The long-lived radionuclide 79Se is one of the elements of concern for the safe storage of high-level nuclear waste, since clay minerals in engineered barriers and natural aquifer sediments strongly adsorb cationic species, but to lesser extent anions like selenate (SeVIO42−) and selenite (SeIVO32−). Previous investigations have demonstrated, however, that SeIV and SeVI are reduced by surface-associated FeII, thereby forming insoluble Se0 and Fe selenides. Here we show that the mixed FeII/III (hydr)oxides green rust and magnetite, and the FeII sulfide mackinawite reduce selenite rapidly (< 1 day) to FeSe, while the slightly slower reduction by the FeII carbonate siderite produces elemental Se. In the case of mackinawite, both S−II and FeII surface atoms are oxidized at a ratio of one to four by producing a defective mackinawite surface. Comparison of these spectroscopic results with thermodynamic equilibrium modeling provides evidence that the nature of reduction end product in these FeII systems is controlled by the concentration of HSe−; Se0 forms only at lower HSe− concentrations related to slower HSeO3− reduction kinetics. Even under thermodynamically unstable conditions, the initially formed Se solid phases may remain stable for longer periods since their low solubility prevents the dissolution required for a phase transformation into more stable solids. The reduction by Fe2+-montmorillonite is generally much slower and restricted to a pH range, where selenite is adsorbed (pH < 7), stressing the importance of a heterogeneous, surface-enhanced electron transfer reaction. Although the solids precipitated by the redox reaction are nanocrystalline, their solubility remains below 6.3 × 10− 8 M. No evidence for aqueous metal selenide colloids nor for Se sorption to colloidal phases was found. Since FeII phases like the ones investigated here should be ubiquitous in the near field of nuclear waste disposals as well as in the surrounding aquifers, mobility of the fission product 79Se may be much lower than previously assumed. 相似文献
The KBS-3 underground nuclear waste repository concept designed by the Swedish Nuclear Fuel and Waste Management Co. (SKB) includes a bentonite buffer barrier surrounding the copper canisters and the iron insert where spent nuclear fuel will be placed. Bentonite is also part of the backfill material used to seal the access and deposition tunnels of the repository. The bentonite barrier has three main safety functions: to ensure the physical stability of the canister, to retard the intrusion of groundwater to the canisters, and in case of canister failure, to retard the migration of radionuclides to the geosphere. Laboratory experiments (< 10 years long) have provided evidence of the control exerted by accessory minerals and clay surfaces on the pore water chemistry. The evolution of the pore water chemistry will be a primordial factor on the long-term stability of the bentonite barrier, which is a key issue in the safety assessments of the KBS-3 concept.In this work we aim to study the long-term geochemical evolution of bentonite and its pore water in the evolving geochemical environment due to climate change. In order to do this, reactive transport simulations are used to predict the interaction between groundwater and bentonite which is simulated following two different pathways: (1) groundwater flow through the backfill in the deposition tunnels, eventually reaching the top of the deposition hole, and (2) direct connection between groundwater and bentonite rings through fractures in the granite crosscutting the deposition hole. The influence of changes in climate has been tested using three different waters interacting with the bentonite: present-day groundwater, water derived from ice melting, and deep-seated brine. Two commercial bentonites have been considered as buffer material, MX-80 and Deponit CA-N, and one natural clay (Friedland type) for the backfill. They show differences in the composition of the exchangeable cations and in the accessory mineral content. Results from the simulations indicate that pore water chemistry is controlled by the equilibrium with the accessory minerals, especially carbonates. pH is buffered by precipitation/dissolution of calcite and dolomite, when present. The equilibrium of these minerals is deeply influenced by gypsum dissolution and cation exchange reactions in the smectite interlayer. If carbonate minerals are initially absent in bentonite, pH is then controlled by surface acidity reactions in the hydroxyl groups at the edge sites of the clay fraction, although its buffering capacity is not as strong as the equilibrium with carbonate minerals. The redox capacity of the bentonite pore water system is mainly controlled by Fe(II)-bearing minerals (pyrite and siderite). Changes in the groundwater composition lead to variations in the cation exchange occupancy, and dissolution–precipitation of carbonate minerals and gypsum. The most significant changes in the evolution of the system are predicted when ice-melting water, which is highly diluted and alkaline, enters into the system. In this case, the dissolution of carbonate minerals is enhanced, increasing pH in the bentonite pore water. Moreover, a rapid change in the population of exchange sites in the smectite is expected due to the replacement of Na for Ca. 相似文献
Fly ash is a hazardous byproduct of municipal solid wastes incineration (MSWI). An alkali activated blast furnace slag-based cementitious material was used to stabilize/solidify the fly ash at experimental level. The characteristics of the stabilized/solidified fly ash, including metal leachability, mineralogical characteristics and the distributions of metals in matrices, were tested by toxic characteristic leaching procedure (TCLP), X-ray diffraction (XRD) and scanning electron microscopy-energy dispersive spectrometer (SEM-EDS) respectively. Continuous acid extraction was utilized to extract metal ions and characterize their leaching behavior. The stabilization/solidification procedure for MSWI fly ash demonstrates a strong fixing capacity for the metals by the formation of C-S-H phase, hydrated calcium aluminosilicate and ettringite. The stabilized/solidified fly ash shows a dense and homogeneous microstructure. Cr is mainly solidified in hydrated calcium aluminosilicate, C-S-H and ettringite phase through physical encapsulation, precipitation, adsorption or substitution mechanisms, and Pb is mainly solidified in C-S-H phase and absorbed in the Si-O structure. 相似文献
Although Beijing has carried out municipal solid waste (MSW) source separation since 1996, it has largely been ineffective. In 2012, a “Green House” program was established as a new attempt for central sorting. In this study, the authors used material flow analysis (MFA) and cost benefit analysis (CBA) methods to investigate Green House’s environment and economic feasibility. Results showed that the program did have significant environmental benefits on waste reduction, which reduced the amount of waste by 34%. If the Green House program is implemented in a residential community with wet waste ratio of 66%, the proportion of waste reduction can reach 37%. However, the Green House is now running with a monthly loss of 1982 CNY. This is mainly because most of its benefits come from waste reduction (i.e., 5878 CNY per month), which does not turn a monetary benefit, but is instead distributed to the whole of society as positive environmental externalities. Lack of government involvement, small program scale, and technical/managerial deficiency are three main barriers of the Green House. We, thus, make three recommendations: involve government authority and financial support, expand the program scale to separate 91.4 tons of waste every month, and use more professional equipment/technologies. If the Green House program can successfully adopt these suggestions, 33.8 tons of waste can be reduced monthly, and it would be able to flip the loss into a profit worth 35034 CNY.
