition, microbial Fe(III)-reduction and the consequent production of Fe(II) can induce the formation of secondary Fe(III)- and Fe(II)-bearing minerals, which may alter the speciation and partitioning of Sb. In this study, we examined Sb behaviour during (1) the microbially-mediated reduction and transformation of Sb(V)-bearing ferrihydrite by the dissimilatory Fe(III)-reducing bacterium, Shewanella putrefaciens (strain CN32), and (2) during the associated abiotic Fe(II)-catalyzed transformation of Sb(V)-bearing ferrihydrite. Antimony K-edge XANES spectroscopy showed negligible reduction of Sb(V) to Sb(III) in both experiments, reflecting the redox stability of Sb(V) under these conditions. X-ray diffraction and Fe K-edge EXAFS spectroscopy revealed that both microbially-mediated Fe(II) production as well as the experimental addition of aqueous Fe(II) under abiotic conditions triggered rapid transformation of the initial ferrihydrite to feroxyhyte (δ′-FeOOH) and goethite (α-FeOOH). Goethite has been widely observed as a product of the Fe(II)-catalyzed transformation of ferrihydrite. However, the present study is the first to document the formation of feroxyhyte via this pathway, with feroxyhyte formation appearing to be favored by the presence of Sb(V). The formation of these secondary Fe(III) oxides was associated with substantial decreases in aqueous Sb concentrations and in the amount of surface-bound Sb (as defined via extractions with 1 M PO 4 3−). This is consistent with the incorporation of Sb(V) into the newly formed feroxyhyte and goethite via substitution for Fe(III). The results of this study provide new perspectives on coupling between Sb geochemistry and Fe mineralogy by showing that microbial Fe(III)-reduction and associated secondary Fe(III)-oxide formation can help to immobilize Sb(V) in reducing environments. [ABSTRACT FROM AUTHOR]

Abstract The development of predictive tools capable of simulating adsorption behavior on goethite (α-FeOOH) surfaces has evolved over the past several decades. Recent research has focused on capturing the variation of surface reactivity and adsorption behavior for different preparations of synthetic goethites. In this research, an approach to estimate modeling parameters based on the specific surface area (SSA) of goethites was established and combined with a Charge Distribution – Multi-site Complexation (CD-MUSIC) surface complexation model. It was assumed that differences in crystal face contributions (CFC), inner-Helmholtz capacitances (C 1), and protonation constants of surface oxygens (pK a 's) among different preparations of goethite contribute to the variation of surface reactivity. Thus, correlations of these modeling parameters with the SSA of a range of goethites were identified by comprehensively combining microscopic, macroscopic, and modeling data reported in literature along with adsorption data collected from macroscopic experiments conducted as part of this study. A CD-MUSIC model shown to be capable of accurately predicting adsorption for several metal ions and oxyanion selenite on a 62.9 m2/g SSA goethite served as the basis for the development of the adsorption modeling approach described in this paper. The predictive capability of the newly developed modeling approach was verified by comparing predictions of protons, SeO 3 2−, and Cd2+ adsorption with experimental data from goethites with SSAs ranging between 21.3 and 105 m2/g; in total, 40 adsorption data sets from 13 different goethites were used for model verification. The results from this study indicate that the variation of surface reactivity of goethites can be successfully simulated by changing CFC, C 1 , and pK 2,singly (i.e. second protonation constant of singly-coordinated oxygens on the goethite surface) based on the SSA, which implies that self-consistent adsorption parameters can be applied to predict adsorption behavior over a range of goethite preparations. [ABSTRACT FROM AUTHOR]

This article presents a set of equations that enables the prediction of sulfate adsorption behavior on all oxide minerals over a wide range of pH, ionic strength, sulfate concentration, and solid/water ratio based on the extended triple-layer model (ETLM). Although surface complexation models including the ETLM have been frequently applied to describe sulfate–surface interactions on oxides, the proposed adsorption stoichiometries and equilibrium constants have been mutually inconsistent even in a specific sulfate–oxide system. Here, we show that the outer-layer capacitance (C 2 ), a TLM parameter that has been traditionally set to 20 µF cm −2 , has a significant impact on the model prediction of sulfate adsorption. With the capacitance value being the same as the inner-layer one (i.e., C 2  = C 1 ), which is a theoretically and spectroscopically reasonable assumption, our ETML calculation adequately represents all adsorption, surface titration, and proton co-adsorption data for various sulfate–oxide systems reported in the literature (i.e., oxides; goethite, ferrihydrite, γ-alumina, gibbsite, and hematite) and those obtained in the present study (i.e., oxide; anatase). The combination of a monodentate-mononuclear inner-sphere ( MM in ) and a bidentate-binuclear outer-sphere ( BB out ) surface complex was found to explain all experimental data. Analysis of the retrieved equilibrium constants for the two surface species with the Born solvation theory led to the development of predictive equations for sulfate adsorption constants on all oxides. Considering the ubiquity of sulfate in natural environments, our proposed model should significantly contribute to a better understanding of the geochemical processes occurring at the mineral–water interface. [ABSTRACT FROM AUTHOR]

(U-Th)/He geochronology of two weathered plateaus in the Carajás Mountains, Pará, Brazil, reveals a history of weathering spanning from ca. 80 Ma to the present for this high elevation (∼720 m) land surface. Cosmogenic 3 He measurements of hematite pebbles and blocks cemented onto the plateaus at two sites, N1 and S11D, yield erosion rates as low as 0.09 and 0.08 m Ma −1 , respectively. Thus, these results confirm that the plateau surfaces are nearly immune to physical erosion for tens of millions of years. (U-Th)/He geochronology of ferruginous duricrusts blanketing the low elevation (250–100 m) plains surrounding the Carajás Mountains yield results consistently younger than ∼10 Ma. The geochronology results also reveal that the low elevation plain is diachronous, becoming progressively younger towards the receding plateaus. The spatial distribution of (U-Th)/He ages permits reconstruction of the history of scarp retreat for the Carajás landscape, showing that scarp retreat along major river valleys may have been as fast as 20 km Ma −1 during tectonically active and humid periods in the Cenozoic. The cessation of scarp retreat at some sites suggests that metamorphosed banded iron-formations and quartzites provide effective barriers to retreating escarpments, helping to preserve some of the oldest continuously exposed land surfaces on Earth. [ABSTRACT FROM AUTHOR]

Gallium (Ga) isotopic fractionation during its adsorption on calcite and goethite was investigated at 20 °C as a function of the solution pH, Ga aqueous concentration and speciation, and the solid to solution ratio. In all experiments Ga was found to be enriched in light isotopes at the solid surface with isotope fractionation △ 71 Ga solid-solution up to −1.27‰ and −0.89‰ for calcite and goethite, respectively. Comparison of Ga isotopic data of this study with predictions for ‘closed system’ equilibrium and ‘Rayleigh fractionation’ models indicates that the experimental data are consistent with a ‘closed system’ equilibrium exchange between the fluid and the solid. The results of this study can be interpreted based on Ga aqueous speciation and the structure of Ga complexes formed at the solid surfaces. For calcite, Ga isotope fractionation is mainly triggered by increased Ga coordination and Ga–O bond length, which vary respectively from 4 and 1.84 Å in Ga(OH) 4 − to 6 and 1.94 Å in the >Ca–O–GaOH(OH 2 ) 4 + surface complex. For goethite, despite the formation of Ga hexa-coordinated >FeOGa(OH) 2 0 surface complexes (Ga–O distances of 1.96–1.98 Å) both at acid and alkaline pH, a similar extent of isotope fractionation was found at acid and alkaline pH, suggesting that Ga(OH) 4 − is preferentially adsorbed on goethite for all investigated pH conditions. In addition, the observed decrease of Ga isotope fractionation magnitude observed with increasing Ga surface coverage for both calcite and goethite is likely related to the formation of Ga surface polymers and/or hydroxides with reduced Ga–O distances. This first study of Ga isotope fractionation during solid-fluid interactions suggests that the adsorption of Ga by oxides, carbonates or clay minerals could yield significant Ga isotope fractionation between secondary minerals and surficial fluids including seawater. Ga isotopes thus should help to better characterize the surficial biogeochemical cycles of gallium and its geochemical analog aluminum. [ABSTRACT FROM AUTHOR]

The reduction potential of Fe(II)-Fe(III) (oxyhydr)oxide systems provides an important control on the biogeochemical cycling of redox-sensitive elements such as carbon and nitrogen as well as trace metals and organic contaminants in natural systems. As such, an in-depth understanding of the factors controlling the reduction potential of such systems is critical to predicting the likely transformation, transport and fate of these species in natural and perturbed environments. In this study the mineralogy and reduction potential of ferrihydrite suspensions at pH 6.50 and pH 7.00 were determined over the course of their Fe(II)-catalyzed transformation to lepidocrocite and goethite using X-ray absorption spectroscopy and mediated electrochemical approaches. The measured reduction potentials were compared to those of analogous Fe(II)-Fe(III) (oxyhydr)oxide suspensions reacted for 5 min containing pure ferrihydrite (Fh), lepidocrocite (L) and goethite (Gt). The reduction potentials of the pure Fe(II)-Fe(III) (oxyhydr)oxide suspensions were, respectively, +47.5, −13.5 and −122.3 mV vs. SHE at pH 6.5, and −22.9, −84.1 and −189.7 mV vs. SHE at pH 7. These values are in good agreement with reduction potentials calculated using the Nernst equation and reported thermodynamic solubility products indicating that these suspensions had reached equilibrium within 5 min. The reduction potential of the pH 6.50 Fe(II)-ferrihydrite suspension decreased from +47.4 mV to –126.4 mV over a week, and from −20.1 mV to −188.4 mV (all vs. SHE) after 24 h at pH 7. The changes in reduction potential over time matched well to those calculated from the relative proportion of each pure Fe(III) (oxyhydr)oxide present suggesting that Fe 3+ activity was influenced by the mix of iron oxides present rather than the most insoluble solid species. Finally, evidence is provided that adsorbed Fe(II) has the capacity to reduce a significantly larger fraction of a reducible species than the aqueous Fe(II) species with which it is in equilibrium. As an Fe(III) (oxyhydr)oxide suspension in equilibrium with aqueous and adsorbed Fe(II) species possesses a single, unique reduction potential, this suggests that adsorbed Fe(II) is a more facile reductant than aqueous Fe(II). [ABSTRACT FROM AUTHOR]

Schwertmannite (SHM) is a powerful scavenger for As(III) leading to As(III)-enriched precipitates around acid mine drainage environments that may become exposed to aqueous Fe(II). In this study we have investigated the stability of pure SHM and SHM containing 0.92 wt% As(III) under Fe(II) aq -rich (0.4–1.0 mM) anoxic conditions using XRD, SEM, Mössbauer and FTIR spectroscopic techniques. Schwertmannite transformation proceeded through an alkalinity-driven pathway releasing sulfate and a Fe(II)-catalyzed pathway that generated lepidocrocite and goethite at pH 6 and 6.9 in the presence of 1 mM Fe(II) aq . Lepidocrocite was found to be needle shaped if the SHM contained As(III) and platy for pure SHM. Goethite had a poor degree of crystallinity in As(III) containing SHM. Pre-adsorption of As(III) inhibited the extent of SHM transformation. Fe(II) sorption onto SHM was pH dependent and reflected a sorption edge with complete consumption at pH 6.9, while only ∼20% were adsorbed at pH 5. Surface coverage with Fe(II) appears to be the key parameter controlling extent and products of the transformation process. As(III) concentrations in solution are controlled by two mechanisms: (1) exchange of As(III) for sulfate upon alkalinity-driven transformation of schwertmannite and (2) re-adsorption to new phases formed upon Fe(II)-catalyzed transformation. The adsorbed As(III) has inhibited the extent of transformation and was partly released with the maximum release at pH 5 (0.5%) in the absence of Fe(II) aq . [ABSTRACT FROM AUTHOR]

Adsorption and redox reactions occur between arsenic-containing pyrite and arsenate, which affect the migration and conversion of arsenic in soils and waters. However, the influence of arsenic incorporated in pyrite on the interaction processes is still enigmatic. In this work, arsenic-containing pyrites were hydrothermally synthesized with composition similar to naturally surface-oxidized pyrites in supergene environments. The effects of arsenic incorporation on the chemical composition and physicochemical properties were analyzed, and the interaction mechanism between arsenic-containing pyrites and aqueous arsenate was also studied within pH 3.0–11.0. Arsenic-containing pyrites with the arsenic contents of 0 (Apy0), 4.4 (Apy5) and 9.9 wt.% (Apy10) were produced in hydrothermal systems. As(III) and As(−I) respectively substituted Fe(II) and S 2 (−II) in the pyrite, and their relative contents respectively reached 76.6% and 17.2% in Apy5, and 91.0% and 8.0% in Apy10. Arsenic substitution resulted in a high content of Fe(III) in the form of Fe(III) S and a decrease in pyrite crystallinity. During the redox processes of arsenic-containing pyrites and arsenate, elemental S 0 , SO 4 2− and goethite were formed as the main products with the adsorption of As(III,V), and As(III) was released due to the collapse of the crystal structure of pyrite and the oxidation of As(−I). Different redox mechanisms were achieved with pH increasing from 3.0 to 11.0 in the reaction system. At pH 3.0–6.0, Fe(III) contributed much to the oxidation of arsenic-containing pyrites, and arsenate and released As(III) were adsorbed on the surface of solid products. At pH 7.0–11.0, aqueous arsenate worked as the major oxidant, and its oxidation capacity increased with increasing pH. When the pH was increased from 3.0 to 7.0 and 11.0, the release ratio of incorporated arsenic from Apy10 particles increased from 34.1% to 45.0% and 56.8%, respectively. The present study facilitates a better understanding about the interaction mechanisms between arsenic-containing pyrite and arsenate in supergene environments. [ABSTRACT FROM AUTHOR]

Nineteen (U-Th)/He ages were determined for eight samples from a core drilled in an ore-grade channel iron deposit (CID) of the Robe Pisolite (Robe Formation) of Mesa J in Western Australia. With one exception, uncorrected ages of the analyzed aliquots range from 6.7 (±0.4) Ma to 30.2 (±3.1) Ma, while molar ratios of Th/U range from 0.42 to 5.06. The exception is an aliquot with an apparent age of 2.7 Ma and Th/U of 5.70. A three-component mixing model involving one generation of goethite and two generations of hematite suggests that the age of crystallization of the oolitic goethites is ∼7 (±1) Ma. If so, the goethites have effectively been closed systems for ∼7 million years and should preserve a stable hydrogen isotope record of late Miocene rainfall in the vicinity of Mesa J. Cenozoic movement of the Australian continent had placed Mesa J and environs in the subtropics at a paleolatitude of about 29 °S during the late Miocene. Al-adjusted δD values of oolitic goethite in the eight CID samples range from −153‰ to −146‰ and imply that the δD of the late Miocene meteoric waters ranged from −61‰ to −53‰, with an average of −56‰. These relatively negative δD values might indicate that near-coastal, late Miocene rain was derived primarily from summer-season tropical cyclones with storm tracks that extended into the subtropics of western Australia. The postulated late Miocene tropical cyclones would have occurred more often and/or exhibited greater intensity at a paleolatitude of 29 °S than is the case for modern sites at approximately 30 °S on the west coast of Australia (e.g., Perth). Higher fluxes of meteoric water in the Miocene summers would have facilitated dissolution and removal of BIF-sourced silica with concomitant enrichment in oxidized Fe. Moreover, wetter late Miocene summers could have promoted multiple cycles of microbially mediated dissolution and recrystallization of Fe(III) oxides in the aerobic systems. The oolitic textures may be indicative of such recycling. However, the oolitic goethites of Mesa J were closed systems after ∼7 Ma. Therefore, the climate in the vicinity of Mesa J seems to have changed in the late Miocene to conditions that did not favor widespread recycling of Fe (III) oxides—perhaps changing from seasonally wet to the modern dry climate. [ABSTRACT FROM AUTHOR]

Oxidation of Mn(II) is an important process that controls the mobility and bioavailability of Mn, as well as the formation of Mn (oxyhydr)oxides in natural systems. It was found that the surfaces of minerals, such as iron (oxyhydr)oxides, can accelerate Mn(II) oxidation to a certain degree, but the underlying mechanism has not been clearly understood. This study explores the reaction pathways and mechanisms of Mn(II) oxidation on ferrihydrite surfaces at neutral pH, commonly found in natural environments, by comparisons with montmorillonite, amorphous Al(OH) 3 , goethite, and magnetite using macroscopic experiments and spectroscopic analyses. Results show that when Mn(II) concentrations are below 4 mM, macroscopic Mn(II) adsorption on the three iron (oxyhydr)oxide surfaces conforms well to the Langmuir equation, with ferrihydrite showing the highest adsorption capacity. With Mn(II) concentrations ranging within 6–24 mM, the adsorbed Mn(II) is mainly oxidized into manganite (γ-MnOOH) and/or feitknechtite (β-MnOOH) by dissolved O 2 , and Mn(II) removal on a unit mass basis in the presence of magnetite is the highest compared with ferrihydrite and goethite. Ferrihydrite, a semiconductor material, shows stronger catalytic ability for Mn(II) oxidation on the same surface area than insulator minerals ( i.e. , montmorillonite and amorphous Al(OH) 3 ). Additionally, the products of Mn(II) oxidation in the presence of semiconductor iron (oxyhydr)oxides ( i.e. , ferrihydrite, goethite, or magnetite) at the same Fe/Mn molar ratio include both manganite and a small amount of Mn(IV) minerals, and the Mn average oxidation states (Mn AOSs) of these products follow the order: magnetite > goethite > ferrihydrite. Magnetite and goethite, with relatively smaller SSAs and lower band gap energies, exhibit greater catalysis for Mn(II) oxidation than ferrihydrite at the same Fe/Mn ratio, which goes against the conventional interfacial effect and is related to the electrochemical properties. Thus, the Mn(II) catalytic oxidation by O 2 on ferrihydrite surfaces should include an electrochemical pathway, i.e. , electron transfer (ET) in the Mn(II)-Conduction Band (CB) Ferrihydrite -O 2 complexes, in addition to the conventional two interfacial catalytic pathways, i.e. , ET in the Mn(II)-Fe(II, III)-O 2 complexes and direct ET in the Mn(II)-O 2 complexes. These results reveal new implications for understanding the processes and mechanisms of Mn(II) oxidation on iron (oxyhydr)oxide surfaces and the abiotic formation of Mn (oxyhydr)oxides in surface environments. [ABSTRACT FROM AUTHOR]