Mechanisms of Arsenic and Antimony Co-sorption onto Jarosite: An X-ray Absorption Spectroscopic Study.

Jarosite, a common mineral in acidic sulfur-rich environments, can strongly sorb both As(V) and Sb(V). However, little is known regarding the mechanisms that control simultaneous co-sorption of As(V) and Sb(V) to jarosite. We investigated the mechanisms controlling As(V) and Sb(V) sorption to jarosite at pH 3 (in dual and single metalloid treatments). Jarosite was found to sorb Sb(V) to a greater extent than As(V) in both single and dual metalloid treatments. Relative to single metalloid treatments, the dual presence of both As(V) and Sb(V) decreased the sorption of both metalloids by almost 50%. Antimony K-edge EXAFS spectroscopy revealed that surface precipitation of an Sb(V) oxide species was the predominant sorption mechanism for Sb(V). In contrast, As K-edge EXAFS spectroscopy showed that As(V) sorption occurred via bidentate corner-sharing complexes on the jarosite surface when Sb(V) was absent or present at low loadings or by formation of similar complexes on the Sb(V) oxide surface precipitate when Sb(V) was present at high loadings. These results point to a novel mechanism by which Sb(V) impacts the co-sorption of As(V). Overall, these findings highlight a strong contrast in the sorption mechanisms of Sb(V) versus As(V) to jarosite under acidic environmental conditions.

Iron Isotopes in Acid Mine Drainage: Extreme and Divergent Fractionation between Solid (Schwertmannite, Jarosite, and Ferric Arsenate) and Aqueous Species.

Examination of stable Fe isotopes is a powerful tool to explore Fe cycling in a range of environments. However, the isotopic fractionation of Fe in acid mine drainage (AMD) has received little attention and is poorly understood. Here, we analyze Fe isotopes in waters and Fe(III)-rich solids along an AMD flow-path. Aqueous Fe spanned a concentration and δ56Fe range of ∼420 mg L-1 and + 0.04‰ at the AMD source to ∼100 mg L-1 and -0.81‰ at ∼450 m downstream. Aqueous As (up to ∼33 mg L-1) and SO42- (up to ∼2000 mg L-1), like aqueous Fe, decreased in concentration down the flow-path. X-ray absorption spectroscopy indicated that downstream attenuation in aqueous Fe, As, and SO42- was due to the precipitation of amorphous ferric arsenate (AFA), schwertmannite, and jarosite. The Fe(III) in these solids displayed extreme variability in δ56Fe, spanning +3.95‰ in AFA near the AMD source to -1.34‰ in schwertmannite at ∼450 m downstream. Similarly, the isotopic contrast between solid Fe(III) precipitates and aqueous Fe (Δ56Feppt-aq) dropped along the flow-path from about +4.1 to -1.1‰. The shift from positive to negative Δ56Feppt-aq reflects divergence between competing equilibrium versus kinetic fractionation processes.

Direct Observation of Nanoparticulate Goethite Recrystallization by Atom Probe Analysis of Isotopic Tracers.

Goethite (α-FeOOH) is dispersed throughout the earth's surface, and its propensity to recrystallize in aqueous solutions determines whether this mineral is a source or sink for critical trace elements in the environment. Under reducing conditions, goethite commonly coexists with aqueous Fe(II) (Fe(II)aq), which accelerates recrystallization by coupled electron transfer and atom exchange. Quantifying the amount of the mineral phase that exchanges its structural Fe(III) atoms with Fe(II)aq is complicated by recrystallization models with untested assumptions of whether, and to what extent, the recrystallized portion of the mineral continues to interact with the solution. Here, we reacted nanoparticulate goethite with 57Fe-enriched Fe(II)aq and used atom probe tomography (APT) to resolve the three-dimensional distribution of Fe isotopes in goethite at the sub nm scale. We found that the 57Fe tracer isotope is enriched in the bulk structure (tens of nanometers deep), with some samples having 57Fe penetration throughout at a level that is similar to the isotopic composition of Fe(II)aq. This suggests that some particles undergo near-complete recrystallization. In other cases, however, the distribution of 57Fe is more heterogeneous and generally concentrates near the particle periphery. Nanoparticle encapsulation and subsequent APT can hence capture hidden recrystallization mechanisms which are critical to predicting mineral reactivity in aqueous solutions.

Recrystallization of Manganite (γ-MnOOH) and Implications for Trace Element Cycling.

The recrystallization of Mn(III,IV) oxides is catalyzed by aqueous Mn(II) (Mn(II)aq) during (bio)geochemical Mn redox cycling. It is poorly understood how trace metals associated with Mn oxides (e.g., Ni) are cycled during such recrystallization. Here, we use X-ray absorption spectroscopy (XAS) to examine the speciation of Ni associated with Manganite (γ-Mn(III)OOH) suspensions in the presence or absence of Mn(II)aq under variable pH conditions (pH 5.5 and 7.5). In a second set of experiments, we used a 62Ni isotope tracer to quantify the amount of dissolved Ni that exchanges with Ni incorporated in the Manganite crystal structure during reactions in 1 mM Mn(II)aq and in Mn(II)-free solutions. XAS spectra show that Ni is initially sorbed on the Manganite mineral surface and is progressively incorporated into the mineral structure over time (13% after 51 days) even in the absence of dissolved Mn(II). The amount of Ni incorporation significantly increases to about 40% over a period of 51 days when Mn(II)aq is present in solution. Similarly, Mn(II)aq promotes Ni exchange between Ni-substituted Manganite and dissolved Ni(II), with around 30% of Ni exchanged at pH 7.5 over the duration of the experiment. No new mineral phases are detected following recrystallization as determined by X-ray diffraction and XAS. Our results reveal that Mn(II)-catalyzed mineral recrystallization partitions Ni between Mn oxides and aqueous fluids and can therefore affect Ni speciation and mobility in the environment.

Oxygen Isotope Evidence for Mn(II)-Catalyzed Recrystallization of Manganite (γ-MnOOH).

Manganese is biogeochemically cycled between aqueous Mn(II) and Mn(IV) oxides. Aqueous Mn(II) often coexists with Mn(IV) oxides, and redox reactions between the two (e.g., comproportionation) are well known to result in the formation of Mn(III) minerals. It is unknown, however, whether aqueous Mn(II) exchanges with structural Mn(III) in manganese oxides in the absence of any mineral transformation (similar to what has been reported for aqueous Fe(II) and some Fe(III) minerals). To probe whether atoms exchange between a Mn(III) oxide and water, we use a (17)O tracer to measure oxygen isotope exchange between structural oxygen in manganite (γ-MnOOH) and water. In the absence of aqueous Mn(II), about 18% of the oxygen atoms in manganite exchange with the aqueous phase, which is close to the estimated surface oxygen atoms (∼11%). In the presence of aqueous Mn(II), an additional 10% (for a total of 28%) of the oxygen atoms exchange with water, suggesting that some of the bulk manganite mineral (i.e., beyond surface) is exchanging with the fluid. Exchange of manganite oxygen with water occurs without any observable change in mineral phase and appears to be independent of the rapid Mn(II) sorption kinetics. These experiments suggest that Mn(II) catalyzes manganese oxide recrystallization and illustrate a new pathway by which these ubiquitous minerals interact with their surrounding fluid.

Iron Atom Exchange between Hematite and Aqueous Fe(II).

Aqueous Fe(II) has been shown to exchange with structural Fe(III) in goethite without any significant phase transformation. It remains unclear, however, whether aqueous Fe(II) undergoes similar exchange reactions with structural Fe(III) in hematite, a ubiquitous iron oxide mineral. Here, we use an enriched (57)Fe tracer to show that aqueous Fe(II) exchanges with structural Fe(III) in hematite at room temperature, and that the amount of exchange is influenced by particle size, pH, and Fe(II) concentration. Reaction of 80 nm-hematite (27 m(2) g(-1)) with aqueous Fe(II) at pH 7.0 for 30 days results in ∼5% of its structural Fe(III) atoms exchanging with Fe(II) in solution, which equates to about one surface iron layer. Smaller, 50 nm-hematite particles (54 m(2) g(-1)) undergo about 25% exchange (∼3× surface iron) with aqueous Fe(II), demonstrating that structural Fe(III) in hematite is accessible to the fluid in the presence of Fe(II). The extent of exchange in hematite increases with pH up to 7.5 and then begins to decrease as the pH progresses to 8.0, likely due to surface site saturation by sorbed Fe(II). Similarly, when we vary the initial amount of added Fe(II), we observe decreasing amounts of exchange when aqueous Fe(II) is increased beyond surface saturation. This work shows that Fe(II) can catalyze iron atom exchange between bulk hematite and aqueous Fe(II), despite hematite being the most thermodynamically stable iron oxide.

Atom exchange between aqueous Fe(II) and structural Fe in clay minerals.

Due to their stability toward reductive dissolution, Fe-bearing clay minerals are viewed as a renewable source of Fe redox activity in diverse environments. Recent findings of interfacial electron transfer between aqueous Fe(II) and structural Fe in clay minerals and electron conduction in octahedral sheets of nontronite, however, raise the question whether Fe interaction with clay minerals is more dynamic than previously thought. Here, we use an enriched isotope tracer approach to simultaneously trace Fe atom movement from the aqueous phase to the solid ((57)Fe) and from the solid into the aqueous phase ((56)Fe). Over 6 months, we observed a significant decrease in aqueous (57)Fe isotope fraction, with a fast initial decrease which slowed after 3 days and stabilized after about 50 days. For the aqueous (56)Fe isotope fraction, we observed a similar but opposite trend, indicating that Fe atom movement had occurred in both directions: from the aqueous phase into the solid and from the solid into aqueous phase. We calculated that 5-20% of structural Fe in clay minerals NAu-1, NAu-2, and SWa-1 exchanged with aqueous Fe(II), which significantly exceeds the Fe atom layer exposed directly to solution. Calculations based on electron-hopping rates in nontronite suggest that the bulk conduction mechanism previously demonstrated for hematite1 and suggested as an explanation for the significant Fe atom exchange observed in goethite2 may be a plausible mechanism for Fe atom exchange in Fe-bearing clay minerals. Our finding of 5-20% Fe atom exchange in clay minerals indicates that we need to rethink how Fe mobility affects the macroscopic properties of Fe-bearing phyllosilicates and its role in Fe biogeochemical cycling, as well as its use in a variety of engineered applications, such as landfill liners and nuclear repositories.

Fe(II)-catalyzed recrystallization of goethite revisited.

Results from enriched (57)Fe isotope tracer experiments have shown that atom exchange can occur between structural Fe in Fe(III) oxides and aqueous Fe(II) with no formation of secondary minerals or change in particle size or shape. Here we derive a mass balance model to quantify the extent of Fe atom exchange between goethite and aqueous Fe(II) that accounts for different Fe pool sizes. We use this model to reinterpret our previous work and to quantify the influence of particle size and pH on extent of goethite exchange with aqueous Fe(II). Consistent with our previous interpretation, substantial exchange of goethite occurred at pH 7.5 (≈ 90%) and we observed little effect of particle size between nanogoethite (average size of 81 × 11 nm; ≈ 110 m(2)/g) and microgoethite (average size of 590 × 42 nm; ≈ 40 m(2)/g). Despite ≈ 90% of the bulk goethite exchanging at pH 7.5, we found no change in mineral phase, average particle size, crystallinity, or reactivity after reaction with aqueous Fe(II). At a lower pH of 5.0, no net sorption of Fe(II) was observed and significantly less exchange occurred accounting for less than the estimated proportion of surface Fe atoms in the particles. Particle size appears to influence the amount of exchange at pH 5.0 and we suggest that aggregation and surface area may play a role. Results from sequential chemical extractions indicate that (57)Fe accumulates in extracted Fe(III) goethite components. Isotopic compositions of the extracts indicate that a gradient of (57)Fe develops within the goethite with more accumulation of (57)Fe occurring in the more easily extracted Fe(III) that may be nearer to the surface.

Controls on Fe(II)-activated trace element release from goethite and hematite.

Electron transfer and atom exchange (ETAE) between aqueous Fe(II) and Fe(III) oxides induces surface growth and dissolution that affects trace element fate and transport. We have recently demonstrated Ni(II) cycling through goethite and hematite (adsorbed Ni incorporates into the mineral structure and preincorporated Ni releases to solution) during Fe(II)-Fe(III) ETAE. However, the chemical parameters affecting net trace element release remain unknown. Here, we examine the chemical controls on Ni(II) and Zn(II) release from Ni- and Zn-substituted goethite and hematite during reaction with Fe(II). Release follows a rate law consistent with surface reaction limited mineral dissolution and suggests that release occurs near sites of Fe(III) reductive dissolution during Fe(II)-Fe(III) ETAE. Metal substituent type affects reactivity; Zn release is more pronounced from hematite than goethite, whereas the opposite trend occurs for Ni. Buildup of Ni or Zn in solution inhibits further release but this resumes upon fluid exchange, suggesting that sustained release is possible under flow conditions. Mineral and aqueous Fe(II) concentrations as well as pH strongly affect sorbed Fe(II) concentrations, which directly control the reaction rates and final metal concentrations. Our results demonstrate that structurally incorporated trace elements are mobilized from iron oxides into fluids without abiotic or microbial net iron reduction. Such release may affect micronutrient availability, contaminant transport, and the distribution of redox-inactive trace elements in natural and engineered systems.

Fe(II)-mediated reduction and repartitioning of structurally incorporated Cu, Co, and Mn in iron oxides.

The reduction of trace elements and contaminants by Fe(II) at Fe(III) oxide surfaces is well documented. However, the effect of aqueous Fe(II) on the fate of redox-active trace elements structurally incorporated into iron oxides is unknown. Here, we investigate the fate of redox-active elements during Fe(II)-activated recrystallization of Cu-, Co-, and Mn-substituted goethite and hematite. Enhanced release of Cu, Co, and Mn to solution occurs upon exposure of all materials to aqueous Fe(II) relative to reactions in Fe(II)-free fluids. The quantity of trace element release increases with pH when Fe(II) is present but decreases with increasing pH in the absence of Fe(II). Co and Mn release from goethite is predicted well using a second-order kinetic model, consistent with the release of redox-inactive elements such as Ni and Zn. However, Cu release and Co and Mn release from hematite require the sum of two rates to adequately model the kinetic data. Greater uptake of Fe(II) by Cu-, Co-, and Mn-substituted iron oxides relative to analogues containing only redox-inactive elements suggests that net Fe(II) oxidation occurs. Reduction of Cu, Co, and Mn in all materials following reaction with Fe(II) at pHs 7.0-7.5 is confirmed by X-ray absorption near-edge structure spectroscopy. This work shows that redox-sensitive elements structurally incorporated within iron oxides are reduced and repartitioned into fluids during Fe(II)-mediated recrystallization. Such abiotic reactions likely operate in tandem with partial microbial and abiotic iron reduction or during the migration of Fe(II)-containing fluids, mobilizing structurally bound contaminants and micronutrients in aquatic systems.

Inhibition of trace element release during Fe(II)-activated recrystallization of Al-, Cr-, and Sn-substituted goethite and hematite.

Aqueous Fe(II) reacts with Fe(III) oxides by coupled electron transfer and atom exchange (ETAE) resulting in mineral recrystallization, contaminant reduction, and trace element cycling. Previous studies of Fe(II)-Fe(III) ETAE have explored the reactivity of either pure iron oxide phases or those containing small quantities of soluble trace elements. Naturally occurring iron oxides, however, contain substantial quantities of insoluble impurities (e.g., Al) which are known to affect the chemical properties of such minerals. Here we explore the effect of Al(III), Cr(III), and Sn(IV) substitution (1-8 mol %) on trace element release from Ni(II)-substituted goethite and Zn(II)-substituted hematite during reaction with aqueous Fe(II). Fe(II)-activated trace element release is substantially inhibited from both minerals when an insoluble element is cosubstituted into the structure, and the total amount of release decreases exponentially with increasing cosubstituent. The limited changes in surface composition that occur following reaction with Fe(II) indicate that Al, Cr, and Sn do not exsolve from the structure and that Ni and Zn released to solution originate primarily from the bulk rather than the particle exterior (upper ~3 nm). Incorporation of Al into goethite substantially decreases the amount of iron atom exchange with aqueous Fe(II) and, consequently, the amount of Ni release from the structure. This implies that trace element release inhibition caused by substituting insoluble elements results from a decrease in the amount of mineral recrystallization. These results suggest that naturally occurring iron oxides containing insoluble elements are less susceptible to Fe(II)-activated recrystallization and exhibit a greater retention of trace elements and contaminants than pure mineral phases.

Copper (Cu) speciation in organic-waste (OW) amended soil: Instability of OW-borne Cu(I) sulfide and role of clay and iron oxide minerals.

The geochemistry of copper (Cu) is generally assumed to be controlled by organic matter in soils. However, the role of clay and iron oxide minerals may be understated. Soil density fractionation, X-ray diffraction (XRD), and X-ray absorption spectroscopy (XAS) were combined to assess the long-term behavior of Cu in an agricultural soil subject to organic waste application. Two unprecedented molecular environments of natural Cu (i.e. Cu inherited from the parent rock) in soils are reported: Cu dimer in the interlayer of vermiculite and Cu structurally incorporated within hematite. Moreover, the soil naturally containing Cu-vermiculite, Cu-hematite, but also Cu-kaolinite (Cutotal = 122 mg·kg-1) was amended over 11 years with Cu-rich pig slurry in which Cu was 100 % Cu(I) sulfide. Natural Cu associated with clay and iron oxide minerals persisted in the amended soil, but the exogenous Cu(I) sulfide was unstable. The increase in Cu concentration in the amended soil to 174 mg·kg-1 was accounted for the increase of Cu sorbed to kaolinite and Cu bound to organic matter. These results are important for better understanding the natural occurrence of Cu in soils and for assessing the environmental impacts of organic waste recycling in agricultural fields.

Trace element catalyses mineral replacement reactions and facilitates ore formation.

Reaction-induced porosity is a key factor enabling protracted fluid-rock interactions in the Earth's crust, promoting large-scale mineralogical changes during diagenesis, metamorphism, and ore formation. Here, we show experimentally that the presence of trace amounts of dissolved cerium increases the porosity of hematite (Fe2O3) formed via fluid-induced, redox-independent replacement of magnetite (Fe3O4), thereby increasing the efficiency of coupled magnetite replacement, fluid flow, and element mass transfer. Cerium acts as a catalyst affecting the nucleation and growth of hematite by modifying the Fe2+(aq)/Fe3+(aq) ratio at the reaction interface. Our results demonstrate that trace elements can enhance fluid-mediated mineral replacement reactions, ultimately controlling the kinetics, texture, and composition of fluid-mineral systems. Applied to some of the world's most valuable orebodies, these results provide new insights into how early formation of extensive magnetite alteration may have preconditioned these ore systems for later enhanced metal accumulation, contributing to their sizes and metal endowment.

Rapid reduction of N-nitrosamine disinfection byproducts in water with hydrogen and porous nickel catalysts.

There is a need for new technologies to rapidly and economically treatwater contaminated with N-nitrosodimethylamine (NDMA) and related compounds because of their high toxicity and recent detection in drinking water sources as a consequence of industrial releases and chlorine disinfection of wastewater effluent Treatment of N-nitrosamines with H2 in conjunction with a high surface area porous nickel material, a model nonprecious metal catalyst, has been evaluated. Experiments show that NDMA is reduced rapidly and catalytically to dimethylamine and N2 (e.g., t1/2 = 1.5 min for 500 mg/L catalyst and PH2 = 1 atm), and kinetic trends are consistent with a surface-mediated mechanism involving scission of the N-nitrosamine N-N bond and subsequent reactions with adsorbed atomic hydrogen. The metal-loading-normalized pseudo-first-order rate constant (77.9 +/- 13.1 L g(Ni)(-1) h(-1)) exceeds values reported for Pd-based catalysts. Several related N-nitrosamines react at rates similar to those of NDMA, indicating a weak dependence on structure. The reaction rates for NDMA reduction are not significantly affected by changing pH, and the presence of high concentrations of many common water constituents (Na+, Ca2+, Mg2+, Cl-, SO4(2-), HCO(3-), and NOM) exerts only a small effect on reaction rates. Nitrate is also reduced by the Ni catalyst, and high nitrate concentrations competitively inhibit the reduction of NDMA. (Bi)sulfide poisons the catalyst by strong chemisorption to the Ni surface. Cost-normalized rate constants for the Ni catalyst are highly favorable compared to Pd-based catalysts, indicating that, with further development, Ni-based catalysts may become attractive alternatives to precious metal catalysts.