Hyperalkaline pH Research Articles

Characterisation of high burnup spent mixed oxide fuel after leaching at hyperalkaline pH in a reducing environment

Microstructural investigations of a Zircaloy-4 clad mixed oxide fuel rod segment with a burnup of 50.3 GWd/tHM after exposure to a synthetic young cementitious water at a hyperalkaline pH of 13.7(2) under reducing atmosphere for about 3.5 years were conducted. A deposit on surfaces exposed to the leachate was observed and attempts were made to identify its composition. Initial scanning electron microscopy/energy dispersive X-ray spectroscopy results indicate that it contains several leachate constituents, as well as Zr and Ti. The presence of Ti indicates corrosion of the autoclave liner during the leaching experiment. Surfaces which were not directly exposed to the leachate revealed additional features, such as distinct ε-particles. Remarkably, these could not be identified on surfaces exposed to the leachate, which may indicate that dissolution of the ε-particles took place as well.Graphical abstract

Modelling the release of Mo, Tc, Ru and Rh from high burnup spent nuclear fuel at alkaline and hyperalkaline pH

The present work shows experimental data on the release of some radionuclides that are forming the so-called ε particles in the spent nuclear fuel (SNF): Mo, Tc, Ru and Rh. The leaching experiments were carried out with a 60 GWd·t−1 burnup SNF at two different pH values, 8.4 and 13.2, and under oxidizing conditions. The modelling of the data showed that the higher release of Mo, Tc, Ru and Rh at pH 13.2 could be due to the higher dissolution rate of the ε-particles.Graphical abstract

Intact polar lipidome and membrane adaptations of microbial communities inhabiting serpentinite-hosted fluids.

The generation of hydrogen and reduced carbon compounds during serpentinization provides sustained energy for microorganisms on Earth, and possibly on other extraterrestrial bodies (e.g., Mars, icy satellites). However, the geochemical conditions that arise from water-rock reaction also challenge the known limits of microbial physiology, such as hyperalkaline pH, limited electron acceptors and inorganic carbon. Because cell membranes act as a primary barrier between a cell and its environment, lipids are a vital component in microbial acclimation to challenging physicochemical conditions. To probe the diversity of cell membrane lipids produced in serpentinizing settings and identify membrane adaptations to this environment, we conducted the first comprehensive intact polar lipid (IPL) biomarker survey of microbial communities inhabiting the subsurface at a terrestrial site of serpentinization. We used an expansive, custom environmental lipid database that expands the application of targeted and untargeted lipodomics in the study of microbial and biogeochemical processes. IPLs extracted from serpentinite-hosted fluid communities were comprised of >90% isoprenoidal and non-isoprenoidal diether glycolipids likely produced by archaeal methanogens and sulfate-reducing bacteria. Phospholipids only constituted ~1% of the intact polar lipidome. In addition to abundant diether glycolipids, betaine and trimethylated-ornithine aminolipids and glycosphingolipids were also detected, indicating pervasive membrane modifications in response to phosphate limitation. The carbon oxidation state of IPL backbones was positively correlated with the reduction potential of fluids, which may signify an energy conservation strategy for lipid synthesis. Together, these data suggest microorganisms inhabiting serpentinites possess a unique combination of membrane adaptations that allow for their survival in polyextreme environments. The persistence of IPLs in fluids beyond the presence of their source organisms, as indicated by 16S rRNA genes and transcripts, is promising for the detection of extinct life in serpentinizing settings through lipid biomarker signatures. These data contribute new insights into the complexity of lipid structures generated in actively serpentinizing environments and provide valuable context to aid in the reconstruction of past microbial activity from fossil lipid records of terrestrial serpentinites and the search for biosignatures elsewhere in our solar system.

Molybdenum release from high burnup spent nuclear fuel at alkaline and hyperalkaline pH

This work presents experimental data and modelling of the release of Mo from high-burnup spent nuclear fuel (63 MWd/kgU) at two different pH values, 8.4 and 13.2 in air. The release of Mo from SF to the solution is around two orders of magnitude higher at pH = 13.2 than at pH = 8.4. The high Mo release at high pH would indicate that Mo would not be congruently released with uranium and would have an important contribution to the Instant Release Fraction, with a value of 5.3%.Parallel experiments with pure non irradiated Mo(s) and XPS determinations indicated that the faster dissolution at pH = 13.2 could be the consequence of the higher releases from metallic Mo in the fuel through a surface complexation mechanism promoted by the OH− and the oxidation of the metal to Mo(VI) via the formation of intermediate Mo(IV) and Mo(V) species.

Metabolic challenges and key players in serpentinite-hosted microbial ecosystems.

Serpentinite-hosted systems are amongst the most challenging environments for life on Earth. Serpentinization, a geochemical alteration of exposed ultramafic rock, produces hydrothermal fluids enriched in abiotically derived hydrogen (H2), methane (CH4), and small organic molecules. The hyperalkaline pH of these fluids poses a great challenge for metabolic energy and nutrient acquisition, curbing the cellular membrane potential and limiting electron acceptor, carbon, and phosphorous availability. Nevertheless, serpentinization supports the growth of diverse microbial communities whose metabolic make-up might shed light on the beginning of life on Earth and potentially elsewhere. Here, we outline current hypotheses on metabolic energy production, carbon fixation, and nutrient acquisition in serpentinizing environments. A taxonomic survey is performed for each important metabolic function, highlighting potential key players such as H2 and CH4 cycling Serpentinimonas, Hydrogenophaga, Methanobacteriales, Methanosarcinales, and novel candidate phyla. Methodological biases of the available data and future approaches are discussed.

Metapangenomic investigation provides insight into niche differentiation of methanogenic populations from the subsurface serpentinizing environment, Samail Ophiolite, Oman.

Serpentinization reactions produce highly reduced waters that have hyperalkaline pH and that can have high concentrations of H2 and CH4. Putatively autotrophic methanogenic archaea have been identified in the subsurface waters of the Samail Ophiolite, Sultanate of Oman, though the strategies to overcome hyperalkaline pH and dissolved inorganic carbon limitation remain to be fully understood. Here, we recovered metagenome assembled genomes (MAGs) and applied a metapangenomic approach to three different Methanobacterium populations to assess habitat-specific functional gene distribution. A Type I population was identified in the fluids with neutral pH, while a Type II and "Mixed" population were identified in the most hyperalkaline fluids (pH 11.63). The core genome of all Methanobacterium populations highlighted potential DNA scavenging techniques to overcome phosphate or nitrogen limitation induced by environmental conditions. With particular emphasis on the Mixed and Type II population found in the most hyperalkaline fluids, the accessory genomes unique to each population reflected adaptation mechanisms suggesting lifestyles that minimize niche overlap. In addition to previously reported metabolic capability to utilize formate as an electron donor and generate intracellular CO2, the Type II population possessed genes relevant to defense against antimicrobials and assimilating potential osmoprotectants to provide cellular stability. The accessory genome of the Mixed population was enriched in genes for multiple glycosyltransferases suggesting reduced energetic costs by adhering to mineral surfaces or to other microorganisms, and fostering a non-motile lifestyle. These results highlight the niche differentiation of distinct Methanobacterium populations to circumvent the challenges of serpentinization impacted fluids through coexistence strategies, supporting our ability to understand controls on methanogenic lifestyles and adaptations within the serpentinizing subsurface fluids of the Samail Ophiolite.

Parapatric speciation of Meiothermus in serpentinite-hosted aquifers in Oman.

The factors that control the distribution and evolution of microbial life in subsurface environments remain enigmatic due to challenges associated with sampling fluids from discrete depth intervals via boreholes while avoiding mixing of fluids. Here, using an inflatable packer system, fracture waters were isolated and collected from three discrete depth intervals spanning >130 m in a borehole intersecting an ultramafic rock formation undergoing serpentinization in the Samail Ophiolite, Sultanate of Oman. Near surface aquifer waters were moderately reducing and had alkaline pH while deeper aquifer waters were reduced and had hyperalkaline pH, indicating extensive influence by serpentinization. Metagenomic sequencing and analysis of DNA from filtered biomass collected from discrete depth intervals revealed an abundance of aerobes in near surface waters and a greater proportion of anaerobes at depth. Yet the abundance of the putatively obligate aerobe, Meiothermus, increased with depth, providing an opportunity to evaluate the influence of chemical and spatial variation on its distribution and speciation. Two clades of Meiothermus metagenome assembled genomes (MAGs) were identified that correspond to surface and deep populations termed Types I (S) and II (D), respectively; both clades comprised an apparently Oman-specific lineage indicating a common ancestor. Type II (D) clade MAGs encoded fewer genes and were undergoing slower genome replication as inferred from read mapping. Further, single nucleotide variants (SNVs) and mobile genetic elements identified among MAGs revealed detectable, albeit limited, evidence for gene flow/recombination between spatially segregated Type I (S) and Type II (D) populations. Together, these observations indicate that chemical variation generated by serpentinization, combined with physical barriers that reduce/limit dispersal and gene flow, allowed for the parapatric speciation of Meiothermus in the Samail Ophiolite or a geologic precursor. Further, Meiothermus genomic data suggest that deep and shallow aquifer fluids in the Samail Ophiolite may mix over shorter time scales than has been previously estimated from geochemical data.

Oxidative dissolution mechanism of both undoped and Gd2O3-doped UO2(s) at alkaline to hyperalkaline pH.

The dissolution rates of unirradiated UO2 and unirradiated UO2 doped with Gd2O3 were determined as a function of pH using flow-through experiments in the presence of O2(g) and bicarbonate. The dissolution rate of non-doped UO2 was very low under hyperalkaline conditions (pH 12-13) whereas it increased drastically as the pH decreased to 9. The dissolution of non-doped UO2 in the pH range of 9-13 was consistent with the oxidative dissolution mechanism already described for UO2 dissolution in the presence of bicarbonate and oxygen. XPS analysis performed on the solid after dissolution experiments at pH 10 and 13 supported the bicarbonate effect to complex UO22+ and accelerate dissolution. Moreover, UO2 doped with Gd2O3 (5 wt% and 10 wt%) showed dissolution rates as low as non-doped UO2 under hyperalkaline conditions, which were maintained throughout the pH range studied (9-13). No substantial differences in the dissolution rates between these two doping levels were found. XPS analysis evidenced a similar surface composition both at pH 10 and 13, with U(V) being the dominant oxidation state. The low dissolution rates were assumed to be a consequence of the gadolinium capacity to retard the oxidation of U(V) to U(VI). The slight increase in dissolution rates observed in the hyperalkaline region was attributed to a shift in the oxidative dissolution mechanism, in which the presence of OH- promotes the formation of soluble uranyl hydroxo complexes.

Coordination motifs of binary neodymium(III) D-gluconate, D-galactonate and L-gulonate complexes and the transition from inner- to outer-sphere coordination in neutral to strongly alkaline medium

The structural aspects of the complexation of Nd(III) in aqueous solutions with D-gluconate, D-galactonate and L-gulonate in the neutral to hyperalkaline pH range have been studied by using 1H and 13C NMR, CD and Raman spectroscopies. Beside the identification of the binding sites, an attempt was made to reveal whether the structure of the complexes depends on the type of the ligand. It was concluded that the carboxylate group of each ligand has an essential role in the coordination to Nd(III). In solutions of pH > 5, other hydroxyl or alkoxide groups are also coordinated. Based on the NMR spectra, the coordination of several C-OH groups can be inferred, and CD measurements strongly suggest that beside the carboxylate, the C4-OH group takes part in the metal ion coordination in the Gluc– and Gal– complexes. On the basis of our observations from all the three spectroscopic methods, Nd(OH)3 units covered by the polyhydroxy carboxylate is the most appropriate model for describing the systems at pH > 12.

Building the bridge between U(VI) and Ca-bentonite – Influence of concentration, ionic strength, pH, clay composition and competing ions

In the context of a high-level nuclear waste disposal, the retention of U(VI) on non-pre-treated Ca-bentonite as potential technical barrier is studied. The objective of this study is to reveal the retention behaviour of U(VI) under extreme geochemical conditions, such as hyperalkaline pH range as well as high salinity at the same time, and taking into account other relevant parameters. This should lead to a better understanding of necessary safety precautions for avoiding a release of U(VI) in the environment. Batch experiments were conducted to determine the influence of the initial U(VI) concentration, salinity, pH value, clay composition and the presence of other elements (Ca(II), I−, Cs(I), Eu(III)). After the sorption experiments, the remaining U(VI) concentration in solution was determined via mass spectrometry with inductively coupled plasma. U(VI) can be immobilised from 10% to 100% under all investigated conditions. Precipitation plays a role in the U(VI) retention but only at higher concentrations (≥10−5 mol L−1). The retention is reversible especially with decreasing pH (<10.5) as the aquo complex Ca2UO2(CO3)3(aq) is formed. Ca(II) strongly enhances the U(VI) adsorption onto Ca-bentonite in the hyperalkaline pH range, probably due to the formation of Ca(II)-bridges. The best retention could be observed on natural bentonite compared to pure montmorillonite and altered bentonite. From a waste cocktail containing important elements of the repository inventory (Cs(I), Eu(III), U(VI) and iodide), only Eu(III) as homologous element to trivalent actinoids competes with U(VI) for binding sites, especially at low metal concentrations, but also facilitates the precipitation at higher concentrations.

Dissolution Kinetics of International Simple Glass and Formation of Secondary Phases at Very High Surface Area to Solution Ratio in Young Cement Water.

Static dissolution experiments were carried out with the reference International Simple Glass under hyperalkaline pH at 70 °C and very high SA/V ratio. Three aspects of glass dissolution behavior were investigated, (1) the rate drop regime and the residual rate (stage II), (2) the formation of secondary phases including thermodynamic aspects, and (3) the microstructure of the interface of altered glass and secondary phases. A very low residual rate of 6 × 10−6 g/m2d was determined based on boron release, which was several orders of magnitude lower than the initial rate established between the start of the experiments and the first sampling on day 59. The presence of a porous layer with a thickness varying between 80 nm and 250 nm and a pore size between 10 nm and 50 nm was observed. CSH phases with a low Ca/Si ratio of 0.3–0.4 and zeolites were also visible at the surface of the altered glass grains, but no glass alteration resumption occurred, probably due to an important pH decrease already at day 59. Thermodynamic calculations assuming congruent glass dissolution and precipitation of the dissolved aqueous species confirmed the precipitation of CSH phases and zeolites.

Molecular Evidence for an Active Microbial Methane Cycle in Subsurface Serpentinite-Hosted Groundwaters in the Samail Ophiolite, Oman.

Serpentinization can generate highly reduced fluids replete with hydrogen (H2) and methane (CH4), potent reductants capable of driving microbial methanogenesis and methanotrophy, respectively. However, CH4 in serpentinized waters is thought to be primarily abiogenic, raising key questions about the relative importance of methanogens and methanotrophs in the production and consumption of CH4 in these systems. Herein, we apply molecular approaches to examine the functional capability and activity of microbial CH4 cycling in serpentinization-impacted subsurface waters intersecting multiple rock and water types within the Samail Ophiolite of Oman. Abundant 16S rRNA genes and transcripts affiliated with the methanogenic genus Methanobacterium were recovered from the most alkaline (pH, >10), H2- and CH4-rich subsurface waters. Additionally, 16S rRNA genes and transcripts associated with the aerobic methanotrophic genus Methylococcus were detected in wells that spanned varied fluid geochemistry. Metagenomic sequencing yielded genes encoding homologs of proteins involved in the hydrogenotrophic pathway of microbial CH4 production and in microbial CH4 oxidation. Transcripts of several key genes encoding methanogenesis/methanotrophy enzymes were identified, predominantly in communities from the most hyperalkaline waters. These results indicate active methanogenic and methanotrophic populations in waters with hyperalkaline pH in the Samail Ophiolite, thereby supporting a role for biological CH4 cycling in aquifers that undergo low-temperature serpentinization.IMPORTANCE Serpentinization of ultramafic rock can generate conditions favorable for microbial methane (CH4) cycling, including the abiotic production of hydrogen (H2) and possibly CH4 Systems of low-temperature serpentinization are geobiological targets due to their potential to harbor microbial life and ubiquity throughout Earth's history. Biomass in fracture waters collected from the Samail Ophiolite of Oman, a system undergoing modern serpentinization, yielded DNA and RNA signatures indicative of active microbial methanogenesis and methanotrophy. Intriguingly, transcripts for proteins involved in methanogenesis were most abundant in the most highly reacted waters that have hyperalkaline pH and elevated concentrations of H2 and CH4 These findings suggest active biological methane cycling in serpentinite-hosted aquifers, even under extreme conditions of high pH and carbon limitation. These observations underscore the potential for microbial activity to influence the isotopic composition of CH4 in these systems, which is information that could help in identifying biosignatures of microbial activity on other planets.

Change in Arsenic Leaching from Silty Soil by Adding Slag Cement

Cementitious materials are commonly used to reinforce the bearing capacity of silty soils. However, there is very little data about how changes in arsenic (As) leaching from silty soils caused by the addition of cementitious materials. Therefore, batch leaching tests were conducted using As-bearing silty soil under different pH conditions. The pH was adjusted by changing the amount of slag cement added or the concentration of sodium hydroxide. This allows us to evaluate the effects of cement on As leaching. In addition, two different additives were applied to reduce As migration. The results show that high concentration of calcium ion (Ca2+) in leachates of soil-cement mixture has a significant effect in reducing the mobility of As even under hyperalkaline pH conditions. Arsenic immobilized by Ca2+ was observed in two patterns. The first mechanism was the help of Ca2+ to reduce the negative electrical potential on the surface of (hydr)oxide minerals under high pH conditions, thereby reducing the mobility of As by adsorption and coagulation of fresh precipitates of Fe and Al hydroxides. The second was the precipitation of calcium carbonate. This precipitate either directly adsorb/co-precipitate As or lower the concentration of strong competing ion, silica, both of which reduced the As mobility. When Ca- or Mg-based additive was added to the silty soil-cement mixture, As concentration in the leachate decreased. These findings are useful in developing sustainable soil-cement reinforcement techniques to avoid contamination.

The Bioreduction of Selenite under Anaerobic and Alkaline Conditions Analogous to Those Expected for a Deep Geological Repository System.

The environmental conditions for the planned geological disposal of radioactive waste —including hyper-alkaline pH, radiation or anoxia—are expected to be extremely harsh for microbial activity. However, it is thought that microbial communities will develop in these repositories, and this would have implications for geodisposal integrity and the control of radionuclide migration through the surrounding environment. Nuclear waste contains radioactive isotopes of selenium (Se) such as 79Se, which has been identified as one of the main radionuclides in a geodisposal system. Here, we use the bacterial species Stenotrophomonas bentonitica, isolated from bentonites serving as an artificial barrier reference material in repositories, to study the reduction of selenite (SeIV) under simulated geodisposal conditions. This bacterium is able to reduce toxic SeIV anaerobically from a neutral to alkaline initial pH (up to pH 10), thereby producing elemental selenium (Se0) nanospheres and nanowires. A transformation process from amorphous Se (a-Se) nanospheres to trigonal Se (t-Se) nanowires, through the formation of monoclinic Se (m-Se) aggregates as an intermediate step, is proposed. The lesser solubility of Se0 and t-Se makes S. bentonitica a potential candidate to positively influence the security of a geodisposal system, most probably with lower efficiency rates than those obtained aerobically.

Thermodynamic model of Ni(II) solubility, hydrolysis and complex formation with ISA

AbstractThe solubility of β–Ni(OH)2(cr) was investigated atT=(22±2)°C in the absence and presence of α-isosaccharinic acid (ISA), the main degradation product of cellulose under alkaline pH conditions. Batch solubility experiments were performed from undersaturation conditions under inert gas (Ar) atmosphere. Solubility experiments in the absence of ISA were conducted in 0.5 and 3.0 M NaCl–NaOH solutions at 7.5≤ pHm≤13 (with pHm=–log10[H+]). XRD analyses of selected solid phases collected after completing the solubility experiments (≈300 days) confirmed that β–Ni(OH)2(cr) remains as solid phase controlling the solubility of Ni(II) in all investigated conditions. Based on the slope analysis (log10[Ni] vs. pHm) of the solubility data and solid phase characterization, the equilibrium reactions β–Ni(OH)2(cr)+2 H+⇔Ni2++2 H2O(l) and β–Ni(OH)2(cr)⇔Ni(OH)2(aq) were identified as controlling the solubility of Ni(II) within the investigated pHmregion. The conditional equilibrium constants determined from the solubility experiments at different ionic strengths were evaluated with the specific ion interaction theory (SIT). In contrast to the current thermodynamic selection in the NEA–TDB, solubility data collected in the present work does not support the formation of the anionic hydrolysis species Ni(OH)3−up to pHm≤13.0. Solubility experiments in the presence of ISA were conducted in 0.5 M NaCl–NaOH–NaISA solutions with 0.01 M≤[NaISA] ≤0.2 M and 9≤ pHm≤13. XRD analyses confirmed that β–Ni(OH)2(cr) is also the solid phase controlling the solubility of Ni(II) in the presence of ISA. Solubility data of all investigated systems can be properly explained with chemical and thermodynamic models including the formation of the complexes NiOHISA(aq), Ni(OH)2ISA−and Ni(OH)3ISA2−. The reported data confirm the low solubility (&lt;10−7M) of Ni(II) in hyperalkaline pH conditions representative of cementitious environments (10≤ pH ≤13), which increases to up to 10−5M in the presence of 0.2 M NaISA. These results significantly improve source term estimations for Ni(II) in environments relevant for the disposal of low and intermediate level radioactive waste (L/ILW). The chemical and thermodynamic models derived in this work can be implemented in geochemical models/calculations, and provide further confidence in the safety analysis of repositories for the disposal of L/ILW.

Modeling Resumption of Glass Alteration Due to Zeolites Precipitation

Under hyper-alkaline pH or relatively high temperatures, a resumption of glass alteration can occur. This sudden acceleration of the glass corrosion rate is almost always associated with zeolites precipitation. Zeolites precipitation consumes silica and aluminum, key elements of the glass surface layer controlling its dissolution. A better understanding and quantification of this mechanism is crucial for predicting glass long-term behavior. Geochemical modeling applied to experimental data is a useful tool to reach that goal. However, it has never been applied successfully so far for modeling the kinetics of that reaction. Within the framework of the GRAAL glass dissolution model, and with simple zeolite precipitation kinetic assumptions, a simulation of glass resumption of alteration is attempted. Concentrations in solution and element mass balance between amorphous and crystallized phases are reproduced. Key parameters are revealed. Better understanding is now achievable through sensitivity studies on minerals stoichiometry and on the respective weight of dissolution and precipitation kinetics in the control of the whole reaction rate.

Influence of Hyper-Alkaline pH Leachate on Mineral and Porosity Evolution in the Chemically Disturbed Zone Developed in the Near-Field Host Rock for a Nuclear Waste Repository

This paper evaluates the effect of hyper-alkaline (NaOH/KOH) leachate on the mineralogy and porosity of a generic quartzo-feldspathic host rock for intermediate- and low-level nuclear waste disposal following permeation of the cementitious repository barrier by groundwater. The analysis is made with reference to expected fluid compositions that may develop by contact of groundwater with the cementitious barrier to form a chemically disturbed zone (CDZ) in the adjacent host rock, as informed by relevant natural analogue sites. Theoretical analysis and numerical modelling is used to explore the influence of different host rock mineral assemblages on changes in pore fluid chemistry, multiple mineral dissolution and precipitation reactions and matrix porosity within the CDZ under these conditions. The numerical modelling accounts for kinetic and surface area effects on the mineral transformation and porosity development for periods of up to 10,000 years travel time from the repository and ambient temperature of \(20\,^{\circ }\hbox {C}\). The analysis shows that dissolution of quartz, feldspar and muscovite in the host rock, by the hyper-alkaline waste leachate, will create relatively high concentrations of dissolved Si and Al in the pore fluid, which migrates as chemical fronts within the CDZ. Precipitation of secondary mineral phases is predicted to occur under these conditions. The increase in matrix porosity that arises from dissolution of primary aluminosilicate minerals is compensated by a reduction in porosity due to precipitation of the secondary phases, but with a net overall increase in matrix porosity. These coupled physical and geochemical processes are most important for contaminant transport in the near-field zone of the CDZ and are eventually buffered by the host rock within 70 m of the repository for the 10,000 year travel time scenario. The predicted changes in matrix porosity may contribute to increased transport of radionuclides in the host rock, in the absence of attenuation by other mechanisms in the CDZ.

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.

Review of the complexation of tetravalent actinides by ISA and gluconate under alkaline to hyperalkaline conditions

Isosaccharinic (ISA) and gluconic acids (GLU) are polyhydroxy carboxylic compounds showing a high affinity to metal complexation. Both organic ligands are expected in the cementitious environments usually considered for the disposal of low- and intermediate-level radioactive wastes. The hyperalkaline conditions imposed by cementitious materials contribute to the formation of ISA through cellulose degradation, whereas GLU is commonly used as a concrete additive. Despite the high stability attributed to ISA/GLU complexes of tetravalent actinides, the number and reliability of available experimental studies is still limited. This work aims at providing a general and comprehensive overview of the state of the art regarding Th, U(IV), Np(IV), and Pu(IV) complexes with ISA and GLU. In the presence of ISA/GLU concentrations in the range 10 − 5 –10 − 2 M and absence of calcium, An(IV)(OH) x (L) y complexes (An(IV) = Th, U(IV), Np(IV), Pu(IV); L = ISA, GLU) are expected to dominate the aqueous speciation of tetravalent actinides in the alkaline pH range. There is a moderate agreement among their stability, although the stoichiometry of certain An(IV)-GLU complexes is still ill-defined. Under hyperalkaline conditions and presence of calcium, the species CaTh(OH) 4(L) 2(aq) has been described for both ISA and GLU, and similar complexes may be expected to form with other tetravalent actinides. In the present work, the available thermodynamic data for An(IV)–ISA/GLU complexes have been reviewed and re-calculated to ensure the internal consistency of the stability constants assessed. Further modelling exercises, estimations based on Linear Free-Energy Relationships (LFER) among tetravalent actinides, as well as direct analogies between ISA and GLU complexes have also been performed. This approach has led to the definition of a speciation scheme for the complexes of Th, U(IV), Np(IV) and Pu(IV) with ISA and GLU forming in alkaline to hyperalkaline pH conditions, both in the absence and presence of calcium.

Interaction of Tournemire argillite (Aveyron, France) with hyperalkaline fluids: Batch experiments performed with powdered and/or compact materials

Argillaceous rocks and concrete matrix are considered as potential host rocks and engineered barrier, respectively for radioactive waste repositories. The concrete matrix could react with the groundwater of the geological site, inducing a drastic change in its chemical composition and pH. Consequently, the physico-chemical properties of the rock in contact with this hyperalkaline fluid may be modified. Therefore, an experimental programme has been developed for examining the physico-chemical changes of claystone in contact with alkaline fluids: batch experiments undertaken as a preliminary step followed by diffusion and percolation experiments in order to describe and to assess the physico-chemical phenomena observed under repository conditions. The first series of batch experiments are carried out in order to study the degradation of the Tournemire argillite properties caused by a fluid resulting from a contact with fresh concrete, considered as the most aggressive in relation to its hyper alkaline pH (≈13). Thus, the influence of several parameters is tested, such as liquid/rock ratio (L/R 3–30 g/g), contact time (1–3 months), temperature (25–70 °C) and oxygen concentration. To compare the effect of the concrete maturity on the argillite physico-chemical damage, the second series of batch experiments are performed with a fluid resulting from a contact with moderately degraded concrete. Experiments are carried out on powdered and compact samples in order to identify structural and geochemical modifications. Before and after contact with simplified concrete fluids, powdered solids were mainly characterised by XRD (with measurements of specific surface area and SEM observations for a selection of samples) whereas compact materials were only observed by SEM. The chemical composition of the recovered solutions was also determined for their major anions and cations with their carbon content and pH values. Interpretations are based on solid analyses and aqueous chemistry. The comparison of results obtained with powdered and compact solids is only feasible for short time experiments. Aqueous chemistry and solid analyses indicate the dissolution of pyrite, dolomite and organic carbon with the precipitation of calcite. Precipitations of zeolites and K-feldspars occur sometimes and are only evidenced by SEM analyses. Nevertheless, silicates dissolution or precipitation is unclear through XRD analyses. Experimental conditions influence widely the intensity/nature of processes and prevent the transposition of data obtained in given conditions to other ones.