Structural incorporation of Neptunyl(V) into Calcite: Interfacial Reactions and Kinetics

In this experimental work the calcite-water interface is characterized by means of zetapotential and surface diffraction measurements. Based on the experimental results a new Basic Stern Surface Complexation model for calcite is developed. Neptunyl(V) adsorption at the calcite surface and incorporation into the calcite structure is studied by batch type adsorption- and mixed flow reactor experiments. Adsorption and incorporation species of Neptunyl are investigated by EXAFS spectroscopy

How well suited are current thermodynamic models to predict or interpret the composition of (Ba,Sr)SO₄ solid-solutions in geothermal scalings?

In this study, we report results of the analysis of a particularly interesting scaling sample from the geothermal plant in Neustadt-Glewe in northern Germany, which contained 19% Galena (PbS) and 81% of a heterogeneous assemblage of (Ba,Sr)SO₄ crystals with varying compositions, 0.15 < X$_{Ba}$ < 0.53. A main fraction of the sample (~56%) has a barite content of X$_{Ba}$ ≈ 0.32. We try to relate the solid composition of the (Ba,Sr)SO₄ solid-solution to the conditions at the geothermal plant concerning temperature, pressure, and solution composition, and discuss it with respect to the challenges in modelling the composition of (Ba,Sr)SO₄ solid-solutions on the basis of thermodynamic mixing models. We note that considerable uncertainties are related to the description of (Ba,Sr)SO₄ formation by means of thermodynamic models. The scaling composition observed in this study would be in line with endmember solubilities as predicted by the PhreeqC-Pitzer database for 70 °C and an interaction parameter, a0 = 1.6. According to such a model, the scaling heterogeneity would reflect bimodal precipitation behaviour due to various degrees of depletion of the brine with respect to X(Ba)($_{aq}$). Minor fluctuations in X(Ba)($_{aq}$): 0.0017 < X(Ba)($_{aq}$) < 0.0042 explain the full range of observed solid compositions. The choice especially of the interaction parameter seems to some extent arbitrary. This knowledge gap strongly limits the interpretation of (Ba,Sr) SO₄ compositions. Thus, it is not possible to distinguish between kinetic and thermodynamic effects on partitioning or to use the solid-solution composition to draw conclusions about the precipitation conditions (e.g. Temperature)

Adsorption of Selenium and Strontium on Goethite: EXAFS Study and Surface Complexation Modeling of the Ternary Systems

Knowledge of the geochemical behavior of selenium and strontium is critical for the safe disposal of radioactive wastes. Goethite, as one of the most thermodynamically stable and commonly occurring natural iron oxy-hydroxides, promisingly retains these elements. This work comprehensively studies the adsorption of Se(IV) and Sr(II) on goethite. Starting from electrokinetic measurements, the binary and ternary adsorption systems are investigated and systematically compared via batch experiments, EXAFS analysis, and CD-MUSIC modeling. Se(IV) forms bidentate inner-sphere surface complexes, while Sr(II) is assumed to form outer-sphere complexes at low and intermediate pH and inner-sphere complexes at high pH. Instead of a direct interaction between Se(IV) and Sr(II), our results indicate an electrostatically driven mutual enhancement of adsorption. Adsorption of Sr(II) is promoted by an average factor of 5 within the typical groundwater pH range from 6 to 8 for the concentration range studied here. However, the interaction between Se(IV) and Sr(II) at the surface is two-sided, Se(IV) promotes Sr(II) outer-sphere adsorption, but competes for inner-sphere adsorption sites at high pH. The complexity of surfaces is highlighted by the inability of adsorption models to predict isoelectric points without additional constraints

Anaerobic corrosion of carbon steel in compacted bentonite exposed to natural opalinus clay porewater: bentonite alternation study

Carbon steel is a potential canister material for the disposal of high-level radioactive waste in deep geological repositories in clays and clay rocks. Bentonite is considered as a potential backfill material for those multi-barrier systems. To predict the long-term performance and for safety assessment the knowledge of canister corrosion behavior is important. The formed corrosion products and mineralogically altered bentonite at the canister/bentonite interface can potentially provide an additional barrier against radionuclide migration. In-situ corrosion experiments were performed at the Mt. Terri underground research laboratory. Coupons of carbon steel were embedded in Volclay MX-80 bentonite with controlled densities, installed in a borehole under simulated repository and anaerobic conditions and exposed to natural Opalinus Clay porewater for a period up to 5.5 years. The bentonite layer at the canister/bentonite interface was characterized by complementary microscopic and spectroscopic techniques (XPS, SEM-EDX, XRD) under anoxic conditions. The interface revealed reddish-brown staining up to 2 mm depth into the bentonite in the zone adjacent to the steel. The SEM-EDX analyses of the interface (embedded crosscut with steel removed) showed calcium and iron enrichment in the bentonite adjacent to the metal. µXRF analysis performed on the bentonite at the interface showed calcium enriched rim up to 100 µm into the bentonite, while µXANES analysis revealed formation of iron silicate compounds in the reacted reddish-brown zone. The steel coupon was removed prior embedding. A line scan from the edge towards bulk bentonite did not indicate any systematic gradient in the Fe2+ / Fe3+ ratio. The formation of mixed Fe2+/3+ silicate compounds appears to be heterogeneous. This work contributes to an increased understanding of steel corrosion mechanisms in clay, which can improve the robustness of canister lifetime predictions. We acknowledge the German Federal Ministry of Education and Research (BMBF) and the Helmholtz association for the financial support. We thank the Mont Terri IC-A Partners and Swisstopo for providing the samples. We acknowledge the provision of the beamtime at the KIT Light Source, KARA, Germany

Quantum Chemical Investigation of the Selenite Incorporation into the Calcite (10-14) Surface

Selenium is a common pollutant in soils and aquifers. The radioisotope $^{79}$Se, an abundant fission product of $^{235}$U, is of particular concern in the context of nuclear waste disposal safety due to its long half-life and its expected high mobility in the multi-barrier system around potential nuclear waste disposal sites. Oxidized selenium species are relatively soluble and show only weak adsorption at common mineral surfaces. However, a possible sorption mechanism for selenium in the geosphere is the structural incorporation of selenium(IV) (selenite, SeO$_3^{2-}$) into calcite (CaCO$_3$). We carried out a detailed quantum chemical study of the incorporation of SeO$_3^{2-}$ into the calcite surface and the subsurface layers. As the main result we present the structural changes upon incorporation of selenite (SeO$_3^{-2}$) into the dry and hydrated calcite ($10\overline{1}4$) surface. For the dry surface we add results for the incorporation into the subsurface layers. This results are complemented by energetic considerations and in turn used to estimate the thermodynamic partition coefficient $\mathbf D$ for SeO$_3^{-2}$ incorporation into the surface and subsurface layers. The results corroborate the recently proposed entrapment model for selenium(IV) coprecipitation with calcite and show that equilibrium incorporation of selenite into calcite may occur in the surface layer, but is practically impossible in subsurface layers or the bulk

Anaerobic corrosion of carbon steel in compacted bentonite exposed to natural Opalinus clay porewater: Bentonite alteration study

Carbon steel is a potential canister material for the disposal of high-level radioactive waste in deep geological repositories in clays and clay rocks. Bentonite is considered as a potential backfill material for those multi-barrier systems. To predict the long-term performance and for safety assessment the knowledge of canister corrosion behavior is important. The formed corrosion products and mineralogically altered bentonite at the canister/bentonite interface can potentially provide an additional barrier against radionuclide migration. In-situ corrosion experiments were performed at the Mt. Terri underground research laboratory. Coupons of carbon steel were embedded in Volclay MX-80 bentonite with controlled densities, installed in a borehole under simulated repository and anaerobic conditions and exposed to natural Opalinus Clay porewater for a period up to 5.5 years. The bentonite layer at the canister/bentonite interface was characterized by complementary microscopic and spectroscopic techniques (XPS, SEM-EDX, XRD) under anoxic conditions. The interface revealed reddish-brown staining up to 2 mm depth into the bentonite in the zone adjacent to the steel. The SEM-EDX analyses of the interface (embedded crosscut with steel removed) showed calcium and iron enrichment in the bentonite adjacent to the metal. µXRF analysis performed on the bentonite at the interface showed calcium enriched rim up to 100 µm into the bentonite, while µXANES analysis revealed formation of iron silicate compounds in the reacted reddish-brown zone. The steel coupon was removed prior embedding. A line scan from the edge towards bulk bentonite did not indicate any systematic gradient in the Fe2+ / Fe3+ ratio. The formation of mixed Fe2+/3+ silicate compounds appears to be heterogeneous. This work contributes to an increased understanding of steel corrosion mechanisms in clay, which can improve the robustness of canister lifetime predictions. We acknowledge the German Federal Ministry of Education and Research (BMBF) and the Helmholtz association for the financial support. We thank the Mont Terri IC-A Partners and Swisstopo for providing the samples. We acknowledge the provision of the beamtime at the KIT Light Source, KARA, Germany

Mineralogical characterization of scalings formed in geothermal sites in the Upper Rhine Graben before and after the application of sulfate inhibitors

Scale formation processes in the surface installations of geothermal power plants may have a negative effect on power plant performance. In addition, scales formed within the geothermal water circuit frequently accumulate natural radionuclides. Consequently, scale formation may lead to radiation dose rates, which are of radiological concern, and deposits, which may have to be disposed as radioactive waste. In order to minimize these problems and to foster geothermal power plant availability, it is of major interest to understand scale formation processes and to develop methods for their inhibition. One important pre-requisite towards this goal is a sound mineralogical and geochemical characterization of the formed material. Geothermal brines at sites in the Upper Rhine Graben are in general highly mineralized and become, upon cooling in the heat exchanger, supersaturated with respect to sulfate solid-solutions, e.g. (Ba,Sr)SO4, and other mineral phases. Some geothermal power plants very successfully tested the application of sulfate scaling inhibitors. Here we present mineralogical analyses of scale samples from geothermal power plants in the Upper Rhine Valley deposited in absence and presence of sulfate scaling inhibitors. Solid samples are investigated using wet-chemistry (after digestion), XRPD, SEM-EDX, XPS, EA-IRMS, Raman spectroscopy, and XANES (for explanation of abbreviations, see main text). Samples of scales deposited in the absence of a sulfate scaling inhibitor mainly consist of two phases. The largest part is made up of a barite type (Ba,Sr,Ca)SO4 solid-solution. Traces of Ra occurring in the scaling are assumed to be incorporated in the barite type solid solution. Further minor phases are sulfide phases, either an Xray amorphous nano-particulate phase or galena (PbS). Since the application of the sulfate inhibitor, sulfate minerals are no longer detectable in the scale samples. Subsequent scalings are Pb-dominated and consist mainly of galena (PbS), elemental lead (Pb), arsenic (As) and antimony (Sb). As and Sb are likely present as a nanocrystalline intermetallic mixed compound ((Sb, As) or Pb3(Sb,As)2S3). The absence of barite-type minerals demonstrates the success of the application of the sulfate inhibitor. The precipitation of elemental Pb, As, and Sb, which are more noble than iron, may enhance the corrosion of mild steel pipes in the geothermal water circuit. Elution tests and oxidation of the scalings upon storage at atmospheric conditions demonstrate that proper disposal of the toxic heavy metal and metalloid containing scalings may be challenging