Samuel Shaw

The kinetics and mechanisms of goethite and hematite crystallization under alkaline conditions, and in the presence of phosphate

Abstract The transformations of 2-line ferrihydrite to hematite (pH 10.7) or goethite (pH 13.7), and of phosphate-doped 2-line ferrihydrite to goethite (pH 13.7), were studied at 60.137 °C using synchrotron- based, in-situ energy dispersive powder diffraction (EDPD). The time-resolved data for the growth of the diffraction peaks were fitted with a pseudo first-order kinetic model. As shown in previous studies, the conditional rate constant of goethite formation increases with increasing pH and is significantly lower than that for hematite crystallization. The activation energies of nucleation for hematite (pH 10.7), pure goethite (pH 13.7), and phosphate-doped goethite (pH 13.7) are 24, 7, and 21 kJ/mol, respectively, whereas the activation energies of crystallization are 69, 39, and 26 kJ/mol. The crystallization of phosphate-doped ferrihydrite produced large rectangular goethite crystals with dense ferrihydrite cores on which the goethite grew epitaxially. The rate of goethite formation is greatly reduced in the presence of phosphate due to an increase in the entropic component of the free energy of activation. This increase in entropy arises from adsorption of phosphate on to the (210) crystal faces, with an associated increase in relative growth rate on the (101) faces.

Microbial Reduction of Fe(III) under Alkaline Conditions Relevant to Geological Disposal

ABSTRACT To determine whether biologically mediated Fe(III) reduction is possible under alkaline conditions in systems of relevance to geological disposal of radioactive wastes, a series of microcosm experiments was set up using hyperalkaline sediments (pH ∼11.8) surrounding a legacy lime working site in Buxton, United Kingdom. The microcosms were incubated for 28 days and held at pH 10. There was clear evidence for anoxic microbial activity, with consumption of lactate (added as an electron donor) concomitant with the reduction of Fe(III) as ferrihydrite (added as the electron acceptor). The products of microbial Fe(III) reduction were black and magnetic, and a range of analyses, including X-ray diffraction, transmission electron microscopy, X-ray absorption spectroscopy, and X-ray magnetic circular dichroism confirmed the extensive formation of biomagnetite in this system. The addition of soluble exogenous and endogenous electron shuttles such as the humic analogue anthraquinone-2,6-disulfonate and riboflavin increased both the initial rate and the final extent of Fe(III) reduction in comparison to the nonamended experiments. In addition, a soluble humic acid (Aldrich) also increased both the rate and the extent of Fe(III) reduction. These results show that microbial Fe(III) reduction can occur in conditions relevant to a geological disposal facility containing cement-based wasteforms that has evolved into a high pH environment over prolonged periods of time (>100,000 years). The potential impact of such processes on the biogeochemistry of a geological disposal facility is discussed, including possible coupling to the redox conditions and solubility of key radionuclides.

Formation of green rust sulfate : a combined in situ time-resolved X-ray scattering and electrochemical study.

The mechanism of green rust sulfate (GR-SO(4)) formation was determined using a novel in situ approach combining time-resolved synchrotron-based wide-angle X-ray scattering (WAXS) with highly controlled chemical synthesis and electrochemical (i.e., Eh and pH) monitoring of the reaction. Using this approach,GR-SO(4) was synthesized under strictly anaerobic conditions by coprecipitation from solutions with known Fe(II)/Fe(III) ratios (i.e., 1.28 and 2) via the controlled increase of pH. The reaction in both systems proceeded via a three-stage precipitation and transformation reaction. During the first stage,schwertmannite (Fe(8)O(8)(OH)(4.5)(SO(4))(1.75)) precipitated directly from solution at pH 2.8-4.5. With increasing pH (>5), Fe(2+) ions adsorb to the surface of schwertmannite and catalyze its transformation to goethite (alpha-FeOOH) during the second stage of the reaction. In the third stage, the hydrolysis of the adsorbed Fe(2+) ions on goethite initiates its transformation to GR-SO(4) at pH >7. The GR-SO(4) then continues to crystallize up to pH approximately 8.5. These results suggest that with an Fe(II)/Fe(III) ratio of < or = 2 in the initial solution the structural Fe(II)/Fe(III) of the GR-SO(4) will be close to that of the starting composition.

Incorporation of uranium into hematite during crystallization from ferrihydrite

Ferrihydrite was exposed to U(VI)-containing cement leachate (pH 10.5) and aged to induce crystallization of hematite. A combination of chemical extractions, TEM, and XAS techniques provided the first evidence that adsorbed U(VI) (≈3000 ppm) was incorporated into hematite during ferrihydrite aggregation and the early stages of crystallization, with continued uptake occurring during hematite ripening. Analysis of EXAFS and XANES data indicated that the U(VI) was incorporated into a distorted, octahedrally coordinated site replacing Fe(III). Fitting of the EXAFS showed the uranyl bonds lengthened from 1.81 to 1.87 Å, in contrast to previous studies that have suggested that the uranyl bond is lost altogether upon incorporation into hematite. The results of this study both provide a new mechanistic understanding of uranium incorporation into hematite and define the nature of the bonding environment of uranium within the mineral structure. Immobilization of U(VI) by incorporation into hematite has clear and important implications for limiting uranium migration in natural and engineered environments.

In-situ synchrotron study of the kinetics, thermodynamics, and reaction mechanisms of the hydrothermal crystallization of gyrolite, Ca16Si24O60(OH)8·14H2O

Abstract The hydrothermal crystallization of gyrolite was studied dynamically at 190-240 °C using synchrotron- based in situ Energy Dispersive Powder Diffraction (EDPD). The reaction mechanism involves the initial crystallization of a calcium silicate hydrate (C-S-H) gel, which has a sheet structure with well ordered Ca(O,OH) layers and disordered silicate layers. This is followed by the intermediate formation of Z-phase which finally transforms to gyrolite. This process involves ordering of the silicate layers and an increase in the order along c. Kinetics data for all stages of the crystallization process were determined by analyzing the growth and decline of various diffraction peaks with time. The activation energy (Ea) (nucleation) for Zphase is ~39 kJ/mol while that for gyrolite is ~56 kJ/mol. Ea (crystallization) of gyrolite is higher at ~80 kJ/mol. The reaction occurs via a two-dimensional, diffusion-controlled mechanism and is a continuous process that suggests that Z-phase is an unstable, transient phase.

A route for the direct crystallization of dolomite

Abstract The direct crystallization of dolomite from an aqueous solution at temperatures between 60-220 °C was followed in situ through time-resolved synchrotron-based energy-dispersive X‑ray diffraction combined with offline high-resolution imaging, X‑ray diffraction, and infrared spectroscopy. Crystalline CaMg(CO3)2 phases form through a three-stage process. In the first stage, a nanoparticulate magnesium-deficient, amorphous calcium carbonate (Mg-ACC) with a nominal formula of Ca0.606Mg0.394CO3·1.37H2O forms. After a temperature-dependent induction time, during stage 2 the Mg-ACC partially dehydrates and orders prior to its rapid (<5 min) crystallization to non-stoichiometric proto-dolomite. This occurs via the dissolution of Mg-ACC, followed by the secondary nucleation of proto-dolomite from solution. The proto-dolomite crystallization proceeds via spherulitic growth that follows a growth front nucleation mechanism with a de-nuovo and continuous formation of nanocrystalline proto-dolomite subunits that form spherical aggregates. In stage three of the reaction, the proto-dolomite transforms to highly crystalline and stoichiometric dolomite on a much longer timescale (hours to days), via an Ostwald-ripening mechanism. Such a three-stage crystallization can explain microbially induced proto-dolomites observed in modern hypersaline settings and may also be the route by which the Cryogenian cap dolomite deposits of the Neoproterozoic formed.

Incorporation and Retention of 99-Tc(IV) in Magnetite under High pH Conditions

Technetium incorporation into magnetite and its behavior during subsequent oxidation has been investigated at high pH to determine the technetium retention mechanism(s) on formation and oxidative perturbation of magnetite in systems relevant to radioactive waste disposal. Ferrihydrite was exposed to Tc(VII)(aq) containing cement leachates (pH 10.5-13.1), and crystallization of magnetite was induced via addition of Fe(II)aq. A combination of X-ray diffraction (XRD), chemical extraction, and X-ray absorption spectroscopy (XAS) techniques provided direct evidence that Tc(VII) was reduced and incorporated into the magnetite structure. Subsequent air oxidation of the magnetite particles for up to 152 days resulted in only limited remobilization of the incorporated Tc(IV). Analysis of both X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) data indicated that the Tc(IV) was predominantly incorporated into the magnetite octahedral site in all systems studied. On reoxidation in air, the incorporated Tc(IV) was recalcitrant to oxidative dissolution with less than 40% remobilization to solution despite significant oxidation of the magnetite to maghemite/goethite: All solid associated Tc remained as Tc(IV). The results of this study provide the first direct evidence for significant Tc(IV) incorporation into the magnetite structure and confirm that magnetite incorporated Tc(IV) is recalcitrant to oxidative dissolution. Immobilization of Tc(VII) by reduction and incorporation into magnetite at high pH and with significant stability upon reoxidation has clear and important implications for limiting technetium migration under conditions where magnetite is formed including in geological disposal of radioactive wastes.

Formation of stable uranium(VI) colloidal nanoparticles in conditions relevant to radioactive waste disposal

The favored pathway for disposal of higher activity radioactive wastes is via deep geological disposal. Many geological disposal facility designs include cement in their engineering design. Over the long term, interaction of groundwater with the cement and waste will form a plume of a hyperalkaline leachate (pH 10-13), and the behavior of radionuclides needs to be constrained under these extreme conditions to minimize the environmental hazard from the wastes. For uranium, a key component of many radioactive wastes, thermodynamic modeling predicts that, at high pH, U(VI) solubility will be very low (nM or lower) and controlled by equilibrium with solid phase alkali and alkaline-earth uranates. However, the formation of U(VI) colloids could potentially enhance the mobility of U(VI) under these conditions, and characterizing the potential for formation and medium-term stability of U(VI) colloids is important in underpinning our understanding of U behavior in waste disposal. Reflecting this, we applied conventional geochemical and microscopy techniques combined with synchrotron based in situ and ex situ X-ray techniques (small-angle X-ray scattering and X-ray adsorption spectroscopy (XAS)) to characterize colloidal U(VI) nanoparticles in a synthetic cement leachate (pH > 13) containing 4.2-252 μM U(VI). The results show that in cement leachates with 42 μM U(VI), colloids formed within hours and remained stable for several years. The colloids consisted of 1.5-1.8 nm nanoparticles with a proportion forming 20-60 nm aggregates. Using XAS and electron microscopy, we were able to determine that the colloidal nanoparticles had a clarkeite (sodium-uranate)-type crystallographic structure. The presented results have clear and hitherto unrecognized implications for the mobility of U(VI) in cementitious environments, in particular those associated with the geological disposal of nuclear waste.

Alteration of sediments by hyperalkaline k-rich cement leachate: Implications for strontium adsorption and incorporation

Results are presented from 1 year batch experiments where K-rich hyperalkaline pH 13.5 young cement water (YCW) was reacted with sediments to investigate the effect of high pH, mineral alteration, and secondary mineral precipitation on (90)Sr sorption. After reaction with YCW, Sr sorption was found to be greater than 75% in all samples up to 365 days and 98% in a sample reacted for 365 days at 70 °C. Scanning electron microscopy analysis of sediment samples reacted at room temperature showed surface alteration and precipitation of a secondary phase, likely a K-rich aluminosilicate gel. The presence of Sr-Si(Al) bond distances in Sr K-edge extended X-ray absorption fine structure (EXAFS) analysis suggested that the Sr was present as an inner-sphere adsorption complex. However, sequential extractions found the majority of this Sr was still exchangeable with Mg(2+) at pH 7. For the sample reacted for 1 year at 70 °C, EXAFS analysis revealed clear evidence for ∼6 Sr-Si(Al) backscatters at 3.45 Å, consistent with Sr incorporation into the neoformed K-chabazite phase that was detected by X-ray diffraction and electron microscopy. Once incorporated into chabazite, (90)Sr was not exchangeable with Mg(2+), and chemical leaching with pH 1.5 HNO3 was required to remobilize 60% of the (90)Sr. These results indicate that, in high pH cementitious leachate, there is significantly enhanced Sr retention in sediments due to changes in the adsorption mechanism and incorporation into secondary silicate minerals. This suggests that Sr retention may be enhanced in this high pH zone and that the incorporation process may lead to irreversible exchange of the contaminant over extended time periods.

Uranium fate during crystallization of magnetite from ferrihydrite in conditions relevant to the disposal of radioactive waste

Abstract Uranium incorporation into magnetite and its behaviour during subsequent oxidation has been investigated at high pH to determine the uranium retention mechanism(s) on formation and oxidative perturbation of magnetite in systems relevant to radioactive waste disposal. Ferrihydrite was exposed to U(VI)aq containing cement leachates (pH 10.5-13.1) and crystallization of magnetite was induced via addition of Fe(II)aq. A combination of XRD, chemical extraction and XAS techniques provided direct evidence that U(VI) was reduced and incorporated into the magnetite structure, possibly as U(V), with a significant fraction recalcitrant to oxidative remobilization. Immobilization of U(VI) by reduction and incorporation into magnetite at high pH, and with significant stability upon reoxidation, has clear and important implications for limiting uranium migration in geological disposal of radioactive wastes.