I08-Scanning X-ray Microscopy beamline (SXM)
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Karin
Eusterhues
,
Juergen
Thieme
,
Sneha
Narvekar
,
Tohru
Araki
,
Majid
Kazemian
,
Burkhard
Kaulich
,
Tom
Regier
,
Jian
Wang
,
Johann
Lugmeier
,
Carmen
Höschen
,
Tim
Mansfeldt
,
Kai Uwe
Totsche
Diamond Proposal Number(s):
[18569]
Abstract: Sorption of organic molecules on mineral surfaces can occur through several binding mechanisms of varying strength. Here, we investigated the importance of inner-sphere P-O-Fe bonds in synthetic and natural mineral-organic associations. Natural organic matter such as water extracted soil organic matter (WESOM) and extracellular polymeric substances (EPS) from liquid bacterial cultures were adsorbed to goethite and examined by FTIR spectroscopy and P K-edge NEXAFS spectroscopy. Natural particles from a Bg soil horizon (Gleysol) were subjected to X-ray fluorescence (XRF) mapping, NanoSIMS imaging, and NEXAFS spectro-microscopy at the P K-edge. Inner-sphere P-O-Fe bonds were identified for both, adsorbed EPS extracts and adsorbed WESOMs. Characteristic infrared peaks for P-O-Fe stretching vibrations are present but cannot unambiguously be interpreted due to possible interferences with mono- and polysaccharides. For the Bg horizon, P was only found on Fe oxides, covering the entire surface at different concentrations, but not on clay minerals. Linear combination fitting of NEXAFS spectra indicates that this adsorbed P is mainly a mixture of orthophosphate and organic P compounds. By combining atomic force microscopy (AFM) images with STXM-generated C and Fe distribution maps, we show that the Fe oxide surfaces were fully coated with organic matter. In contrast, clay minerals revealed a much lower C signal. The C NEXAFS spectra taken on the Fe oxides had a substantial contribution of carboxylic C, aliphatic C, and O-alkyl C, which is a composition clearly different from pure adsorbed EPS or aromatic-rich lignin-derived compounds. Our data show that inner-sphere P-O-Fe bonds are important for the association of Fe oxides with soil organic matter. In the Bg horizon, carboxyl groups and orthophosphate compete with the organic P compounds for adsorption sites.
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Sep 2023
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I22-Small angle scattering & Diffraction
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Adelaide
Lerebours
,
Justyn
Regini
,
Roy A.
Quinlan
,
Toshihiro
Wada
,
Barbara
Pierscionek
,
Martin
Devonshire
,
Alexia A.
Kalligeraki
,
Alice
Uwineza
,
Laura
Young
,
John M.
Girkin
,
Phil
Warwick
,
Kurt
Smith
,
Masato
Hoshino
,
Kentaro
Uesugi
,
Naoto
Yagi
,
Nick
Terrill
,
Olga
Shebanova
,
Tim
Snow
,
Jim T.
Smith
Diamond Proposal Number(s):
[17075]
Open Access
Abstract: Recent studies apparently finding deleterious effects of radiation exposure on cataract formation in birds and voles living near Chernobyl represent a major challenge to current radiation protection regulations. This study conducted an integrated assessment of radiation exposure on cataractogenesis using the most advanced technologies available to assess the cataract status of lenses extracted from fish caught at both Chernobyl in Ukraine and Fukushima in Japan. It was hypothesised that these novel data would reveal positive correlations between radiation dose and early indicators of cataract formation.
The structure, function and optical properties of lenses were analysed from atomic to millimetre length scales. We measured the short-range order of the lens crystallin proteins using Small Angle X-Ray Scattering (SAXS) at both the SPring-8 and DIAMOND synchrotrons, the profile of the graded refractive index generated by these proteins, the epithelial cell density and organisation and finally the focal length of each lens.
The results showed no evidence of a difference between the focal length, the epithelial cell densities, the refractive indices, the interference functions and the short-range order of crystallin proteins (X-ray diffraction patterns) in lens from fish exposed to different radiation doses. It could be argued that animals in the natural environment which developed cataract would be more likely, for example, to suffer predation leading to survivor bias. But the cross-length scale study presented here, by evaluating small scale molecular and cellular changes in the lens (pre-cataract formation) significantly mitigates against this issue.
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Aug 2023
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B18-Core EXAFS
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Connaugh M.
Fallon
,
William R.
Bower
,
Brian A.
Powell
,
Francis R.
Livens
,
Ian C.
Lyon
,
Alana E.
Mcnulty
,
Kathryn
Peruski
,
J. Frederick W.
Mosselmans
,
Daniel I.
Kaplan
,
Daniel
Grolimund
,
Peter
Warnicke
,
Dario
Ferreira-Sanchez
,
Marja Siitari
Kauppi
,
Gianni F.
Vettese
,
Samuel
Shaw
,
Katherine
Morris
,
Gareth T. W.
Law
Diamond Proposal Number(s):
[16611, 16939, 17243]
Open Access
Abstract: Uranium dioxide (UO2) and metaschoepite (UO3•nH2O) particles have been identified as contaminants at nuclear sites. Understanding their behavior and impact is crucial for safe management of radioactively contaminated land and to fully understand U biogeochemistry. The Savannah River Site (SRS) (South Carolina, USA), is one such contaminated site, following historical releases of U-containing wastes to the vadose zone. Here, we present an insight into the behavior of these two particle types under dynamic conditions representative of the SRS, using field lysimeters (15 cm D x 72 cm L). Discrete horizons containing the different particle types were placed at two depths in each lysimeter (25 cm and 50 cm) and exposed to ambient rainfall for 1 year, with an aim of understanding the impact of dynamic, shallow subsurface conditions on U particle behavior and U migration. The dissolution and migration of U from the particle sources and the speciation of U throughout the lysimeters was assessed after 1 year using a combination of sediment digests, sequential extractions, and bulk and μ-focus X-ray spectroscopy. In the UO2 lysimeter, oxidative dissolution of UO2 and subsequent migration of U was observed over 1–2 cm in the direction of waterflow and against it. Sequential extractions of the UO2 sources suggest they were significantly altered over 1 year. The metaschoepite particles also showed significant dissolution with marginally enhanced U migration (several cm) from the sources. However, in both particle systems the released U was quantitively retained in sediment as a range of different U(IV) and U(VI) phases, and no detectable U was measured in the lysimeter effluent. The study provides a useful insight into U particle behavior in representative, real-world conditions relevant to the SRS, and highlights limited U migration from particle sources due to secondary reactions with vadose zone sediments over 1 year.
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Dec 2022
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I20-Scanning-X-ray spectroscopy (XAS/XES)
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Diamond Proposal Number(s):
[21441]
Open Access
Abstract: Selenium (Se) is a toxic contaminant with multiple anthropogenic sources, including 79Se from nuclear fission. Se mobility in the geosphere is generally governed by its oxidation state, therefore understanding Se speciation under variable redox conditions is important for the safe management of Se contaminated sites. Here, we investigate Se behavior in sediment groundwater column systems. Experiments were conducted with environmentally relevant Se concentrations, using a range of groundwater compositions, and the impact of electron-donor (i.e., biostimulation) and groundwater sulfate addition was examined over a period of 170 days. X-Ray Absorption Spectroscopy and standard geochemical techniques were used to track changes in sediment associated Se concentration and speciation. Electron-donor amended systems with and without added sulfate retained up to 90% of added Se(VI)(aq), with sediment associated Se speciation dominated by trigonal Se(0) and possibly trace Se(-II); no Se colloid formation was observed. The remobilization potential of the sediment associated Se species was then tested in reoxidation and seawater intrusion perturbation experiments. In all treatments, sediment associated Se (i.e., trigonal Se(0)) was largely resistant to remobilization over the timescales of the experiments (170 days). However, in the perturbation experiments, less Se was remobilized from sulfidic sediments, suggesting that previous sulfate-reducing conditions may buffer Se against remobilization and migration.
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Apr 2022
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B18-Core EXAFS
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Diamond Proposal Number(s):
[13890]
Open Access
Abstract: Major uranium (U) deposits worldwide are exploited by acid leaching, known as ‘in-situ recovery’ (ISR). ISR involves the injection of an acid fluid into ore-bearing aquifers and the pumping of the resulting metal-containing solution through cation exchange columns for the recovery of dissolved U. Rehabilitation of ISR-impacted aquifers could be achieved through natural attenuation, or via biostimulation of autochthonous heterotrophic microorganisms due to the associated acid neutralization and trace metal immobilization.
In this study, we analyzed the capacity of pristine aquifer sediments impacted by diluted ISR fluids to buffer pH and immobilize U. The experimental setup consisted of glass columns, filled with sediment from a U ore-bearing aquifer, through which diluted ISR fluids were flowed continuously. The ISR solution was obtained from ISR mining operations at the Muyunkum and Tortkuduk deposits in Kazakhstan. Following this initial phase, columns were biostimulated with a mix of molasses, yeast extract and glycerol to stimulate the growth of autochthonous heterotrophic communities. Experimental results showed that this amendment efficiently promoted the activity of acid-tolerant bacterial guilds, with pH values rising from 4.8 to 6.5–7.0 at the outlet of the stimulated columns. The reduction of sulfate, nitrate, and metals as well as dissimilatory nitrate reduction to ammonia induced the rise in pH values, in agreement with geochemical modelling results. Biostimulation efficiently promoted the complete immobilization of U, with the accumulation of up to 3343 ppm in the first few centimeters of the columns. Synchrotron analysis and SEM-EDS revealed that up to 60% of the injected hexavalent U was immobilized as tetravalent non-crystalline U onto bacterial cell surfaces. 16S rDNA amplicon analysis and qPCR data suggested a predominant role played for members of the Phylum Firmicutes (from the genera Clostridium, Pelosinus and Desulfosporosinus) in biological U reduction and immobilization.
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Jan 2022
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I14-Hard X-ray Nanoprobe
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Kazuya
Morooka
,
Eitaro
Kurihara
,
Masato
Takehara
,
Ryu
Takami
,
Kazuki
Fueda
,
Kenji
Horie
,
Mami
Takehara
,
Shinya
Yamasaki
,
Toshihiko
Ohnuki
,
Bernd
Grambow
,
Gareth T. W.
Law
,
Joyce W. I.
Ang
,
William R.
Bower
,
Julia
Parker
,
Rodney
Ewings
,
Satoshi
Utsunomiya
Diamond Proposal Number(s):
[21246]
Abstract: A contaminated zone elongated toward Futaba Town, north-northwest of the Fukushima Daiichi Nuclear Power Plant (FDNPP), contains highly radioactive particles released from reactor Unit 1. There are uncertainties associated with the physio-chemical properties and environmental impacts of these particles. In this study, 31 radioactive particles were isolated from surface soils collected 3.9 km north-northwest of the FDNPP. Two of these particles have the highest particle-associated 134+137Cs activity ever reported for Fukushima (6.1 × 105 and 2.5 × 106 Bq per particle after decay-correction to March, 2011). The new, highly-radioactive particle labeled FTB1 is an aggregate of flaky silicate nanoparticles with an amorphous structure containing ~0.8 wt% Cs, occasionally associated with SiO2 and TiO2 inclusions. FTB1 likely originates from the reactor building, which was damaged by a H2 explosion, after adsorbing volatilized Cs. The 134+137Cs activity in the other highly radioactive particle labeled FTB26 exceeded 106 Bq. FTB26 has a glassy carbon core and a surface that is embedded with numerous micro-particles: Pb–Sn alloy, fibrous Al-silicate, Ca-carbonate or hydroxide, and quartz. The isotopic signatures of the micro-particles indicate neutron capture by B, Cs volatilization, and adsorption of natural Ba. The composition of the micro-particles on FTB26 reflects the composition of airborne particles at the moment of the H2 explosion. Owing to their large size, the health effects of the highly radioactive particles are likely limited to external radiation during static contact with skin; the highly radioactive particles are thus expected to have negligible health impacts for humans. By investigating the mobility of the highly radioactive particles, we can better understand how the radiation dose transfers through environments impacted by Unit 1. The highly radioactive particles also provide insights into the atmospheric conditions at the time of the Unit 1 explosion and the physio-chemical phenomena that occurred during reactor meltdown.
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Feb 2021
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B18-Core EXAFS
I18-Microfocus Spectroscopy
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Eitaro
Kurihara
,
Masato
Takehara
,
Mizuki
Suetake
,
Ryohei
Ikehara
,
Tatsuki
Komiya
,
Kazuya
Morooka
,
Ryu
Takami
,
Shinya
Yamasaki
,
Toshihiko
Ohnuki
,
Kenji
Horie
,
Mami
Takehara
,
Gareth T. W.
Law
,
William
Bower
,
J. Frederick W.
Mosselmans
,
Peter
Warnicke
,
Bernd
Grambow
,
Rodney C.
Ewing
,
Satoshi
Utsunomiya
Diamond Proposal Number(s):
[21211]
Abstract: Traces of Pu have been detected in material released from the Fukushima Daiichi Nuclear Power Plant (FDNPP) in March of 2011; however, to date the physical and chemical form of the Pu have remained unknown. Here we report the discovery of particulate Pu associated with cesium-rich microparticles (CsMPs) that formed in and were released from the reactors during the FDNPP meltdowns. The Cs-pollucite-based CsMP contained discrete U(IV)O2 nanoparticles, <~10 nm, one of which is enriched in Pu adjacent to fragments of Zr-cladding. The isotope ratios, 235U/238U, 240Pu/239Pu, and 242Pu/239Pu, of the CsMPs were determined to be ~0.0193, ~0.347, and ~0.065, respectively, which are consistent with the calculated isotopic ratios of irradiated-fuel fragments. Thus, considering the regional distribution of CsMPs, the long-distance dispersion of Pu from FNDPP is attributed to the transport by CsMPs that have incorporated nanoscale fuel fragments prior to their dispersion up to 230 km away from the Fukushima Daiichi reactor site.
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Nov 2020
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B18-Core EXAFS
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Diamond Proposal Number(s):
[18561]
Abstract: Pine biomass (Pine), pine gasification biochar (PG) and pine biomass loaded with TiO2 (Pine/TiO2) were used as sorbent materials to remove Cr(III) or Cr(VI) ions from aqueous solutions. Our results showed that Pine/TiO2 had an improved adsorption capacity respect to Pine being the adsorption capacity for Cr(VI), 12.8 mg/g, much larger than for Cr(III), 1.23 mg/g. On the other hand, PG showed much higher adsorption for Cr(III), 12.4 mg/g, than Pine/TiO2, and negligible adsorption for Cr(VI). To understand this species-dependent adsorption behavior, the adsorption mechanisms, sorbents morphology and functional sites were characterized using a multi-technique approach. The chemical state and local coordination structure of the adsorbed Cr species was studied by X-ray absorption spectroscopy (XAS). Our results show that the adsorption of Cr(III) occurred mainly through cation exchange with mineral elements in PG biochar, whereas the Cr(III) adsorption by functional groups (carboxyl and hydroxyl groups) dominate in the biomass sorbent. The enhancement of Cr(VI) adsorption in Pine/TiO2 can be explained by the presence of TiOH2+ groups present in the surface of theTiO2 microparticles. X-ray absorption spectroscopy (XAS) results reveal that Cr(VI) reduces to Cr(III) after being adsorbed by the sorbent materials.
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Nov 2020
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I18-Microfocus Spectroscopy
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Diamond Proposal Number(s):
[12696]
Open Access
Abstract: Vanadium is a toxic metal present in alkaline leachates produced during the weathering of steel slags. Slag leaching can therefore have deleterious effects on local watercourses due to metal toxicity, the effects of the high pH (9–12.5) and rapid carbonation (leading to smothering of benthic communities). We studied the fate and behaviour of V in slag leachate both through field observations of a heavily affected stream (Howden Burn, Consett UK) and in controlled laboratory experiments where slag leachates were neutralised by CO2 ingassing from air. V was found to be removed from leachates downstream from the Howden Burn source contemporaneously with a fall in pH, Ca, Al and Fe concentrations. In the neutralisation experiments pH reduced from 12 → 8, and limited quantities of V were incorporated into precipitated CaCO3. The presence of kaolinite clay (i.e. SiOH and AlOH surfaces) during neutralisation experiments had no measureable effect on V uptake in the alkaline to circumneutral pH range. XANES analysis showed that V was present in precipitates recovered from experiments as adsorbed or incorporated V(V) indicating its likely presence in leachates as the vanadate oxyanion (HVO42−). Nano-scale particles of 2-line ferrihydrite also formed in the neutralised leachates potentially providing an additional sorption surface for V uptake. Indeed, removal of V from leachates was significantly enhanced by the addition of goethite (i.e. FeOOH surfaces) to experiments. EXAFS analysis of recovered goethite samples showed HVO42− was adsorbed by the formation of strong inner-sphere complexes, facilitating V removal from solution at pH < 10. Results show that carbonate formation leads to V removal from leachates during leachate neutralisation, and the presence of both naturally occurring and neoformed Fe (oxy)hydroxides provide a potent sink for V in slag leachates, preventing the spread of V in the environment.
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Dec 2018
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I20-Scanning-X-ray spectroscopy (XAS/XES)
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Open Access
Abstract: Cr(VI) is an important contaminant found at sites where chromium ore processing residue (COPR) is deposited. No low cost treatment exists for Cr(VI) leaching from such sites. This study investigated the mechanism of interaction of alkaline Cr(VI)-containing leachate with an Fe(II)-containing organic matter rich soil beneath the waste. The soil currently contains 0.8% Cr, shown to be present as Cr(III)(OH)3 in EXAFS analysis. Lab tests confirmed that the reaction of Cr(VI) in site leachate with Fe(II) present in the soil was stoichiometrically correct for a reductive mechanism of Cr accumulation. However, the amount of Fe(II) present in the soil was insufficient to maintain long term Cr(VI) reduction at historic infiltration rates. The soil contains a population of bacteria dominated by a Mangroviflexus-like species, that is closely related to known fermentative bacteria, and a community capable of sustaining Fe(III) reduction in alkaline culture. It is therefore likely that in situ fermentative metabolism supported by organic matter in the soil produces more labile organic substrates (lactate was detected) that support microbial Fe(III) reduction. It is therefore suggested that addition of solid phase organic matter to soils adjacent to COPR may reduce the long term spread of Cr(VI) in the environment.
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Jan 2016
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