Daniel E.
Crean
a,
Martin C.
Stennett
a,
Francis R.
Livens
b,
Daniel
Grolimund
c,
Camelia N.
Borca
c and
Neil C.
Hyatt
*a
aImmobilisation Science Laboratory, Department of Materials Science and Engineering, The University of Sheffield, UK. E-mail: n.c.hyatt@sheffield.ac.uk
bCentre for Radiochemistry Research, Department of Chemistry, The University of Manchester, UK
cSwiss Light Source, Paul Scherrer Institute, Villigen, Switzerland
First published on 29th June 2020
An environmentally aged radioactive particle of UFeO4 recovered from soil contaminated with munitions depleted uranium (DU) was characterised by microbeam synchrotron X-ray analysis. Imaging of uranium speciation by spatially resolved X-ray diffraction (μ-XRD) and X-ray absorption spectroscopy (μ-XAS) was used to localise UFeO4 in the particle, which was coincident with a distribution of U(V). The U oxidation state was confirmed using X-ray Absorption Near Edge Structure (μ-XANES) spectroscopy as +4.9 ± 0.15. Le-Bail fitting of the particle powder XRD pattern confirmed the presence of UFeO4 and a minor alteration product identified as chernikovite (H3O)(UO2)(PO4)·3H2O. Refined unit cell parameters for UFeO4 were in good agreement with previously published values. Uranium–oxygen interatomic distances in the first co-ordination sphere were determined by fitting of Extended X-ray Absorption Fine Structure (μ-EXAFS) spectroscopy. The average first shell U–O distance was 2.148 ± 0.012 Å, corresponding to a U valence of +4.96 ± 0.13 using bond valence sum analysis. Using bond distances from the published structure of UFeO4, U and Fe bond valence sums were calculated as +5.00 and +2.83 respectively, supporting the spectroscopic analysis and confirming the presence of a U(V)/Fe(III) pair. Overall this investigation provides important evidence for the stability of U(V) ternary oxides, in oxic, variably moist surface environment conditions for at least 25 years.
Environmental significanceThe long term environmental behaviour and health risk posed by depleted uranium particles depends critically on uranium speciation, which is of importance in managing and remediating contaminated land. In particular, oxic and variably moist surface conditions are expected to promote oxidation and dissolution of U(V) phases to form U(VI) species. Here, we demonstrate the long term (>25 year) stability of UFeO4, under such conditions, formed by testing of depleted uranium munitions, using multi-modal X-ray microanalysis. The broader significance of this study provides evidence for the environmental stability of U(V) phases of relevance to environmental contamination by radioactive particles from nuclear fuel cycle and other activities. |
In this study, information on the chemical speciation of U in a particle containing the ternary oxide UFeO4 is established by multi-modal synchrotron X-ray microscopy. Ternary compounds in the U–Fe–O system are of interest in the interaction of uranium wastes with iron oxides3 and as a component of corium in severe nuclear power plant accidents.4,5 Iron is ubiquitous in structural components of nuclear reactor systems, and in particular, some modern nuclear reactor designs employ hematite as a sacrificial barrier in core catcher systems.6 Compounds of Fe and U have also been previously described as minority phases in some hot particles.7
In the U–Fe–O system two ternary oxides are known, UFeO4 and UFe2O6, the latter suggested to be stable only at high pressure.3,8–11 UFeO4 crystallises in an orthorhombic system with space group Pbcn,8,10,11 and a similarly structured ternary oxide in the U–Cr–O ternary system (UCrO4) has also been synthesised and characterised.11–13 The oxidation state of uranium in these compounds was first inferred as U(V) by measurement of a small magnetic moment on the U atom,12,14 and more recently verified by X-ray Absorption Spectroscopy and X-ray Photoelectron Spectroscopy, with supporting evidence from DFT calculations.11,15 Pentavalent uranium disproportionates to U(IV) and U(VI) in aqueous systems, and as such is rarely found in geologic materials.16 However, many compounds of U(V) have been characterised, including some rare examples of naturally occurring U(V) minerals, of which wyartite (CaU5+(UO2)2(CO3)O4(OH)(H2O)7) was the first to be identified.17 The most common co-ordination environment for U(V) is pentagonal bipyramidal,18 although some structures containing U(V) in 8-fold19 and distorted octahedral environments are reported.16 The U sites in UFeO4 and UCrO4 are octahedral with differing extents of distortion.8,10–12
The high X-ray photon flux and small spot size achievable with modern microfocus synchrotron X-ray beamlines allows the use of localised X-ray absorption spectroscopy (XAS) techniques to probe the oxidation state and chemical environment of elements in radioactive and hot particles, which may not be amenable to regular preparation or characterisation methods.20,21 The particle in this study was recovered from soils contaminated as a result of depleted uranium munitions test firing.22 The use of these techniques offers a direct measure of the uranium oxidation state to demonstrate the presence of U(V) in UFeO4, and provides evidence on the environmental behaviour of this compound. Coupled with refinement of micro X-ray diffraction data, and elemental analysis by microfocus X-ray fluorescence spectroscopy (μ-XRF), these techniques provide an integrated methodology for detailed chemical characterisation of radioactive and hot particles of a scale commensurate with, or greater, than the X-ray footprint.
X-ray fluorescence (μ-XRF) spectra were collected using a silicon drift detector (KETEK instruments) placed at 90° to the incident beam. 2D X-ray diffraction (XRD) patterns were recorded using a PILATUS 100K Hybrid Photon Counting (HPC) pixel array detector25 mounted 46 mm behind the sample with a tungsten beamstop in place. The μ-XRD setup was calibrated with respect to a silicon standard (NIST 640c), and the angular resolution was approximately 0.1° 2θ. Incident photon energy for μ-XRF and μ-XRD was 17.500 keV (λ = 0.70849 Å).
Extended X-ray absorption fine structure (μ-EXAFS) spectroscopy was performed in fluorescence mode at the uranium L3 edge. Data were collected across an energy range of 16.900 keV to 18.000 keV. Raw XAS data were processed using the program Athena27 to remove the absorption edge background. EXAFS data were self-absorption corrected with an idealised composition of only UFeO4 using the Troger algorithm implemented in Athena.27,28 Theoretical backscattering path phase and amplitude functions were calculated using FEFF 6 and fit to the data using the Artemis/IFEFFIT software package.27,29 Fits were performed to Fourier transformed R-space data with k-weights of 1, 2 and 3 to reduce parameter correlation.
The spatial distribution of uranium oxidation state was determined using a μ-XAS mapping approach.22,31,32 Maps of absorption co-efficient were constructed by μ-XRF mapping divided by incident intensity (I0) at two energies in the U L3 XANES region (17.168 keV and 17.850 keV), normalised with respect to post-edge energy (17.500 keV). The estimated oxidation state was calculated from the per-pixel absorption coefficient with reference to a linear calibration relationship derived from uranium standard spectra (see Fig. S2†). Maps of oxidation state at both energies showed good agreement and were averaged. It should be noted that both the average local structure of the absorber element and oxidation state determine the normalised absorption at each pixel, and, therefore, this approach affords a map of chemical speciation contrast. Nevertheless, by choosing the excitation energies with due care, and with validation using an independent technique, is possible to construct chemical speciation maps dominated by oxidation state contrast. Our choice of excitation energies is based on an earlier investigation, in which optimisation allowed differentiation of U3O7 and U3O8 by chemical speciation mapping, verified by μ-XRD.22
Fig. 1 U and Fe X-ray fluorescence (a and b), uranium redox (c) and crystalline uranium phase (d) chemical imaging of a DU particle containing UFeO4. |
Fig. 1d shows an approximately circular domain of UFeO4 (∼10 μm), with a similar shaped region of elevated fluorescence intensity observed in both uranium and iron elemental maps (Fig. 1a and b). These distributions suggest a spherical particle, which is a common morphology for residues formed from the firing of DU munitions against hard targets, due to the low melting point of metallic uranium.23 Such particles have been observed previously in soils from this site, comprising primarily U3O8 and U4O7; a comprehensive account is given by Crean et al. and Sajih et al.23,24Meta-ankoleite, a uranyl phosphate hydrate (K(UO2)(PO4)·3H2O), and isostructural chernikovite ((H3O)(UO2)(PO4)·3H2O), are also present as widespread alteration products formed from partial weathering of DU particles in the soil.22 Mapping of uranium oxidation state provides information on U speciation in the sample. Areas of U(VI) correspond well to the distribution of meta-ankoleite/chernikovite in the sample, whereas the central region has a reduced composition which correlates well with the distribution of UFeO4. The oxidation state varies in the range 5.2–5.4 in this central domain, consistent with the presence of pentavalent U in UFeO4 as suggested by Bacmann et al. and evidenced by Guo et al.11,14 In Fig. 1b, Fe Kα emission was also observed, over a wide area, adjacent to the UFeO4 particle. μ-XRD analysis of this area produced only diffuse scatter, implying the presence of an Fe rich non-crystalline mineral phase.
U–Fe phases are thought to be produced by high temperature interactions (T ∼ 3000 °C (ref. 34)) which arise on impact of DU munitions with steels in armour plate. Laves phases such as UFe2 have been observed in DU residues,6 and UFeO4 can form as a minority high temperature oxidation product of this phase.35 In this particle however, the lack of other UFe2 oxidation products (such as UO2 or FeO35) suggests that UFeO4 may form as a primary species. The presence of a UFeO4 particle in these soils shows that this phase can persist in oxic, variably moist surface environment conditions, which may be expected to promote oxidation and dissolution of U(V) phases to U(VI) species.
Quantitative analysis of powder diffraction data was performed using a Le Bail intensity extraction method.36 A low number of randomly oriented crystallites in the particle was evident as ‘spots’ rather than full rings in the 2D diffraction pattern (Fig. 2). Although the angular position of reflections is unaffected, this limits a full structural analysis (e.g. by Rietveld refinement) as the intensity of reflections in the pattern are distorted. This has been previously noted as a problem in the refinement of μ-XRD data.37
The Le Bail method removes the link between the model structure and peak intensities, and allows unit cell parameters to be refined without a structural model, independent of preferred orientation effects. However for low symmetry systems this approach may incorrectly resolve closely spaced peaks, as intensities are not constrained by a structural model.38 To overcome this, the results of Le Bail fitting are recommended to be compared with results from fitting to a structural model, even if this is imperfect.38 In this study good agreement between Le-Bail refined unit cell parameters (Table 1) and a limited Rietveld analysis (data not shown) was observed.
Fraction (wt%) | a (Å) | b (Å) | c (Å) | Volume (Å3) | ||
---|---|---|---|---|---|---|
Phase 1 | ||||||
UFeO4 | Refined | 95.91(4) | 4.8930(5) | 11.9065(8) | 5.1086(5) | 297.62(5) |
UFeO4 | Bacmann et al.7 | — | 4.888 | 11.937 | 5.11 | 298.15 |
Read et al.8 | 4.8844(2) | 11.9328(5) | 5.1070(2) | 297.66(2) | ||
Guo et al.11 | 4.8858(1) | 11.9288(2) | 5.1072(1) | 297.65(1) | ||
Phase 2 | ||||||
Meta-ankoleite | Refined | 4.10(5) | 7.0265(6) | 7.0265(6) | 18.0275(4) | 890.06(14) |
Meta-ankoleite | Fitch et al.33 | — | 6.993 | 6.993 | 17.7839 | 869.87 |
Chernikovite | Ross39 | — | 7.020 | 7.020 | 18.086 | 891.29 |
The pattern was adequately described (χ2 = 6.48, Rwp = 13.7%, Rp = 6.43%) with contributions from UFeO4 as the majority phase (95.9 wt%) with a minority presence of a secondary phase (4.1 wt%) modelled initially as meta-ankoleite. The good agreement of the refined and published unit cell values for UFeO4 (ref. 7, 8 and 11) gives quantitative identification of this species in the particle, and allows correlation of our XAS data with the published structure.
Refined unit cell parameters (Table 1) for the secondary phase show good agreement with the structure of chernikovite (H3O)(UO2)(PO4)·3H2O,39 which is isostructural with meta-ankoleite. These minerals have layered uranyl and phosphate polyhedral chains, with interlayers of water and cations of different size, which allows discrimination based on the unit cell size. Uranyl-phosphate-hydrate phases have been identified in other particles from this sample site at the Eskmeals range, linked to corrosion of DU oxide particles over extended periods of time in a waste disposal pit for contaminated timbers.22 The co-location of minor amounts of chernikovite in this particle may suggest weathering of the UFeO4 phase. However, the majority of the remaining particle is still composed of UFeO4, and the particle size is consistent with primary unaltered uranium oxide particles observed at this site,22,24 indicating an extent of longer term environmental stability over at least 25 years of exposure to the surface environment.
Due to the structural similarity between UFeO4 and UCrO4, qualitative XRF spectroscopy was performed to confirm the identity of the primary U species. Fig. 3 shows that the particle is composed mainly of U and Fe, with only trace levels of Cr present. This result compares well with the refined unit cell parameters which are in good agreement with the presence of UFeO4 only. To distinguish between chernikovite and meta-ankoleite, energy dispersive XRF spectroscopy is not useful as interference with U M emissions (U Mβ = 3339.8 eV) prevents confirmation of the presence of K (K Kα = 3313.8 eV) in the sample, and secondary phase identification relies on refined unit cell parameters only.
Fig. 3 Qualitative XRF spectrum of the particle from Fig. 1 in which maximum counts for U Lα1 (4.8 × 105) and Fe Kα1 (5.2 × 104) compared to Cr Kα1 (6.3 × 102) indicate that the U ternary oxide phase is UFeO4 rather than UCrO4. The excitation energy was 17.500 keV. |
Although damped by self-absorption, near edge structure suggests a U chemical environment distinct from that observed in UO2 and UO3 (Fig. 4). In particular, the multiple scattering resonance at an energy 10–15 eV greater than the white line observed in the UO3 spectrum, related to multiple scattering of the linear uranyl U(V/VI) structural unit (OUO+/2+), was not observed in the sample spectrum.40 The strongest post-edge oscillation occurs at a similar energy (17230 eV) to that of the non-uranyl U(V) standard, and agrees well with other published XANES spectra of U(V) compounds and that recently published for UFeO4.11,16,21,35,41 The use of XANES spectroscopy provides further direct evidence for the presence of U(V) in UFeO4, supporting the recent XAS and XPS studies of Guo et al.,11 and earlier inferences of Bacmann et al.14
XAS mapping (Fig. 1c) provides a more rapid method than XANES analysis to determine the spatial variation in oxidation state. Good agreement between the oxidation state determined by XANES (+4.90 ± 0.15) and XAS redox mapping (particle average +5.20 ± 0.15) provides indication that U oxidation state throughout the particle is pentavalent. XAS mapping also reveals that the U(V) oxidation state is homogenous in the particle (Fig. 1c), and agrees well with the distribution of UFeO4 determined by XRD phase mapping (Fig. 1d). Due to the co-associated chernikovite phase, incorporating the uranyl species, XPS could not be applied to reliably infer the U oxidation state in the particle.
Fig. 5 shows the k2-weighted EXAFS spectra and fits for k- and R-space from the UFeO4 particle, with the fit detailed in Table 2. The intensity in R-space is consistent with the published structure of UFeO4, with an intense and broad second peak arising from a number of scatterers in a complex second shell. Although the published structure of UFeO4 indicates U in a distorted octahedral co-ordination, the R-space resolution offered by μ-EXAFS (ΔR = 0.262 Å) analysis shows this as a single intense peak at 1.55 Å (Fig. 5), corresponding to an average U–O distance of ∼2.15 Å with phase correction. This shell was fitted using backscattering phase and amplitude terms calculated for the middle path length (R0 = 2.155 Å), with the path degeneracy (N) fixed at 6 instead of 2. The EXAFS path length for this shell was refined to 2.148 ± 0.012 Å (Table 1), representing an average of the U–O distances in the distorted first shell geometry. This is agrees well with the mean crystallographic (Rc) U–O distance calculated from the published crystallographic structures of UFeO4 (Rc = 2.148 and 2.168 Å),8,10 and that from a recent EXAFS investigation (R = 2.148 Å).11
Fig. 5 Uranium LIII edge EXAFS spectra from a UFeO4 particle. Left – background subtracted k2-weighted EXAFS spectrum. Right – Fourier transform magnitude (k2 weighted). |
Shell | Path | N | R (Å) | σ 2 (Å2) | Global parameters | |
---|---|---|---|---|---|---|
a Co-ordination number increased from crystallographic value to account for averaging of multiple indistinguishable paths. b S 0 2 fixed to 0.95. c Average σ2 fit for all second shell paths. | ||||||
1 | O 2.1 | 6a | 2.148(14) | 0.0031(11) | ΔE0 (eV) | 2.1(1.3) |
S 0 2 | 0.95 | |||||
2 | Fe 1.1 | 1 | 3.274(16) | 0.0036(16)c | ||
2 | O 1.2 | 2 | 3.288(16) | 0.0036(16)c | G.O.F. | |
2 | O 2.3 | 2 | 3.667(18) | 0.0036(16)c | Red χ2 | 6.72 |
2 | Fe 1.3 | 6 | 3.735(19) | 0.0036(16)c | R (%) | 1.45 |
The second co-ordination shell in UFeO4 is apparent as a broad peak in the μ-EXAFS data in the region 2.5–3.7 Å. The crystal structure shows this is expected to comprise 2 distinct O subshells and 3 Fe subshells. However, the close spatial relation of these paths and the limited number of available independent data points (Nidp = 9.53) mean it is not possible to resolve individual EXAFS parameters (σ2, ΔR) for these paths. For the second shell paths in Table 2, changes in path length were described with a single scaling factor multiplied by the path length, and a single mean squared path length variation (σ2) was used. This two parameter model for the second shell allows a reasonable fit to the data and extraction of useful chemical information from the first shell, in particular the average U–O distance as discussed above. This value can be used to confirm the oxidation state of U in UFeO4 by bond valence sum analysis.
We also considered the possibility that the U environment in UFeO4 could be an average of U(V) as a result of plausible combinations of U(IV) and U(VI) environments. This involved modelling the EXAFS data using two U cores, initially configured as equal ratios of U(IV) and U(VI) in octahedral co-ordination to fit the first shell of the |FT k2χ(k)|. The UIVO6 environment was modelled with 6 × dU–O = 2.281 Å and σ2 = 0.003 Å2, based on the environment in UTi2O6.44 The UVIO6 environment was modelled as: non-uranyl U(VI), with 6 × dU–O = 2.07 Å and σ2 = 0.003 Å2; or uranyl U(VI) with 2 × dU–Oyl = 1.798 Å, 4 × dU–O = 2.275 Å and σ2 = 0.003 Å2 (using the mean distances for such environments determined from a comprehensive literature survey and analysis45). When the proportions of the environments and path lengths were refined, the models converged to mean path lengths of ∼2.13 Å, implying a single U environment. To develop further insight, we computed the k2χ(k) and |FT k2χ(k)| of plausible combinations of U(IV) and U(VI), using our initial models with FEFF 6 in the Artemis/IFEFFIT software package.27,29 We compared the component and resultant calculations with that for the single U(V) environment determined in Table 2. The results of this analysis show that plausible bounding combinations of U(IV) and U(VI), charge compensated by Fe(III) and/or Fe(II), are unable to accurately approximate a single U(V) environment (Fig. S3†). Thus we conclude that UFeO4 incorporates U(V) in octahedral co-ordination, rather than a combination of U(IV) and U(VI) charge compensated by Fe(III) and/or Fe(II).
Bond valence sum analysis may also be applied to bond distances calculated from the published crystal structures,8,10 which yield a bond valence sum of 5.0, which is in excellent agreement with the oxidation state of U determined by XANES and EXAFS for this particle. A corresponding Fe valence may also be calculated using the published crystal structures – as the oxidation state of uranium has been determined as U(V), bond valence parameters for Fe(III)–O bonding were used (R0 = 1.759 Å, B = 0.37),38 yielding an average Fe bond valence sum in UFeO4 of 2.83 for the structures of Bacmann et al. and Read et al.,8,10 in agreement with the analysis of 57Fe Mossbauer data by Guo et al.11 These analyses give further confirmation that the cation pair in UFeO4 is U(V)/Fe(III).
The oxidation state of uranium in UFeO4 was determined as U(V) by microfocus synchrotron chemical imaging, μ-XANES and μ-EXAFS spectroscopies. Unit cell parameters of UFeO4 were refined by Le Bail fitting of powder XRD data, revealing values consistent with the structure of UFeO4 determined by Bacmann et al. and Read et al.8,10 This structure was used as an input to calculate EXAFS path amplitudes and phase shifts, which were found to fit well to the data, and agree well with the results of the recent EXAFS study of Guo et al.11 Bond valence analysis of the EXAFS refined U–O bond and of the U and Fe sites in the original structure suggests a U(V)/Fe(III) couple, and confirms early studies of UFeO4 in which U(V) was inferred,12,14 and more recent U L3 XAS and XPS studies.11
This study demonstrates the utility of microbeam X-ray experiments to extract chemical information from challenging samples by a range of complementary analyses, which may be of interest in characterisation of secondary minerals, alteration products and other materials for which bulk samples are not available for conventional characterisation regimes. This approach is particularly suitable for radioactive and hot particles as it non-destructive, thereby preserving the limited sample for other complementary analyses and allowing safe containment of the material.
Footnote |
† Electronic supplementary information (ESI) available. See DOI: 10.1039/d0em00243g |
This journal is © The Royal Society of Chemistry 2020 |