Acidified suspensions of Al-saturated kaolinite, montmorillonite, mica, illite, and biotite in 10−3 M NaNO3 were potentiometrically titrated with 0.1 N NaOH and 0.1 N HNO3 in succession in a CO2-free nitrogen atmosphere. The resulting curves were compared with those for Al(NO3)3 solutions of similar Al concentration in the supernatant solution and corrected for Al in the entrained solution in the clay.

Base titrations of Al ions adsorbed on all the minerals, except montmorillonite, showed two pH inflections separated by a buffering range. With montmorillonite, there were three pH inflections similar to those for Al in solution. The first inflections in the titration of suspensions occurred at lower pHs and were less pronounced than for Al in solution. These represent the titration of H3O+ sorbed during the pretreatment. The buffering by adsorbed Al ions is also less than that by Al in solution.

The OH− used up by adsorbed Al ions between the first and last inflections was equal to, or slightly greater than, the CEC of the minerals, except for mica where it was more than twice the CEC, because new interlayer surfaces were formed during the acid pretreatment. Acid titration curves of Al ions in the adsorbed and solution states showed hysteresis when related to the base titration curves. The use of two titration speeds (3 and 0.3 pH units/hr) only slightly affected the titration curves of the minerals suggesting that the observed effects were not caused by lack of equilibrium with added base or acid.

Disposal of Finnish spent nuclear fuel is planned to be based on the KBS-3 repository concept. The role of the bentonite buffer in this concept is essential, and thus the behaviour of the bentonite has to be known. The experiments in this paper concentrated on providing information about the effects of carbon dioxide CO2(g) partial pressure on compacted sodium bentonite, giving an insight into the buffering capacity. The experimental setup consisted of a hermetic box which had a CO2-adjusted atmosphere, and the bentonite was in contact with this atmosphere through water reservoirs. The results indicated that it is possible to measure online the changing pH in the porewater inside compacted bentonite using IrOx electrodes. It was found that the pH fell if the CO2 partial pressure increased above atmospheric conditions. The experimental results indicated a greater fall in pH than in our model in the test cases where CO2 was present. The pH in the experiment with 0 PCO2 remained nearly constant throughout the 5 month period. On the other hand, the pH dropped to near 6 with 0.3 PCO2 and to 5.5 with 1 PCO2.

At the post-closure stage of a geological disposal facility for higher activity radioactive waste several species of gas are likely to be generated in the near-field environment. These could alter the sealing and chemical properties of the bentonite buffer and the local geochemical environment significantly. The authors' attempt to simulate multicomponent gas flow through variably saturated porous media is presented. Governing equations have been developed for a reactive gas-flow model to simulate the thermo-hydro-gas-chemical-mechanical behaviour, with specific reference to the performance of highly compacted bentonite buffer subjected to repository gas generation and migration. The developed equations have been included in the bespoke numerical model COMPASS and some generic simulations are also presented. The model presented extends current capability to assess buffer performance.

A range of potential concepts for the geological disposal of high level wastes and spent fuel are being studied and considered in the UK. These include concepts that use bentonite as a buffer material around the waste containers. The bentonite will be required to fulfil certain safety functions, the most important being (1) to protect the waste containers from detrimental thermal, hydraulic, mechanical and chemical processes; and (2) to retard the release of radionuclides from any waste container that fails. The bentonite should have a low permeability and a high sorption capacity.

These safety functions could be challenged by certain features, events and processes (FEPs) that may occur during the evolution of the disposal system. A consideration of how these FEPs may affect the safety functions can be used to identify and to prioritize the important areas for research on bentonite. We identify these important areas (which include hydration of compacted bentonite, illitization and erosion of bentonite), and describe how they are being investigated in current international research on bentonite.

The Äspö EBS Task Force is a collaborative international project designed to carry out research on bentonite. In 2011, the Nuclear Decommissioning Authority Radioactive Waste Management Directorate joined the EBS Task Force partly to benefit from its collective experience. The work of the EBS Task Force is split into two research subareas: (1) the THM subarea, which includes tasks to understand homogenization of bentonite as it resaturates, to investigate the hydraulic interaction between bentonite and fractured rock, and to model in situ experiments; and (2) the THC subarea, which includes tasks to investigate the issue of understanding transport through bentonite, and to model in situ experiments. In particular, the bentonite rock interaction experiment is a large-scale in situ experiment concerned with understanding groundwater exchange across bentonite rock interfaces, with the objective of establishing better understanding of bentonite wetting. In this paper, we describe our work to model the spatial and temporal resaturation of bentonite buffer in a fractured host rock.

Over the last five decades private and national energy programmes worldwide have been producing a variety of radioactive wastes. One of the safest ways of disposing of this waste is to bury it deep underground in purpose-built geological disposal facilities. Currently, there is no operating geological repository in Europe for high-level waste but the goal of the IGD-TP is that the first repository shall be fully operational before the year 2025. Several studies and experiments are ongoing at various potential repository sites in Europe with the goal to establish general approaches that can be adapted for any country in need of a geological repository.

The Swedish Nuclear Fuel and Waste Management Co (SKB) in Sweden and Posiva Oy in Finland are developing a method for geological disposal of high-level long-lived nuclear waste in crystalline rock, the KBS-3 method. KBS-3V (vertical) is both organizations reference design, but KBS-3H (horizontal) emplacement is also being researched as a potential alternative. Of high importance in the development is demonstrating the technical feasibility in situ of safe and reliable construction, manufacturing, disposal and sealing of such geological disposal facilities. Parts of these demonstrations are carried out under the framework of EurAtom/FP7 and one of these projects is the LUCOEX project where SKB is demonstrating horizontal emplacement, the Multi Purpose Test (MPT), and Posiva is demonstrating vertical buffer installation processes.

The MPT includes the key components of the horizontal design and comprises all essential steps; manufacturing of the full-scale components, their assembly, installation in the drift and monitoring of the early buffer evolution. The MPT installation was successfully performed in late 2013. By combining the components, an initial verification of the design implementation has been achieved. At the same time, integrating the components has meant the recognition of some design weaknesses and the design will be updated accordingly.

Posiva's KBS-3V buffer installation equipment that places buffer blocks with high precision in vertical deposition holes is currently being developed and will be tested during 2014 and 2015 in real underground conditions. The machine uses vacuum lifting tools for moving the buffer blocks and laser scanning technology to position both the machine and blocks. Functionality of the concept and equipment selected will be confirmed by the tests and the installation tests will provide important information about the suitability of the selected buffer dimensions and tolerances.

In the deep geological disposal of nuclear waste in crystalline rock, erosion of the bentonite buffer may occur during periods of glaciation. Previous researchers have examined the mechanism and rates of extrusion and erosion for purified montmorillonite samples in smooth planar fractures. In this paper, we investigate the influence of using MX-80 material (as delivered, i.e. including accessory minerals) and a naturally varying aperture on bentonite erosion. A bespoke fracture flow cell was constructed for this purpose and flow through conducted with deionized water. Throughout the experiment, gravimetric analysis was undertaken on the effluent and the swelling pressure of the bentonite monitored. Quantitative image analysis of the extrusion process was also undertaken. When the swelling pressure data were analysed, alongside both the oscillations in erosion rate and the area of the accessory-mineral ring, a two-stage mechanism governing the erosion process became apparent. Once an accessory-mineral ring had formed at the edge of the extruded material, further increases in swelling pressure resulted in a breach in the accessory-mineral ring, triggering an erosive period during which, the mineral ring was supplemented with additional minerals. The cycle repeated until the ring was sufficiently strong that it remained intact. This observed process results in erosion rates one order of magnitude less than those currently used in long-term safetycase calculations.

Compacted bentonite is to be used as a buffer material between waste canisters and the bedrock in the deep geological disposal of high-level nuclear waste in several countries. In spite of the fact that such large bentonite systems have long equilibration times, estimation of the material properties and performance in repository conditions is often based on short-term, laboratory-scale experiments. Sample-preparation procedures in these experiments may differ from the natural evolution of the bentonite in the repository, however, affecting the bentonite properties. The present study reports the influence on the structure of clay tactoids of four different preparation procedures of water-saturated, compacted MX-80 bentonite samples using four target dry bulk densities. Small-angle X-ray scattering was used to illustrate the differences between the samples. The different treatments of the bentonite samples may lead to different structural features. Clear differences between low-density samples prepared using different procedures were observed. The influence of the preparation methods was less, but still noticeable, for the high-density samples.

The study investigated housing tenure as a factor moderating the effects of loneliness and socio-economic status (SES) on quality of life (control and autonomy, pleasure, and self-realisation) over a two-year period for older adults. Data from the 2010 and 2012 waves of the New Zealand Health, Work, and Retirement Study were analysed. Using case-control matching, for each tenant (N = 332) we selected a home-owner (N = 332) of the same age, gender, ethnicity, SES, working status and urban/rural residence. Structural equation modelling was employed to examine the impact of SES, housing tenure and loneliness on quality of life over time. Emotional loneliness exerted a significant negative main effect on control and autonomy and pleasure. Tenure and SES influenced control and autonomy, but not pleasure or self-realisation. Tenure moderated the effect of emotional loneliness on control and autonomy, with the negative effect of emotional loneliness weaker for home-owners compared to renters. Tenure moderated the effect of SES on control and autonomy, with the positive impact of SES stronger for home-owners. Findings suggest that owners capitalise on their material and financial resources more than tenants in terms of their quality of life. In addition, home-ownership can act as a protective factor against the harmful effects of emotional loneliness in old age.

When discs of red beet (Beta vulgaris L.) root were immersed in various concentrations of glyphosate [N-(phosphonomethyl)glycine] either in phosphate (pH 6.8) or citrate (pH 6.2) buffer, no efflux of betacyanin occurred even after 1 week. This suggests that glyphosate had little or no effect on membrane permeability. When beet discs were immersed in distilled water containing glyphosate, the betacyanin efflux increased with time and concentration. Measurement of pH indicated that the solutions were strongly acidic at first, but tended to approach a pH of 6.0 over 8 h, after which time betacyanin efflux slowed down or stopped. The tissue was able to buffer the solutions sufficiently to prevent further efflux. When tissue discs were immersed in a series of citrate buffer ranging from pH 3 to 6.2, efflux occurred at pH 3 and slightly at pH 6.2. Efflux was not altered significantly with the addition of glyphosate.

Increasing the pH of the spray water to solubilize the weak acid herbicide nicosulfuron and then decreasing pH below its pKa so that it converts into a neutral form enhances biological activity under some conditions. The water-dispersible granule formulation of nicosulfuron starts as dispersed particles. Adding 1% wt/wt K3PO4 solubilizes nicosulfuron and increases its activity compared to its dispersion without base. The type of buffer and the surfactant HLB or hydrophilic lipophilic balance, a measure of the molecular balance of the hydrophilic and lipophilic groups, altered the activity of nicosulfuron. Adding 1% wt/wt K3PO4 increases the pH, and the optimum HLB ranged from 13 to 17 on large crabgrass. Adding 1% wt/wt H3PO4 reduces the pH and lowers the optimum HLB range from 10 to 14 on large crabgrass. Adding the acidic buffer converts the solubilized nicosulfuron into its neutral form and increases activity under some surfactant conditions. Thus, neutral nicosulfuron is more active with lipophilic surfactants, while ionic nicosulfuron is more active with hydrophilic surfactants. When tested on other species, low HLB surfactants are the most active at low pH. These results support the concept that the physicochemical properties of the herbicide, adjuvants, and weed species should be matched for optimum activity.

Adjuvants that increase the pH of the spray mixture and solubilize nicosulfuron can enhance biological activity under specific conditions. These conditions include high nicosulfuron rates, difficult-to-control weeds, low spray volumes, and initially acidic spray conditions. The most effective pH adjusters are tribasic potassium phosphate, sodium carbonate, and triethanolamine. In low spray volumes, these adjusters make the spray mixture alkaline and often enhance the activity of nicosulfuron on common cocklebur and large crabgrass. Alkaline conditions rapidly dissolve the sulfonylurea particles and enhance activity with crop oil concentrate, modified seed oil, and hydrophilic nonionic surfactants. pH adjusters did not enhance activity with lipophilic surfactants. Ammonium sulfate slightly increases the pH of spray mixtures and increases nicosulfuron activity depending on species, adjuvant type, and pH adjuster. These results generally support the concept that herbicide solubilization is necessary to maximize the foliar activity.

Inorganic oxides exhibit numerous applications influenced by particle size and morphology. While industrial methods for forming oxides involve harsh conditions, nature has the ability to form intricate structures of silicon dioxide (silica) using small peptides and polyamines under environmentally friendly conditions. Recent research has demonstrated that these biomaterials will precipitate other inorganic oxides, such as titanium dioxide (titania). Using the diatom-derived R5 peptide, new peptides with systematic changes (e.g., truncation and substitution) in the R5 primary structure were surveyed for reactivities and the impact on the morphology of the titania. The results demonstrated that (i) basic residues are vital to initiating the reaction, and a minimum local concentration is necessary to sustain the precipitation, (ii) residues containing hydroxyl side chains are important to imparting morphological control on the precipitate, and (iii) buffer conditions can dramatically alter both precipitation and morphology.

The brown macroalga Laminaria saccharina exhibits a type of HCO3− utilization that could be almost completely inhibited either by proton buffers or by acetazolamide, an inhibitor of extracellularly operating carbonic anhydrase. This means of HCO3− utilization featured properties similar to direct HCO3− uptake in that photosynthetic rates were proportional to the HCO3− concentration of the seawater over a wide pH range (pH 7·0–9·5). Despite this, it must be characterized as carbonic anhydrase-catalysed external HCO3− dehydration and not as direct HCO3− uptake. A mechanism is suggested involving a CO2-concentrating capability located at the cell membrane. This mechanism, which might be common in brown algae, is suggested to have an adaptational advantage in colder regions of the sea (as compared with the direct HCO3− uptake of green macroalgae). This means of HCO3− utilization is inhibited even by fairly low concentrations of buffer, with consequences for the interpretation of earlier experimental studies on L. saccharina (and possibly other brown algae). These consequences relate both to ecology (e.g. determination of inorganic C affinity) and physiology (e.g. assessing mechanisms for inorganic C uptake).