Specific surface area determinations on intact drillcores and evaluation of extrapolation methods for rock matrix surfaces.

Permanent storage of spent nuclear fuel in crystalline bedrock is investigated in several countries. For this storage scenario, the host rock is the third and final barrier for radionuclide migration. Sorption reactions in the crystalline rock matrix have strong retardative effects on the transport of radionuclides. To assess the barrier properties of the host rock it is important to have sorption data representative of the undisturbed host rock conditions. Sorption data is in the majority of reported cases determined using crushed rock. Crushing has been shown to increase a rock samples sorption capacity by creating additional surfaces. There are several problems with such an extrapolation. In studies where this problem is addressed, simple models relating the specific surface area to the particle size are used to extrapolate experimental data to a value representative of the host rock conditions. In this article, we report and compare surface area data of five size fractions of crushed granite and of 100 mm long drillcores as determined by the Brunauer Emmet Teller (BET)-method using N(2)-gas. Special sample holders that could hold large specimen were developed for the BET measurements. Surface area data on rock samples as large as the drillcore has not previously been published. An analysis of this data show that the extrapolated value for intact rock obtained from measurements on crushed material was larger than the determined specific surface area of the drillcores, in some cases with more than 1000%. Our results show that the use of data from crushed material and current models to extrapolate specific surface areas for host rock conditions can lead to over estimation interpretations of sorption ability. The shortcomings of the extrapolation model are discussed and possible explanations for the deviation from experimental data are proposed.

Determination of sorption properties of intact rock samples: new methods based on electromigration.

Two new methods for determining sorption coefficients in large rock samples have been developed. The methods use electromigration as a means to speed up the transport process, allowing for fast equilibration between rock sample and tracer solution. An electrical potential gradient acts as a driving force for transport in addition to the concentration gradient and forces the cations through the rock sample towards the cathode. The electrical potential gradient induces both electromigration and electroosmotic flow with a resulting solute transport that is large compared to diffusive fluxes. In one of the methods, the solute is driven through the sample and collected at the outlet side. In the other, simpler method, the rock sample is equilibrated by circulating the solute through the sample. The equilibration of rock samples, up to 5 cm in length, with an aqueous solution has been accomplished within days to months. Experiments using cesium as a sorbing tracer yield results consistent with considerably more time demanding in-diffusion experiments. These methods give lower distribution coefficients than those obtained using traditional batch experiments with crushed rock.

Long-term oxygen depletion from infiltrating groundwaters: model development and application to intra-glaciation and glaciation conditions.

Processes that control the redox conditions in deep groundwaters have been studied. The understanding of such processes in a long-term perspective is important for the safety assessment of a deep geological repository for high-level nuclear waste. An oxidising environment at the depth of the repository would increase the solubility and mobility of many radionuclides, and increase the potential risk for radioactive contamination at the ground surface. Proposed repository concepts also include engineered barriers such as copper canisters, the corrosion of which increases considerably in an oxidising environment compared to prevailing reducing conditions. Swedish granitic rocks are typically relatively sparsely fractured and are best treated as a dual-porosity medium with fast flowing channels through fractures in the rock with a surrounding porous matrix, the pores of which are accessible from the fracture by diffusive transport. Highly simplified problems have been explored with the aim to gain understanding of the underlying transport processes, thermodynamics and chemical reaction kinetics. The degree of complexity is increased successively, and mechanisms and processes identified as of key importance are included in a model framework. For highly complex models, analytical expressions are not fully capable of describing the processes involved, and in such cases the solutions are obtained by numerical calculations. Deep in the rock the main source for reducing capacity is identified as reducing minerals. Such minerals are found inside the porous rock matrix and as infill particles or coatings in fractures in the rock. The model formulation also allows for different flow modes such as flow along discrete fractures in sparsely fractured rocks and along flowpaths in a fracture network. The scavenging of oxygen is exemplified for these cases as well as for more comprehensive applications, including glaciation considerations. Results show that chemical reaction kinetics control the scavenging of oxygen during a relatively short time with respect to the lifetime of the repository. For longer times the scavenging of oxygen is controlled by transport processes in the porous rock matrix. The penetration depth of oxygen along the flowpath depends largely on the hydraulic properties, which may vary significantly between different locations and situations. The results indicate that oxygen, in the absence of easily degradable organic matter, may reach long distances along a flow path during the life-time of the repository (hundreds to thousands of metres in a million years depending on e.g. hydraulic properties of the flow path and the availability of reducing capacity). However, large uncertainties regarding key input parameters exist leading to the conclusion that the results from the model must be treated with caution pending more accurate and validated data. Ongoing and planned experiments are expected to reduce these uncertainties, which are required in order to make more reliable predictions for a safety assessment of a nuclear waste repository.

Accumulation of heavy metals in the Oostriku peat bog, Estonia: determination of binding processes by means of sequential leaching.

The Oostriku peat bog (central Estonia) has been exposed to metal-rich groundwater discharge over a long period of time and has accumulated high concentrations of Fe (up to 40 wt-%), heavy metals (e.g. Pb, Zn, Mn, Cu), and As. In this study, the peat was characterised with respect to composition and metal content with depth. The peat pore water was analysed and compared to a spring water emerging at the site. Sequential extraction, using a Tessier scheme optimised for iron-rich sediments, was used to understand the relative roles of binding mechanisms involved in the retention of different metals in the peat. Significant difference in depth distribution was found between different metals bound in the peat, which was partly attributed to varying compositions of the peat with depth and different dominant binding mechanisms for different metals.

The long-term evolution of and transport processes in a self-sustained final cover on waste deposits.

A new principle for confinement of waste based on a self-sustained seal is presented. The top cover is considered to consist of two main layers; an organic carbon rich surface layer that is able to support vegetation and an inorganic layer beneath it. The function of the cover is to mitigate oxidation and acidification of landfilled waste and hence the release of toxic metals. It is suggested that forest soil formation and soil development could prove to be valuable information sources for the study of the long-term behaviour of a final cover on waste deposits. Since the cover is expected to develop in northern temperate climate the focus is on Spodosol soil. A number of simulations of the long-term behaviour of the final self-sustained landfill cover are made, including the rates of influx of oxygen into the cover. A cover having a large portion of organic matter compared with a cover with no organics can considerably decrease the oxygen concentration and thus the influx of oxygen into a landfill. The calculated oxygen intrusion rate for the former case is of the order of 0.05 kg m(-2) year(-1). Degradation of the organics produces acids. Our simulations indicate that the pH-buffering capacity of the mineral layer, represented by calcite and primary rock minerals, will last for many thousands of years.

Rock matrix diffusivity determinations by in-situ electrical conductivity measurements.

A fast method to determine rock matrix diffusion properties directly in the bedrock would be valuable in the investigation of a possible site for disposal of nuclear waste. An "effective diffusivity borehole log" would provide important information on the variability of this entity over the area studied. As opposed to traditional matrix diffusion laboratory experiments, electrical conductivity measurements are fast, inexpensive and also easy to carry out in-situ. In this study, electrical resistivity data from borehole logging, as well as from measurements on the actual core, is evaluated with the purpose of extracting matrix diffusivity data. The influence of migration of ions in the electrical double layer, which can be of great importance in low ionic strength pore water, is also considered in evaluating the in-situ data to accurately determine the effective pore diffusivity. The in-situ data compare fairly well to those measured in the rock core.

Long-term processes in waste deposits.

A conceptual model, which is a unitary and continuous description of the overall processes in waste deposits, has been developed. In the model the most important processes governing the long-term fate of organic matter in landfills and the transport and retention of toxic metals are included. With the model as a base, a number of scenarios with different levels of complexity have been defined and studied in order to carry out long-term assessments of the chemical evolution in waste deposits for industrial and municipal solid waste containing much organic matter and the leaching of toxic metals. The focus of the modelling has been to quantify the important processes occurring after the methane production phase has ceased, i.e. during the humic phase. The scenarios include the main mechanisms based on various transport processes as well as different landfill constructions, e.g. binding capacities of sulfides and humic substances. They also include transport mechanisms by which the reactant oxygen can intrude into a deposit, sorption capacities of hydrous ferric oxides, and pH-buffering reactions, etc. Scoping calculations have shown that the binding capacity of humic substances is sufficient to bind all toxic metals (Cd, Cr, Pb, Zn and Hg). In addition, the humics could also bind a smaller part of Ca, Fe and Al, provided much of the organic waste remain as humic substances. Sulfides on the other hand can bind approximately twice the amount of all toxic metals. The binding capacity of hydrous ferric oxides, which can be formed by oxidation reactions during the humic phase, is estimated to be three times the total content of metals that can sorb on hydrous ferric oxides. In the studied landfill the pH-buffering capacity, primarily represented by calcite, is estimated to be 1 mol/kg dry waste. Quantifications indicate that the alkalinity of the wastes is high enough to buffer the acidity produced by the oxidation of sulfides and by the degradation of organic matter, as well as that added by acid precipitation. Therefore, the main conclusion is that higher remobilisation rates of heavy metals due to lowering of pH are not expected for many thousands of years.

Long-term fate of organics in waste deposits and its effect on metal release.

The long-term chemical evolution in waste deposits and the release of toxic metals was investigated. The degradation of organic matter and hence the potential efflux of heavy metals in a long-term perspective was studied by defining some scenarios for waste deposits containing organic compounds, different longevity and functions of covers and different water and air intrusion rates. The scenarios were based on various transport processes as well as different landfill constructions. The rates of influx of oxygen into both saturated and partially saturated landfills have been estimated. Each scenario takes the form of a mathematical model. The starting point for all the studied cases is the humic phase, i.e. the phase after the methane production has stopped. Based on the different cases studied, it appeared that landfills where the waste is below the water table could have advantages over the other cases. Recognizing that this option is not accepted in most countries we, nevertheless, suggested it should be reevaluated. The main conclusion is that the degradation of humic matter and hence the release of toxic metals can be substantially decreased if potential build-up of hydraulic gradients are avoided and if the landfill is located below the water surface. A conceivable alternative construction would be to place it in a depression--either natural or artificial--and to construct it so that under normal conditions it would always be water-saturated.