Experimental and modeling studies on sorption and diffusion of radium in bentonite

The sorption and desorption behavior of radium on bentonite and purified smectite was investigated as a function of pH, ionic strength and liquid to solid ratio by batch experiments. The distribution coefficients (Kd) were in the range of 10(2) to > 10(4) ml g-1 and depended on ionic strength and pH. Most of sorbed Ra was desorbed by 1 M KCl. The results for purified smectite indicated that Ra sorption is dominated by ion exchange at layer sites of smectite, and surface complexation at edge sites may increase Ra sorption at higher pH region. Reaction parameters between Ra and smectite were determined based on an interaction model between smectite and groundwater. The reaction parameters were then used to explain the results of bentonite by considering dissolution and precipitation of minerals and soluble impurities. The dependencies of experimental Kd values on pH, ionic strength and liquid to solid ratio were qualitatively explained by the model. The modeling result for bentonite indicated that sorption of Ra on bentonite is dominated by ion exchange with smectite. The observed pH dependency was caused by changes of Ca concentration arising from dissolution and precipitation of calcite. Diffusion behavior of Ra in bentonite was also investigated as a function of dry density and ionic strength. The apparent diffusion coefficients (Da) obtained in compacted bentonite were in the range of 1.1 x 10(-11) to 2.2 x 10(-12) m2 s-1 and decreased with increasing in dry density and ionic strength. The Kd values obtained by measured effective diffusion coefficient (De) and modeled De were consistent with those by the sorption model in a deviation within one order of magnitude.     

The influence of colloid formation in a granite groundwater bentonite porewater mixing zone on radionuclide speciation

In the context of deep geological storage of high level nuclear waste the repository will be designed as multiple barrier system including bentonite as buffer/backfill material and the host rock formation as geological barrier. The engineered barrier (bentonite) will be in contact with the host rock formation and consequently it can be expected that bentonite porewater will mix with formation groundwater. We simulate in this study the mixing of Grimsel groundwater (glacial melt water) with synthetic Febex porewater (assuming already saturated state) in a batch-type study and investigate the formation of colloids by laser-induced breakdown detection (LIBD) and SEM-EDX as well as the changes in radionuclide (U, Th, Eu) speciation via ultrafiltration or via time-resolved laser fluorescence spectroscopy (TRLFS) analysis in the case of Cm(III). Based on PHREEQC saturation index (SI) calculations a precipitation of calcite might be expected at low Febex porewater (FPW) content (< 20%), fluorite precipitation at FPW contents < 60% and gibbsite precipitation at FPW contents above 10%. The colloids generated in the mixing zone aggregate when the synthetic FPW content exceeds 10%. LIBD analysis of the time-dependent colloid generation/aggregation revealed a low concentration of colloids to be stable with an estimated plateau value around 100–200 ppt and an average colloid diameter around 30 nm after 140 days reaction time at FPW admixture > 10%. SEM/EDX mostly identifies Al/Si containing colloidal phases and some sulfates could be found under certain admixture ratios. TRLFS studies show that the Cm speciation is strongly influenced by colloid formation in all solutions. In the Febex pore water/GGW mixing zone with high groundwater contents (> 80%) colloids are newly formed and Cm is almost quantitatively associated with most likely polysilicilic acid colloids.     

Dissolved organic matter effects on the performance of a barrier to polycyclic aromatic hydrocarbon transport by groundwater

In order to contain the movement of organic contaminants in groundwater, a subsurface sorption barrier consisting of sand or clay minerals coated with a cationic surfactant has been proposed. The effectiveness of such a sorption barrier might be affected by the presence of dissolved organic matter (DOM) in the groundwater. To study the impact of DOM on barrier performance, a series of batch experiments were performed by measuring naphthalene and phenanthrene sorption onto sand coated with cetylpyridinium chloride (CPC) and bentonite coated with hexadecyltrimethylammonium bromide (HDTMA) in the presence of various concentrations of DOM. The overall soil-water distribution coefficient (K*) of naphthalene and phenanthrene onto CPC-coated sand decreased with increasing DOM concentration, whereas the K* of the compounds onto HDTMA-coated bentonite slightly increased with increasing DOM concentration. To describe the overall distribution of polycyclic aromatic hydrocarbons (PAHs) in the systems, a competitive multiphase sorption (CMS) model was developed and compared with an overall mechanistic sorption (OMS) model. The modeling studies showed that while the OMS model did not explain the CPC-coated sand experimental results, a model that included competitive sorption between DOM and PAH did. The experimental results and the modeling study indicated that there was no apparent competition between DOM and PAH in the HDTMA-coated bentonite system, and indicated that in groundwater systems with high DOM, a barrier using HDTMA-coated bentonite might be more effective.     

Solute transport properties of compacted Ca-bentonite used in FEBEX project

The present Spanish concept of a deep geological high level waste repository includes an engineered clay barrier around the canister. The clay presents a very high sorption capability for radionuclides and a very small hydraulic conductivity, so that the migration process of solutes is limited by sorption and diffusion processes. Therefore, diffusion and distribution coefficients in compacted bentonite (i.e. in "realistic" liquid to solid ratio conditions) are the main parameters that have to be obtained in order to characterise solute transport that could be produced after the canister breakdown. Through-Diffusion (TD) and In-Diffusion (ID) experiments with HTO, Sr, Cs and Se were carried out using compacted FEBEX bentonite, which is the reference material for the Spanish concept of radioactive waste disposal. Experiments were interpreted by means of available analytical solutions that allow the estimation of diffusion coefficients and, in some cases, distribution coefficients. Analytical solutions are simple to use, but rely on hypotheses that do not hold in all the experiments. These experiments were interpreted also using an automatic parameter estimation code that overcomes the limitations of analytical solutions. Numerical interpretation allows the simultaneous estimation of porosity, diffusion and distribution coefficients, accounts for the role of porous sinters and time-varying boundary concentrations, and can use different types of raw concentration data.     

Variation of the Relative Humidity of Air Released from Canisters after Ambient Sampling

ABSTRACT

Dalton's law of partial pressures and the hypothesis that water vapor equilibrium in a canister is identical to that established above liquid water are used to predict the variation of the percent relative humidity (%RH) of air released from canisters used in ambient air sampling, typically 6-L canisters pressurized with 18 L of air. When (and if) the water vapor partial pressure in a canister exceeds its saturation vapor pressure, water vapor condensation begins and the condensation rate equals the sampling rate of water vapor into the canister. Under constant temperature conditions, the air subsequently released from the canister is less humid than the original sample, following the relationship %RH = 100% (6 L/V_s) for V_s> V_r, where V_s is the residual air volume (referenced to atmospheric pressure), and V_r is shown to depend on the %RH of the ambient air sample. V_r is the residual air volume at which water is completely removed (except for adsorbed water vapor) from the canister wall. For V_s < V_r, the predicted %RH is constant and equal to its value at V_r. Experimental values agree reasonably well with predictions at both high (90%) and low (34%) RH. However, experimental values are often slightly displaced (usually towards lower values of %RH) for mid-range %RH (61%) and variations in %RH near V_r change from canister to canister.     

Sensitivity analysis of radionuclide migration in compacted bentonite: a mechanistic model approach

Mechanistic model calculations for the migration of Cs, Ra, Am and Pb in compacted bentonite have been carried out to evaluate sensitivities with respect to different parameter variations. A surface chemical speciation/electric double layer model is used to calculate: (i) porewater composition and radionuclide speciation in solution and at the bentonite surface, yielding the distribution of mobile and sorbed species and (ii) interaction of diffusing species with negatively charged pore walls to obtain diffusion parameters. The basic scenario considers the interaction of compacted bentonite with a fresh-type groundwater; variations include the presence of bentonite impurities and saline groundwater. It is shown that these scenarios result in significant variations of porewater composition that affect migration via three mechanisms that can partly compensate each other: (1) effects on sorption through radionuclide complexation in solution, and competition of major cations for surface sites; (2) changes in radionuclide solution speciation leading to different diffusing species under different conditions; (3) effects on diffusion through changes in the electric double layer properties of the clay pores as a function of ionic strength.     

Interaction of latex colloids with mineral surfaces and Grimsel granodiorite

Bentonite clay is considered as possible backfill material for nuclear waste repositories in crystalline rock. The same material may also be a source of clay colloids, which may act as carriers for actinide ions possibly released from the repository. Depending on the geochemical parameters, these colloids may be retained by interaction with mineral surfaces of the host rock. In the present study interaction of carboxylated fluorescent latex colloids, used as a model for bentonite colloids, with natural Grimsel granodiorite and some of its component minerals is studied by fluorescence microscopy and SEM/EDX. The experiments are carried out by varying the pH from 2–10. Strong adsorption is observed at pH values close to or below the points of zero charge (pH_pzc) of the mineral surfaces. The influence of Eu(III), used as a chemical homologue for trivalent actinide ions, on colloid adsorption is investigated. Depending on mineral phase and pH, a significant increase of colloid adsorption is observed in the presence of Eu(III).     

In situ anion diffusion experiments using radiotracers

Diffusion experiments in compacted bentonite have been carried out in situ using the borehole laboratory CHEMLAB. The "ordinary" anion iodide and the redox-sensitive pertechnetate ion have been investigated. In spite of strongly reducing groundwater conditions, technetium was found to diffuse mostly unreduced as TcO4-, although in some spots in the compacted clay, the activity was significantly higher, which may be explained by reduction of some TcO4- by iron-containing minerals in the bentonite. The measured concentration profiles in the clay cannot be accommodated by assuming one single diffusion process. The experimental data are modeled assuming two diffusion paths, intralamellar diffusion and diffusion in external water. The apparent diffusivity for the intralamellar diffusion was found to be 8.6 x 10(-11) m2 s(-1) for iodide with a capacity factor of 0.1, while the apparent diffusivity for the diffusion in external water was found to be 5 x 10(-14) m2 s(-1) with alpha=2.26. The corresponding values for Tc were found to be Da= 6 x 10(-11) m2 s(-1), alpha=0.1 and Da= 1 x 10(-13) m2 s(-1), alpha=0.46, respectively. The diffusion constants and capacity factors obtained in this study are in accordance with data from laboratory experiments.     

Ion chemistry of waters impounded by the Ziqlab dam, Jordan, and weathering processes – a case study

The area included in the present investigation is that surrounding Ziqlab dam in the northern Jordan Valley. The water chemistry of the impounded lake shows that it is dominated by Mg, Ca, Na and HCO₃. These waters reflects the dominance of carbonate weathering with some contribution of silicates. Mg + Ca + Na and HCO₃ + Cl account for about 90% of the total cations and anions. X-ray analysis shows that, kaolinte and illite are the dominant clay minerals in sediments behind Ziqlab dam. Anthropogenic activities within the Ziqlab catchments area contribute to increasing of the ionic concentrations. These include various development activities in the catchments area, waste disposal (especially the untreated municipal and domestic sewage) into the Ziqlab River, and agricultural activities. Ziqlab dam water chemistry is within the range of stability field of kaolinite.     

Physicochemical controls on initiation and evolution of desiccation cracks in sand-bentonite mixtures: X-ray CT imaging and stochastic modeling

The shrink-swell behavior of active clays in response to changes in physicochemical conditions creates great challenges for construction of geotechnical barriers for hazardous waste isolation, and is of significant importance for management of agricultural and natural resources. Initiation and evolution of desiccation cracks in active clays are strongly dependent on physicochemical initial and boundary conditions. To investigate effects of bentonite content (20, 40, 60%), pore fluid chemistry (0.05 and 0.5M NaCl) and drying rates (40 and 60°C) on cracking behavior, well-controlled dehydration experiments were conducted and X-ray Computed Tomography (CT) was applied to visualize and quantify geometrical features of evolving crack networks. A stochastic model based on the Fokker-Plank equation was adopted to describe the evolution of crack aperture distributions (CAD) and to assess the impact of physicochemical factors on cracking behavior. Analyses of crack porosity and crack specific surface area showed that both clay content and temperature had larger impact on cracking than pore fluid concentration. More cracks formed at high bentonite contents (40 and 60%) and at high drying rate (60°C). The drift, diffusion and source terms derived from stochastic analysis indicated that evaporative demand had greater influence on the dynamics of the CAD than solution chemistry.     

Diffusion of radionuclides in concrete and concrete-bentonite systems

Various construction materials are under consideration for nuclear waste repositories. Two important materials are concrete and bentonite clay, which will act as mechanical barriers and prevent convective water flow. These barriers will also retard transport (diffusion controlled) of dissolved radionuclides by a combination of mechanical constraints and chemical interactions with the solid.An important issue is the possible change of the initial sodium bentonite into the calcium form due to interaction with calcium from the concrete. The initial leaching of concrete was studied using radioactive spiked concrete in contact with compacted bentonite.Measurement were made of the diffusion of Cs, Am and Pu into 5 different types of concrete in contact with pore water. The diffusivity measured for Cs agrees reasonably well with data found in the literature. No movement could be measured for Am and Pu (< 0.2 mm), even though the contact times were extremely long (2.5 and 5 yr, respectively). The diffusion of Na, Ca and Cs from concrete into bentonite was also measured.     

Application of passive sorbent tube and canister samplers for volatile organic compounds at refinery fenceline locations in Whiting,Indiana

Select volatile organic compounds (VOCs) in ambient air were measured at four fenceline sites at a petroleum refinery in Whiting, IN, using modified EPA Method 325 A/B with passive tubes and EPA Compendium Method TO-15 with canister samplers. One-week, time-integrated samplers were deployed for 8 weeks with tubes and canister samplers deployed in duplicate. Good precision was obtained from the duplicate tubes (<7%) and duplicate canisters (≤10%) for BTEX, perchloroethylene, and styrene. The tubes yielded statistically significantly higher concentrations than canisters for benzene, toluene, ethylbenzene, and m,p-xylene. However, all differences were estimated to be <0.1 ppbv. No concentration differences among the four Whiting sites were found for any of the VOCs.

Implications: Recently enacted EPA Methods 325A/B use passive-diffusive tube samplers to measure benzene at refinery fenceline locations. This pilot study presents VOC data applying a modified version of EPA Method 325 A/B and its comparison to EPA Compendium Method TO-15 canister samplers at four refinery fenceline sites. The findings from this study provide additional confidence in application of the tube method at refineries to ascertain VOC source influence since tube and canister samplers were comparable and good precision was obtained from duplicate sampling for both methods. No overall difference in these reported VOC concentrations was found between Whiting sites for tubes or canisters.     

Effect of temperature on the containment properties of argillaceous rocks: The case study of Callovo-Oxfordian claystones

Heat generated by high level radioactive wastes could alter the performance of a clay repository. It was intended to investigate the effect of such a thermal period on the diffusive properties of Callovo-Oxfordian claystones. Thus, through-diffusion experiments with HTO, Cl-36, Na-22 and Cs-137 were performed before, during and after stages of heating at 80°C that lasted for up to one year. A special attention was paid to limit the occurrence of any chemical disturbance. Therefore (i) the temperature was raised to 80°C, then progressively brought back to 21°C, thanks to three intermediate temperature stages, and (ii) specific synthetic solutions were used for each temperature, chemistry of which being close to the equilibrium state, especially with respect to the carbonate and sulphate minerals. It was found that experiments carried out at 80°C showed a clear increase of the effective diffusion coefficient values for the four tracers with respect to those obtained at 21°C (by a factor of 3 for HTO and Cl-36, 5 for Na-22 and 2 for Cs-137). On the other hand, the porosity and rock capacity values did not exhibit any significant discrepancy between 21°C and 80°C, indicating no observable damage of both the pore conducing network and the sorption properties of clay minerals. The Stokes-Einstein relationship, based on the temperature dependency of the viscosity of bulk water, could be used to describe the temperature dependence of the diffusion of HTO and Cl-36 but failed to describe the diffusive evolution of the two sorbing cations, Na-22 and Cs-137. Furthermore, experiments performed after the thermal period led to diffusive properties well matching those obtained before heating. All these results suggest that at the lab scale the heating of rock samples would not alter the claystone containment properties.     

Modelling geochemical and microbial consumption of dissolved oxygen after backfilling a high level radiactive waste repository

Dissolved oxygen (DO) left in the voids of buffer and backfill materials of a deep geological high level radioactive waste (HLW) repository could cause canister corrosion. Available data from laboratory and in situ experiments indicate that microbes play a substantial role in controlling redox conditions near a HLW repository. This paper presents the application of a coupled hydro-bio-geochemical model to evaluate geochemical and microbial consumption of DO in bentonite porewater after backfilling of a HLW repository designed according to the Swedish reference concept. In addition to geochemical reactions, the model accounts for dissolved organic carbon (DOC) respiration and methane oxidation. Parameters for microbial processes were derived from calibration of the REX in situ experiment carried out at the Asp? underground laboratory. The role of geochemical and microbial processes in consuming DO is evaluated for several scenarios. Numerical results show that both geochemical and microbial processes are relevant for DO consumption. However, the time needed to consume the DO trapped in the bentonite buffer decreases dramatically from several hundreds of years when only geochemical processes are considered to a few weeks when both geochemical reactions and microbially-mediated DOC respiration and methane oxidation are taken into account simultaneously.     

用丙二醇碳酸酯对膨润土进行活化的研究

膨润土及其产品GCL正广泛应用于城市垃圾填埋场的防渗系统中。但是膨润土的膨胀性能在成分复杂的液体(如渗滤液)中会大幅下降,从而直接影响防渗效果。在分析中,利用丙二醇碳酸酯对钠基膨润土进行活化,提高其耐化学性,并分析了其性能改善的机理。     

The role of aqueous iron(II) and manganese(II) in sub-aqueous active barrier systems containing natural clinoptilolite

Increasing attention is being placed on capping as a relatively new option in managing both contaminated sediments and dredged materials, due to its economic and environmental benefits. Capping denotes the placement of a cover onto potentially hazardous sediments or dredged material dumps to inhibit the transfer of contaminants into the water column. Retention of divalent iron and manganese cations using sandy capping layers containing natural zeolites as a reactive additive (active barrier systems, ABS) is evaluated in this study. Three different natural zeolite (clinoptilolite) rocks, two from deposits in Australia and one from a North-American deposit, were investigated and compared with respect to their mineralogical, physical and chemical properties. In particular, results from batch and column experiments show that ABS based on these materials can efficiently demobilise iron and manganese from percolating, anoxic pore water by cation exchange under favourable conditions. The retention, however, may be reduced strongly where competitive exchange with divalent cations such as calcium prevails or where mobile colloidal pore water constituents such as clay minerals or humic substances bind fractions of the dissolved iron or manganese. Therefore, the potential of ABS as a means for in situ remediation has to be evaluated diligently with particular regard to the pore water composition of the sediment to be capped.     

Formation mechanism of hydrogeochemical characterization of mineral water in Antu County,Changbai Mountain area

Antu County in the Changbai Mountains is an important source of mineral water, but there is a lack of research on the source of groundwater characteristic components, affecting the protection of water resources. This study obtained hydrochemical and isotopic data (28 groups in total, April and September in 2019) by summarizing research and sampling data in order to identify the formation process of characteristics. The formation mechanism of the characteristic components was revealed using geostatistical, isotopic, and hydrogeochemical inversion simulations. The results show that the metasilicic acid is a common component of groundwater water chemistry in the study area. The water body primarily receives stable recharge from low-mineralized precipitation with ages ranging from 27.7 to 38.4 years and recharge elevations ranging from 1160 to 2393 m, providing ample time for water–rock interaction. The dissolution of olivine, pyroxene, albite, and other siliceous minerals is the source of characteristic components, and deep faults and deep basalt heat flow are the key conditions for the formation of metasilicic acid. When low-mineralized precipitation recharges the underground aquifer, it dissolves the silica-aluminate and silicon-containing minerals in the surrounding rocks through the water–rock action under the effect of CO₂, causing a large amount of metasilic acid to dissolve into the groundwater and forming metasilic acid-type mineral water.

     

Removal of As,Mn, Mo,Se, U,V and Zn from groundwater by zero-valent iron in a passive treatment cell: reaction progress modeling

Three treatment cells were operated at a site near Durango, CO. One treatment cell operated for more than 3 years. The treatment cells were used for passive removal of contamination from groundwater at a uranium mill tailings repository site. Zero-valent iron [Fe(0)] that had been powdered, bound with aluminosilicate and molded into plates was used as a reactive material in one treatment cell. The others used granular Fe(0) and steel wool. The treatment cells significantly reduced concentrations of As, Mn, Mo, Se, U, V and Zn in groundwater that flowed through it. Zero-valent iron [Fe(0)], magnetite (Fe3O4), calcite (CaCO3), goethite (FeOOH) and mixtures of contaminant-bearing phases were identified in the solid fraction of one treatment cell. A reaction progress approach was used to model chemical evolution of water chemistry as it reacted with the Fe(0). Precipitation of calcite, ferrous hydroxide [Fe(OH)2] and ferrous sulfide (FeS) were used to simulate observed changes in major-ion aqueous chemistry. The amount of reaction progress differed for each treatment cell. Changes in contaminant concentrations were consistent with precipitation of reduced oxides (UO2, V2O3), sulfides (As2S3, ZnS), iron minerals (FeSe2, FeMoO4) and carbonate (MnCO3). Formation of a free gas phase and precipitation of minerals contributed to loss of hydraulic conductivity in one treatment cell.     

Numerical simulation of reactive processes in an experiment with partially saturated bentonite

Bentonites are preferred materials for use as engineered barriers for high-level nuclear waste repositories. Simulation of geochemical processes in bentonite is therefore important for long-term safety assessment of those repositories. In this work, the porewater chemistry of a bentonite sample subject to simultaneous heating and hydration, as studied by Cuevas et al. [Cuevas, J., Villar, M., Fernández, A., Gómez, P., Martín, P., 1997. Porewaters extracted from compacted bentonite subjected to simultaneous heating and hydration. Applied Geochemistry 12, 473-481.], was assessed with a non-isothermal reactive transport model by coupling the geochemical software PHREEQC2 with the object-oriented FEM simulator GeoSys/RockFlow. Reactive transport modelling includes heat transport, two-phase flow, multicomponent transport and geochemical reactions in the liquid phase, i.e. ion exchange, mineral dissolution/precipitation and equilibrium reactions. Simulations show that the easily soluble minerals in bentonite determine the porewater chemistry. Temperature affects both two-phase flow and geochemical reactions. Porosity change due to dissolution/precipitation is low during the experiment. However, changes of the effective porosity caused by bentonite swelling can be very large. The simulated results agree well with the experimental data.