C. Drew Tait

Coprecipitation of Uranium(VI) with Calcite: XAFS, micro-XAS, and luminescence characterization

X-ray absorption and luminescence spectroscopies have been used to characterize the local structure and coordination of uranium(VI) species coprecipitated with calcite (CaCO3) from room-temperature aqueous solutions. Different solution chemistries and pHs are found to result in differences in the equatorial coordination of the uranyl species (UO2 ) incorporated in the calcite, with multiple coordination environ- ments of uranyl evident in one sample. Differences in the equatorial coordination between the aqueous uranyl species and those found in the calcite indicate that coordination changes occur during incorporation of at least some species. This contrasts with previous findings showing no change in equatorial coordination during uranyl incorporation into aragonite, and may explain the greater incorporation in this latter phase. The absence of calcium backscatterers and well defined structure beyond the equatorial shell is consistent with disorder associated with disruption of the local calcite structure. This may indicate an inability of the uranyl unit to assume a stable structural environment in the host calcite, which could decrease the stability of uranyl- containing calcite. Calcite single crystals grown in uranyl-containing solutions exhibit polygonized spiral growth hillocks on (101 ¯4) surfaces composed of four vicinal surfaces, consistent with face symmetry. Micro-X-ray fluorescence reveals that uranium is differentially incorporated between nonequivalent vicinal surfaces, reflecting step- selective incorporation of uranyl species during growth. Micro-X-ray absorption near-edge structure spectra from the nonequivalent vicinal faces fail to reveal any differences in speciation between the vicinals or that might account for the presence of the multiple coordination environments identified by luminescence and X-ray absorption spectroscopies. Copyright

Speciation of aqueous gold(III) chlorides from ultraviolet/visible absorption and Raman/resonance Raman spectroscopies

Abstract Gold(III) speciation in a one molar NaCl aqueous solution at ambient temperature and pressure was determined as a function of pH using ultraviolet/visible (UV/vis) absorption and Raman/resonance Raman (RR) spectroscopies. Gold concentrations in the solutions studied by UV/vis spectroscopy were ~10 −4 M whereas those studied by Raman spectroscopy were ~10 −2 M. Changes in the intensity and positions of ligand-to-metal charge transfer bands in the UV/vis spectra of the Au(III) chloride solutions with increasing pH are consistent with replacement of chloride by hydroxide ligands. Changes in the number, position, and intensity of Raman and RR spectra of the same solutions are also consistent with successive replacement of chloride by hydroxide ligands in the first coordination sphere of four-coordinated Au(III) with increasing pH. Our Raman and UV/vis data are broadly consistent with earlier speciation predictions based on a variety of chemical measurements, but demonstrate that the mixed chloro-hydroxo complexes are more stable than predicted on the basis of theoretically estimated stability constants.

Solubilization of plutonium hydrous oxide by iron-reducing bacteria

The removal of plutonium from soils id challenging because of its strong sorption to soils and limited solubility, Microbial reduction of metals is known to affect the speciation and solubility of sparingly soluble metals in the environment, notably iron and manganese. The similarity in reduction potential for [alpha]-FeOOH(s) and hydrous PuO[sub 2](s) suggests that iron-reducing bacteria may also reduce and solubilize plutonium. Bacillus strains were used to demonstrate that iron-reducing bacteria mediate the solubilization of hydrous PuO[sub 2](s) under anaerobic conditions. Up to [approximately]90% of the PuO[sub 2] was biosolubilized in the presence of nitrilotriacetic acid (NTA) within 6-7 days. Biosolubilization occurred to a lesser extent ([approximately] 40%) in the absence of NTA. Little PuO[sub 2] solubilization occurred in sterile culture media or in the presence of a non-iron-reducing Escherichia coli. These observations suggest a potentially attractive, environmentally benign strategy for the remediation of Pu-contaminated soils. 26 refs., 5 figs., 2 tabs.

Neptunium and Plutonium Solubilities in a Yucca Mountain Groundwater

Solubilities of neptunium and plutonium were studied in J-13 groundwater (ionic strength of about 3.7 mmol; total dissolved carbonate of 2.8 mmol) from the proposed Yucca Mountain Nuclear Waste Repository site, Nevada, at three different temperatures (25, 60, and 90 °C) and pH values (6.0, 7.0, and 8.5). Experiments were performed from both over- and undersaturation at defined CO2 partial pressures. The solubility of 237Np from oversaturation ranged from a high of (9.40 ± 1.22) × 10-4 M at pH 6.0 and 60 °C to a low of (5.50 ± 1.97) × 10-6 M at pH 8.5 and 90 °C. The analytical results of solubility experiments from undersaturation (temperatures of 25 and 90 °C and pH values 6, 7, and 8.5) converged on these values. The 239/240Pu solubilities ranged from (4.70 ± 1.13) × 10-8 M at pH 6.0 and 25 °C to (3.62 ± 1.14) × 10-9 M at pH 8.5 and 90 °C. In general, both neptunium and plutonium solubilities decreased with increasing pH and temperature. Greenish-brown crystalline Np2O5·xH2O was identified as the solubil...

Speciation of aqueous palladium(II) chloride solutions using optical spectroscopies

Abstract Spectroscopic measurements of palladium(II) chloride solutions have been performed under ambient to elevated temperature conditions with systematic changes in pH and [Cl−1]. Spectral signatures from electronic absorption spectra (Uv/Vis) and Raman vibrational spectra were determined, and these were subsequently used to systematically map out species along several paths of the predominance diagram. The species PdCl x (H 2 O) 4−x 2−x (x = 2, 3, or 4) and Pd(OH)2 were observed, along with a precipitation product formed from > 10 μM [Pd2+]solutions under near-neutral conditions. The elemental composition of the precipitation product was examined with a scanning electron micrograph (SEM) and was found to contain chloride as well as palladium. While sub-stoichiometric amounts of available OH− ligand produced UV/ Vis solution spectra likely to be from mixed Pd-Cl-OH species, the pH field of these species would be vanishingly small at low, geologically relevant palladium ion concentrations where [OH−]is no longer the limiting reagent in the transformation. In mildly acidic media, where chloropalladium(II) species predominate, elevated temperatures (up to 90°C) cause lower charged palladium-chloride species to be favored, consistent with the lowered dielectric constant of water at higher temperatures.

OXIDATION STATE DETERMINATION OF PLUTONIUM AQUO IONS USING X-RAY ABSORPTION SPECTROSCOPY

Abstract Four oxidation states (III, IV, V, and VI) of Pu may coexist under environmentally relevant conditions. An efficient method to determine the states actually present in various matrices would enhance the ability to model the fate and transport of plutonium in process streams and in the environment. This communication establishes that the L3 X-ray absorption near-edge structure (XANES) spectra of Pu are primarily determined by the valence state and the presence or absence of the trans dioxo moiety, consistent with previous U and Np XANES studies. The edge energies were observed to shift progressively to higher energy with increasing valence, with an average 1.68 eV increase per formal oxidation state increase. In addition, the general spectral shape of the (III) and (IV) species is clearly different from the dioxo-containing (V) and (VI) species, with the first maximum much larger and sharper for the (III) and (IV) spectra than for the (V) and (VI) spectra.

A Raman spectroscopic study of arsenite and thioarsenite species in aqueous solution at 25 °C

The Raman spectra of thioarsenite and arsenite species in aqueous solution were obtained at room temperature. Solutions at constant ΣAs + ΣS of 0.1 and 0.5 mol kg-1 were prepared with various ΣS/ΣAs ratios (0.1–9.0) and pH values (~7–13.2). Our data suggest that the speciation of As under the conditions investigated is more complicated than previously thought. The Raman measurements offer evidence for at least six separate S-bearing As species whose principal bands are centered near 365, 385, 390, 400, 415 and 420 cm-1. The data suggest that at least two different species may give rise to bands at 385 cm-1, bringing the probable minimum number of species to seven. Several additional species are possible but could not be resolved definitively. In general, the relative proportions of these species are dependent on total As concentration, ΣS/ΣAs ratio and pH. At very low ΣS/ΣAs ratios we also observe Raman bands attributable to the dissociation products of H3AsO3(aq). Although we were unable to assign precise stoichiometries for the various thioarsenite species, we were able to map out general pH and ΣS/ΣAs conditions under which the various thioarsenite and arsenite species are predominant. This study provides a basis for more detailed Raman spectroscopic and other types of investigations of the nature of thioarsenite species.

Solubility and spectroscopic studies of the interaction of palladium with simple carboxylic acids and fulvic acid at low temperature

Abstract The interaction of Pd with some O-donor organic acid anions has been investigated using solubility measurements and a variety of spectroscopic techniques (UV-visible, Raman, FTIR, 13C NMR). Some of the ligands investigated (acetate, oxalate and fulvic acid) occur naturally in relatively high concentrations, whereas others (phthalate and salicylate) serve as models of potential binding sites on humic and fulvic acids. Solubility measurements show that the presence of acetate, phthalate, salicylate and fulvic acid (oxalate was not studied via solubility methods) can increase the mobility of Pd over various pH ranges, depending on the organic ligand. In the case of acetate, UV-visible and Raman spectroscopy (13C NMR results were inconclusive) provide strong evidence for the formation of electrostatically bound, possibly outer-sphere palladium acetate complexes. Oxalate was confirmed by UV-visible and FTIR spectroscopy to compete favorably with chloride (0.56 M NaCl) for Pd even at oxalate concentrations as low as 1 mM at pH = 6–7. Available data from the literature suggest that oxalate may have an influence on Pd mobility at free oxalate concentrations as low as 10−8–10−9 M. UV-visible spectroscopy provides evidence of an initially rapid, followed by a slower, reaction between PdCl42− and o-phthalate ion. Our findings lend support to the idea that similar binding sites on fulvic acid may be capable of complexing and solubilizing Pd in the natural environment. Although thermodynamic data are required to fully quantify the extent, it is concluded that simple carboxylic acid anions and/or fulvic and humic acids should be capable of significantly enhancing Pd transport in the surficial environment by forming truly dissolved complexes. On the other hand, flocculation of fulvic/humic acids, owing to changing ionic strengths or pH, or adsorption of these acids onto mineral surfaces, may also provide effective means of immobilizing Pd. These results have applications in exploration geochemistry and disposal of radioactive waste containing 107Pd.

Chemical Speciation of Neptunium(VI) under Strongly Alkaline Conditions. Structure, Composition, and Oxo Ligand Exchange

Hexavalent neptunium can be solubilized in 0.5-3.5 M aqueous MOH (M = Li(+), Na(+), NMe4(+) = TMA(+)) solutions. Single crystals were obtained from cooling of a dilute solution of Co(NH3)6Cl3 and NpO2(2+) in 3.5 M [N(Me)4]OH to 5 °C. A single-crystal X-ray diffraction study revealed the molecular formula of [Co(NH3)6]2[NpO2(OH)4]3·H2O, isostructural with the uranium analogue. The asymmetric unit contains three distinct NpO2(OH)4(2-) ions, each with pseudooctahedral coordination geometry with trans-oxo ligands. The average Np═O and Np-OH distances were determined to be 1.80(1) and 2.24(1) Å, respectively. EXAFS data and fits at the Np L(III)-edge on solid [Co(NH3)6]2[NpO2(OH)4]3·H2O and aqueous solutions of NpO2(2+) in 2.5 and 3.5 M (TMA)OH revealed bond lengths nearly identical with those determined by X-ray diffraction but with an increase in the number of equatorial ligands with increasing (TMA)OH concentration. Raman spectra of single crystals of [Co(NH3)6]2[NpO2(OH)4]3·H2O reveal a ν1(O═Np═O) symmetric stretch at 741 cm(-1). Raman spectra of NpO2(2+) recorded in a 0.6-2.2 M LiOH solution reveal a single ν1 frequency of 769 cm(-1). Facile exchange of the neptunyl oxo ligands with the water solvent was also observed with Raman spectroscopy performed with (16)O- and (18)O-enriched water solvent. The combination of EXAFS and Raman data suggests that NpO2(OH)4(2-) is the dominant solution species under the conditions of study and that a small amount of a second species, NpO2(OH)5(3-), may also be present at higher alkalinity. Crystal data for [Co(NH3)6]2[NpO2(OH)4]3·H2O: monoclinic, space group C2/c, a = 17.344(4) Å, b = 12.177(3) Å, c = 15.273 Å, β = 120.17(2)°, Z = 4, R1 = 0.0359, wR2 = 0.0729.

A Model for Trivalent Actinides in Media Containing High Carbonate Concentrations − Structural Characterization of the Lanthanide Tetracarbonate [Co(NH3)6][Na(μ-H2O)(H2O)4]2[Ho(CO3)4]·4H2O

The identity of the limiting HoIII species in aqueous solutions with high carbonate concentrations has been determined to be Ho(CO3)45−. Single crystals of [Co(NH3)6][Na(μ−H2O)(H2O)4]2[Ho(CO3)4]·4H2O were obtained by the addition of [Co(NH3)6]3+ to an aqueous 0.04 M solution of HoIII in 2.1 M Na2CO3. The asymmetric unit contains the anion, [Ho(CO3)4]5−, a [Co(NH3)6]3+ cation and two Na+ cations, which are bound to H2O molecules in an edge-sharing bioctahedral geometry. The [Ho(CO3)4]5− anion is eight coordinate with four bidentate carbonate ligands bound to the Ho atom. The molecule has essentially C2v symmetry with two coplanar carbonates making a vane, which is perpendicular to a similar vane produced by the other two carbonate ligands. An alternative way to this view molecule is through the geometry of the C atoms, which are found in a distorted tetrahedron. The average Ho−O distance was determined to be 2.361(5) A, while the average Ho−C distance was 2.784(6) A. The IR and Raman spectra were determined in both the solid state and solution in order to confirm the solution speciation. The Raman data show a single CO32− stretch for the solid at 1062 cm−1. The solution data show multiple peaks with the most prominent being at 1048 cm−1, which is consistent with the literature reports of an equilibrium mixture. The IR data for the solids confirm the X-ray results showing bidentate carbonate ligands by the splitting of the ν3 band of the CO32−. The crystal data for [Co(NH3)6][Na(μ-H2O)(H2O)4]2[Ho(CO3)4]·4H2O are as follows: monoclinic space group P2/n, a = 8.7091(5) A, b = 10.8744(6) A, c = 15.7971(9) A, β = 93.117(1)°, Z = 2, R1 = 0.0307, wR2 = 0.0756.