Widespread occurrences of phyllosilicates, predominantly nontronite and Mg saponite, in the Noachian‐aged crust of Mars place constraints on water availability and surface conditions. However, the ...Noachian atmosphere likely lacked oxidants capable of forming nontronite from the basaltic crust and its origins are thus uncertain. In this study, scenarios for the formation of iron‐bearing phyllosilicates from the weathering and hydrothermal alteration of Martian basalt were investigated using geochemical modeling to establish plausible pathways of nontronite generation and the effect of redox conditions on associated secondary phases. Hydrothermal alteration produced FeII and Mg saponite, serpentine, and zeolites at 100°C and chlorite, prehnite, and talc at 250°C, consistent with phases observed in crater deposits on Mars. Anoxic weathering produced primarily FeII and Mg saponite. High water‐rock ratios produced Al‐clays and amorphous silica and high pCO2 conditions inhibited smectite formation because of carbonate precipitation. Oxic weathering produced primarily nontronite and Mg saponite. Later oxidation of anoxic weathering products also formed nontronite‐Mg saponite assemblages; oxidation products of hydrothermal assemblages included nontronite, Mg saponite, and either Al smectites or residual zeolites or prehnite. These calculations demonstrate that there are multiple plausible routes to form Fe/Mg smectites on early Mars and that an oxidizing atmosphere need not have existed in the Noachian. Decoupling iron oxidation from initial clay formation raises the possibilities that Mars transitioned to conditions favoring widespread iron oxidation after phyllosilicate formation ceased and that residual, unoxidized ferrous iron phyllosilicates still exist today in the Martian subsurface.
Key Points
Multiple geochemically plausible routes exist for forming nontronite on Mars
Iron oxidation on Mars may have occurred later than phyllosilicate formation
Early Mars need not have had an oxidizing atmosphere
Ordering of interfacial water at the hematite and corundum (0
0
1)–water interfaces has been characterized using in situ high resolution specular X-ray reflectivity measurements. The hematite (0
0
1) ...surface was prepared through an annealing process to produce a surface isostructural with corundum (0
0
1), facilitating direct comparison. Interfacial water was found to display a similar structure on this pair of isostructural surfaces. A single layer of adsorbed water having a large vibrational amplitude was present on each surface and additional ordering of water extended at least 1
nm into the bulk fluid, with the degree of ordering decreasing with increasing distance from the surfaces. Consistent with prior studies of the (0
1
2) and (1
1
0) surfaces of hematite and corundum, the configuration of water above the (0
0
1) surfaces is primarily controlled by the surface structure, specifically the arrangement of surface functional groups. However, interfacial water at the (0
0
1) surfaces displayed significantly larger vibrational amplitudes throughout the interfacial region than at other isostructural sets of hematite and corundum surfaces, indicating weaker ordering. Comparison of the vibrational amplitudes of adsorbed water on a series of oxide, silicate, and phosphate mineral surfaces suggests that the presence or absence of a substantial interfacial electrostatic field is the primary control on water ordering and not the surface structure itself. On surfaces for which charge originates dominantly through protonation–deprotonation reactions the controlling factor appears to be whether conditions exist where most functional groups are uncharged as opposed to the net surface charge. The doubly coordinated functional groups on hematite and corundum (0
0
1) surfaces are largely uncharged under slightly acidic to circumneutral pH conditions, leading to weak ordering, whereas singly coordinated groups on (0
1
2) and (1
1
0) surfaces of these phases are always charged, even when the net surface charge is zero, and induce strong water ordering. Surfaces lacking structural charge can thus be divided into two distinct classes that induce either strong or weak ordering of interfacial water. Surface functional group coordination is the ultimate control on this division as it determines the charge state of such groups under different protonation configurations. Ion adsorption and electron transfer processes may differ between these classes of surfaces because of the effect of water ordering strength on interfacial capacitances and hydrogen bonding.
The mobility of hexavalent uranium in soil and groundwater is strongly governed by adsorption to mineral surfaces. As strong naturally occurring adsorbents, manganese oxides may significantly ...influence the fate and transport of uranium. Models for U(VI) adsorption over a broad range of chemical conditions can improve predictive capabilities for uranium transport in the subsurface. This study integrated batch experiments of U(VI) adsorption to synthetic and biogenic MnO2, surface complexation modeling, ζ-potential analysis, and molecular-scale characterization of adsorbed U(VI) with extended X-ray absorption fine structure (EXAFS) spectroscopy. The surface complexation model included inner-sphere monodentate and bidentate surface complexes and a ternary uranyl-carbonato surface complex, which was consistent with the EXAFS analysis. The model could successfully simulate adsorption results over a broad range of pH and dissolved inorganic carbon concentrations. U(VI) adsorption to synthetic δ-MnO2 appears to be stronger than to biogenic MnO2, and the differences in adsorption affinity and capacity are not associated with any substantial difference in U(VI) coordination.
The potential for new U.S. regulations for Cr(VI) in drinking water have spurred strong interests in improving technologies for Cr(VI) removal. This study examined iron electrocoagulation for Cr(VI) ...removal at conditions directly relevant to drinking water treatment. Cr(VI) is chemically reduced to less soluble Cr(III) species by the Fe(II) produced from an iron anode, and XANES spectra indicate that the Cr is entirely Cr(III) in solid-phases produced in electrocoagulation. The dynamics of Cr(VI) removal in electrocoagulation at pH 6 and pH 8 at both oxic and anoxic conditions can be described by a new model that incorporates Fe(II) release from the anode and heterogeneous and homogeneous reduction of Cr(VI) by Fe(II). Heterogeneous Cr(VI) reduction by adsorbed Fe(II) was critical to interpreting Cr(VI) removal at pH 6, and the Fe- and Cr-containing EC product was found to catalyze the redox reaction. Dissolved oxygen (DO) did not observably inhibit Cr(VI) removal because Fe(II) reacts with DO more slowly than it does with Cr(VI), and Cr(VI) removal was faster at higher pH. Even in the presence of common groundwater solutes, iron electrocoagulation lowered Cr(VI) concentrations to levels well below California's 10 μg/L.
Iron oxides are ubiquitous in soils and sediments and play a critical role in the geochemical distribution of trace elements and heavy metals via adsorption and coprecipitation. The presence of ...organic acids may potentially alter how metals associate with iron oxide minerals through a series of cooperative or competitive processes: solution complexation, ternary surface complexation, and surface site competition. The macroscopic and molecular-scale effects of these processes were investigated for Ni adsorption to hematite and goethite at pH 7 in the presence of oxalate. The addition of this organic acid suppresses Ni uptake on both minerals. Aqueous speciation suggests that this is dominantly the result of oxalate complexing and solubilizing Ni. Comparison of the Ni surface coverage to the concentration of free (uncomplexed) Ni
in solution suggests that the oxalate also alters Ni adsorption affinity. EXAFS and ATR-FTIR spectroscopies indicate that these changes in binding affinity are due to the formation of Ni-oxalate ternary surface complexes. These observations demonstrate that competition between dissolved oxalate and the mineral surface for Ni overwhelms the enhancement in adsorption associated with ternary complexation. Oxalate thus largely enhances Ni mobility, thereby increasing micronutrient bioavailability and inhibiting contaminant sequestration.
Adsorption and subsequent reduction of U(VI) on Fe(II)-bearing clay minerals can control the mobility of uranium in subsurface environments. Clays such as montmorillonite provide substantial amounts ...of the reactive surface area in many subsurface environments, and montmorillonite-containing materials are used in the storage of spent nuclear fuel. We investigated the extent of reduction of U(VI) by Fe(II)-bearing montmorillonite at different pH values and sodium concentrations using X-ray absorption spectroscopy and chemical extractions. Nearly complete reduction of U(VI) to U(IV) occurred at a low sodium concentration at both pH 3 and 6. At pH 6 and a high sodium concentration, which inhibits U(VI) binding at cation-exchange sites, the extent of U(VI) reduction was only 70%. Surface-bound U(VI) on unreduced montmorillonite was more easily extracted into solution with bicarbonate than surface-bound U(IV) generated by reduction of U(VI) on Fe(II)-bearing montmorillonite. We developed a nonelectrostatic surface complexation model to interpret the equilibrium adsorption of U(IV) on Fe(II)-bearing montmorillonite as a function of pH and sodium concentration. These findings establish the potential importance of structural Fe(II) in low iron content smectites in controlling uranium mobility in subsurface environments.
Iron oxide minerals are ubiquitous in soils, sediments, and aquatic systems and influence the fate and availability of trace metals. Ferrihydrite is a common iron oxide of nanoparticulate size and ...poor crystallinity, serving as a thermodynamically unstable precursor to more crystalline phases. While aging induces such phase transformations, these are accelerated by the presence of dissolved Fe(II). However, the impact of trace metals on Fe(II)-catalyzed ferrihydrite phase transformations at ambient temperatures and the associated effects on trace metal speciation has seen limited study. In the present work, phase transformations of ferrihydrite that contains the trace metal zinc in its structure were investigated during aging at ambient temperature in the presence of two different Fe(II) concentrations at pH 7. X-ray diffraction reveals that low Fe(II) concentration (0.2 mM) generates hematite plus minor lepidocrocite, whereas high Fe(II) concentration (1.0 mM) produces a magnetite-lepidocrocite mixture. In both cases, a substantial fraction of ferrihydrite remains after 12 days. In contrast, zinc-free ferrihydrite forms primarily lepidocrocite and goethite in the presence of 0.2 mM Fe(II), with minor hematite and a trace of ferrihydrite remaining. For 1.0 mM Fe(II), magnetite, goethite, and lepidocrocite form when zinc is absent, leaving no residual ferrihydrite. Transformations of zinc-ferrihydrite produce a transient release of zinc to solution, but this is nearly quantitatively removed into the mineral products after 1 h. Extended X-ray absorption fine structure spectroscopy suggests that zinc partitions into the newly formed phases, with a shift from tetrahedral to a mixture of tetrahedral and octahedral coordination in the 0.2 mM Fe(II) system and taking on a spinel-like local structure in the 1.0 mM Fe(II) reaction products. This work indicates that substituting elements in ferrihydrite may play a key role in promoting the formation of hematite in low temperature systems, such as soils or sediments. In addition, the retention of zinc in the products of ferrihydrite phase transformation shows that trace metal micronutrients and contaminants may not be mobilized under circumneutral conditions despite the formation of more crystalline iron oxides. Furthermore, mass balance requires that the abundance and isotopic composition of iron oxide-associated zinc, and possibly other trace metals, in the rock record may be retained during diagenetic phase transformations of ferrihydrite if catalyzed by dissolved Fe(II).
Layered Mn oxide minerals (phyllomanganates) often control trace metal fate in natural systems. The strong uptake of metals such as Ni and Zn by phyllomanganates results from adsorption on or ...incorporation into vacancy sites. Mn(II) also binds to vacancies and subsequent comproportionation with structural Mn(IV) may alter sheet structures by forming larger and distorted Mn(III)O
octahedra. Such Mn(II)-phyllomanganate reactions may thus alter metal uptake by blocking key reactive sites. Here we investigate the effect of Mn(II) on Ni and Zn binding to phyllomanganates of varying initial vacancy content (δ-MnO
, hexagonal birnessite, and triclinic birnessite) at pH 4 and 7 under anaerobic conditions. Dissolved Mn(II) decreases macroscopic Ni and Zn uptake at pH 4 but not pH 7. Extended X-ray absorption fine structure spectroscopy demonstrates that decreased uptake at pH 4 corresponds with altered Ni and Zn adsorption mechanisms. These metals transition from binding in the interlayer to sheet edges, with Zn increasing its tetrahedrally coordinated fraction. These effects on metal uptake and binding correlate with Mn(II)-induced structural changes, which are more substantial at pH 4 than 7. Through these structural effects and the pH-dependence of Mn(II)-metal competitive adsorption, system pH largely controls metal binding to phyllomanganates in the presence of dissolved Mn(II).
The dynamics of trace metals at mineral surfaces influence their fate and bioaccessibility in the environment. Trace metals on iron (oxyhydr)oxide surfaces display adsorption-desorption hysteresis, ...suggesting entrapment after aging. However, desorption experiments may perturb the coordination environment of adsorbed metals, the distribution of labile Fe(III), and mineral aggregation properties, influencing the interpretation of labile metal fractions. In this study, we investigated irreversible binding of nickel, zinc, and cadmium to goethite after aging times of 2-120 days using isotope exchange. Dissolved and adsorbed metal pools exchange rapidly, with half times <90 min, but all metals display a solid-associated fraction inaccessible to isotope exchange. The size of this nonlabile pool is the largest for nickel, with the smallest ionic radius, and the smallest for cadmium, with the largest ionic radius. Spectroscopy and extractions suggest that the irreversibly bound metals are incorporated in the goethite structure. Rapid exchange of labile solid-associated metals with solution demonstrates that adsorbed metals can sustain the dissolved pool in response to biological uptake or fluid flow. Trace metal fractions that irreversibly bind following adsorption provide a contaminant sequestration pathway, limit the availability of micronutrients, and record metal isotope signatures of environmental processes.
Iron-based electrocoagulation can be highly effective for Cr(VI) removal from water supplies. However, the presence of humic acid (HA) inhibited the rate of Cr(VI) removal in electrocoagulation, with ...the greatest decreases in Cr(VI) removal rate at higher pH. This inhibition was probably due to the formation of Fe(II) complexes with HA that are more rapidly oxidized than uncomplexed Fe(II) by dissolved oxygen, making less Fe(II) available for reduction of Cr(VI). Close association of Fe(III), Cr(III), and HA in the solid products formed during electrocoagulation influenced the fate of both Cr(III) and HA. At pH 8, the solid products were colloids (1-200 nm) with Cr(III) and HA concentrations in the filtered fraction being quite high, while at pH 6 these concentrations were low due to aggregation of small particles. X-ray diffraction and X-ray absorption fine structure spectroscopy indicated that the iron oxides produced were a mixture of lepidocrocite and ferrihydrite, with the proportion of ferrihydrite increasing in the presence of HA. Cr(VI) was completely reduced to Cr(III) in electrocoagulation, and the coordination environment of the Cr(III) in the solids was similar regardless of the humic acid loading, pH, and dissolved oxygen level.
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