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Studded tyres made of tungsten carbide cobalt (WC-Co) are in the Northern countries commonly used during the winter time. Tungsten (W)-containing nano- and micron-sized particles have been detected close to busy roads in several European countries. Other typical traffic wear particles consist of copper (Cu). The aims of this study were to investigate particle stability and transformation/dissolution properties of nanoparticles (NPs) of WC-Co compared with NPs of tungsten carbide (WC), cobalt (Co), and Cu. Their physicochemical characteristics (primarily surface oxide and charge) are compared with their extent of sedimentation and metal release in synthetic surface water (SW) with and without two different model organic molecules, 2,3- and 3,4-dihydroxybenzoic acid (DHBA) mimicking certain sorption sites of humic substances, for time periods up to 22 days. The WC-Co NPs possessed a higher electrochemical and chemical reactivity in SW with and without DHBA molecules as compared with NPs of WC, Co, and Cu. Co was completely released from the WC-Co NPs within a few hours of exposure, although it remained adsorbed/bonded to the particle surface and enabled the adsorption of negatively charged DHBA molecules, in contrast with the WC NPs (no adsorption of DHBA). The DHBA molecules were found to rapidly adsorb on the Co and Cu NPs. The sedimentation of the WC and WC-Co NPs was not influenced by the presence of the 2,3- or 3,4-DHBA molecules. A slight influence (slower sedimentation) was observed for the Co NPs, and a strong influence (slower sedimentation) was observed for the Cu NPs in SW with 2,3-DHBA compared with SW alone. The extent of metal release increased in the order: WC < Cu < Co < WC-Co NPs. All NPs released more than 1 wt-% of their metal total mass. The release from the Cu NPs was most influenced by the presence of DHBA molecules. [ABSTRACT FROM AUTHOR]

Abstract: Silica sol, i.e., colloidal SiO2, may be used as a low-pH injection grout for very fine fractures in the construction of deep geological repositories for radioactive waste in Sweden and in Finland. If the bentonite barrier encounters SiO2-colloid particles under conditions favorable for aggregation, there is concern that it will modify the bentonite barrier at the bentonite/bedrock interface. In this study qualitative experiments were performed with mixed dispersions of SiO2-colloids and bentonite or homo-ionic Na/Ca-montmorillonite. Samples were prepared at different colloid concentrations and treated under various conditions such as low and high ionic strength (0.3M NaCl), as well as dehydration and redispersing. Free swelling and settling experiments were performed in order to qualitatively compare the conditions in which SiO2-colloids affect the bulk/macro properties of bentonite. In order to study specific SiO2-colloid/montmorillonite interactions and preferred type of initial aggregation, dilute dispersions of homo-ionic montmorillonite dispersions mixed with varying concentrations of SiO2-colloids were prepared and selected samples were characterized by PCS, SEM/EDS, AFM and PXRD. The results from this study show that bentonite and montmorillonite particles can be modified by SiO2-colloids when mixed in comparable amounts, due to dehydration or high ionic strength. Some indications for increased colloidal stability for the SiO2-colloid modified clay particles were also found. From the AFM investigation it was found that initial attachment of the SiO2-colloids in Na+ dominated samples seemed to occur on the edges of the montmorillonite layers. In Ca2+ dominated samples not subjected to excess NaCl, SiO2-colloid sorption onto the faces of the montmorillonite layers was also found. In all, contact between the bentonite barrier and ungelled Silica sol should preferably be avoided. [Copyright &y& Elsevier]

Abstract: In many concepts for final storage of spent nuclear fuel bentonite will be used as an engineered barrier, mainly due to its inertness, plasticity and ability to retard transport of radionuclides by adsorption. In the event of water-bearing fractures making contact with the bentonite barrier, generation and transport of colloidal particles will strongly depend on groundwater composition and the surface properties of the colloidal particles. The bentonite barrier will unavoidably be exposed to ionizing radiation from the spent nuclear fuel but very little is known about effects of ionizing radiation on bentonite concerning colloidal stability. In this work we have studied the effect of γ-radiation on the stability of dilute colloidal Na+-montmorillonite dispersions using a Cs-137 γ-source (doses of 0–53.2 kGy). Aggregation kinetics and sedimentation experiments revealed significant radiation effects, evident as increased colloid stability. The only rationale for this is a γ-radiation induced increase in surface potential. The effects appeared to depend on the Na+-montmorillonite concentration in the irradiated dispersions, indicating that the change in surface potential is induced by aqueous radiolysis products. [Copyright &y& Elsevier]

Abstract: Through-diffusion experiments in bentonite with humic colloids in the size range of 1–10nm were carried out. Bentonite was compacted to 0.6–1.8g/cm3 dry density and equilibrated with 0.01 and 0.1M NaClO4 solutions. Experiments with Eu(III) diffusing in the absence and presence of humics were run in parallel, as well as Co(II) diffusing through compacted bentonite in the presence of humics. The humic colloid diffusion experiments were run for 60 days and the humic concentration in the outlet solutions measured at time intervals. The experimental breakthrough curves for humic substances (HS) as well as the HS, Co(II) and Eu(III) profiles in the bentonite were simulated using the finite difference based computer code ANADIFF. Regardless of the compaction and ionic strength of solutions, humic colloids diffused through the compacted bentonite. The effects of humic colloids on both Co(II) and Eu(III) sorption as well as on diffusion were significant. The apparent diffusivity (D a) increased significantly for both Co(II) and Eu(III) when humic colloids were present and the distribution coefficient (K d) values decreased. [Copyright &y& Elsevier]

Sorption of Ni(II) onto chlorite surfaces was studied as a function of pH (5–10), ionic strength (0.01–0.5M) and Ni concentration (10−8–10−6 M) in an Ar atmosphere using batch sorption with radioactive 63Ni as tracer. Such studies are important since Ni(II) is one of the major activation products in spent nuclear fuel and sorption data on minerals such as chlorite are lacking. The sorption of Ni(II) onto chlorite was dependent on pH but not ionic strength, which indicates that the process primarily comprises sorption by surface complexation. The maximum sorption was at pH∼8 (Kd =∼10−3 cm3/g). Desorption studies over a period of 1–2weeks involving replacement of the aqueous solution indicated a low degree of desorption. The acid–base properties of the chlorite mineral were determined by titration and described using a non-electrostatic surface complexation model in FITEQL. A 2-pK NEM model and three surface complexes, Chl_OHNi2+, Chl_OHNi(OH)+ and Chl_OHNi(OH)2, gave the best fit to the sorption results using FITEQL. The high Kd values and low degree of desorption observed indicate that under expected groundwater conditions, a large fraction of Ni(II) that is potentially leachable from spent nuclear fuel may be prevented from migrating by sorption onto chlorite surfaces. [ABSTRACT FROM AUTHOR]

Abstract: Compacted and water saturated bentonite will be used as an engineered barrier in deep geological repositories for radioactive waste in many countries. Due to the high dose rate of ionizing radiation outside the canisters holding the nuclear waste, radiolysis of the interlayer and pore water in the compacted bentonite is unavoidable. Upon reaction with the oxidizing and reducing species formed by water radiolysis (OH•, e− (aq), H•, H2O2, H2, HO2 •, H3O+), the overall redox properties in the bentonite barrier may change. In this study the influence of γ-radiation on the structural Fe(II)/FeTot ratio in montmorillonite and its reactivity towards hydrogen peroxide (H2O2) was investigated in parallel experiments. The results show that under anoxic conditions the structural Fe(II)/FeTot ratio of dispersed Montmorillonite increased from ≤3 to 25–30% after γ-doses comparable to repository conditions. Furthermore, a strong correlation between the structural Fe(II)/FeTot ratio and the H2O2 decomposition rate in montmorillonite dispersions was found. This correlation was further verified in experiments with consecutive H2O2 additions, since the structural Fe(II)/FeTot ratio was seen to decrease concordantly. This work shows that the structural iron in montmorillonite could be a sink for one of the major oxidants formed upon water radiolysis in the bentonite barrier, H2O2. [Copyright &y& Elsevier]

In this work we have experimentally studied the impact of bentonite clay on the process of radiation-induced copper corrosion in anoxic water. The motivation for this is to further develop our understanding of radiation-driven processes occurring in deep geological repositories for spent nuclear fuel where copper canisters containing the spent nuclear fuel will be embedded in compacted bentonite. Experiments on radiation-induced corrosion in the presence and absence of bentonite were performed along with experiments elucidating the impact irradiation on the Cu 2+ adsorption capacity of bentonite. The experiments presented in this work show that the presence of bentonite clay has no or very little effect on the magnitude of radiation-induced corrosion of copper in anoxic aqueous systems. The absence of a protective effect similar to that observed for radiation-induced dissolution of UO 2 is attributed to differences in the corrosion mechanism. This provides further support for the previously proposed mechanism where the hydroxyl radical is the key radiolytic oxidant responsible for the corrosion of copper. The radiation effect on the bentonite sorption capacity of Cu 2+ (reduced capacity) is in line with what has previously been reported for other cations. The reduced cation sorption capacity is partly attributed to a loss of Al-OH sites upon irradiation. [ABSTRACT FROM AUTHOR]

Abstract: Compacted bentonite is proposed as an engineered barrier in many concepts for disposal of high level nuclear waste. After the initial deposition however, the bentonite barrier will inevitably be exposed to ionizing radiation (mainly γ) under anoxic conditions. Because of this, the effects of γ-radiation on the apparent diffusivity values and sorption coefficients in bentonite for Cs+ and Co2+ were tested under different experimental conditions. Radiation induced effects on sorption were in general more noticeable for Co2+ than for Cs+, which generally showed no significant differences between irradiated and unirradiated clay samples. For Co2+ however, the sorption to irradiated MX80 was significantly lower than to the unirradiated clay samples regardless of the experimental conditions. This implies that γ-radiation may alter the surface characteristics contributing to surface complexation of Co2+. With the experimental conditions used, however, the effect of decreasing sorption was not large enough to be reflected on the obtained D a values. [Copyright &y& Elsevier]