Dissolution experiments in halite cores: comparisons in cavity shape and controls between brine and seawater experiments

There is an increasing need for underground storage of natural gas (and potentially hydrogen) to meet the UK’s energy demands and ensure its energy security. In addition, the growth of renewable energy technologies, such as wind power, will be facilitated by the development of grid-scale energy storage facilities to balance grid demand. One solution lies in creating large-scale compressed-air energy storage (CAES) facilities underground. Whilst a number of lithologies offer storage potential, only three operational CAES facilities exist in the UK. They are constructed in specifically designed solution-mined salt (halite) caverns, similar to those currently used for natural gas storage. The influences exerted on salt dissolution by petrology, structure and fabric during cavern construction are not fully understood, with some occurences of caverns with noncircular cross-sections being less than optimum for gas storage and especially CAES

Validation of a gravimetric PM2.5 impactor using particle sizing techniques

Particulate matter sampling was conducted at Ballidon Quarry, Ballidon, Derbyshire. The quarry is owned and managed by Tarmac Trading Ltd. (Tarmac). The monitoring station deployed comprised two DS500X gravimetric samplers fitted with PM2.5 impactors, that were placed side by side in the primary crusher shed during February 2016. Monitoring was conducted over three, seven day periods. Particulate matter from six filters and oversize particulate matter collected from the impactor plates were analysed by BGS on behalf of DustScan using Scanning Transmission Electron Microscopy and Laser Diffraction granulometry. The results of the work show that the DS500X fitted with a PM2.5 size selective impactor is capable of separating particles with a projected area diameter of ≤ 2.5 μm from ambient air, retaining themon filter media for subsequent quantification. The overall median particle size recorded on the filters was 0.46 μm, the mean was 0.74 μm and the 95th percentile was 2.15 μm (n = 6343). A number of observations were made during this study and included in the full report which should be considered when interpreting the results

Retention of chlorine-36 by a cementitious backfill

Radial diffusion experiments have been carried out to assess the migration of 36Cl, as chloride, through a cementitious backfill material. Further experiments in the presence of cellulose degradation products were performed to assess the effect of organic ligands on the extent and rate of chloride diffusion. Results show that breakthrough of 36Cl is dependent on chloride concentration: as the carrier concentration increases, both breakthrough time and the quantity retained by the cement matrix decreases. Experiments in the presence of cellulose degradation products also show a decrease in time to initial breakthrough. However, uptake at various carrier concentrations in the presence of organic ligands converges at 45% of the initial concentration as equilibrium is reached. The results are consistent with organic ligands blocking sites on the cement that would otherwise be available for chloride binding, though further work is required to confirm that this is the case. Post-experimental digital autoradiographs of the cement cylinders, and elemental mapping showed evidence of increased 36Cl activity associated with black ash-like particles in the matrix, believed to correspond to partially hydrated glassy calcium-silicate-sulfate-rich clinker

Unusual morphologies and the occurrence of pseudomorphs after ikaite (CaCO3•6H2O) in fast growing, hyperalkaline speleothem

Unusual speleothem, associated with hyperalkaline (pH>12) groundwaters have formed within a shallow, abandoned railway tunnel at Peak Dale, Derbyshire, UK. The hyperalkaline groundwaters are produced by the leaching of a thin layer (<2 m) of old lime kiln waste above the soil-bedrock surface above the tunnel by rainwater. This results in a different reaction and chemical process to that more commonly associated with the formation of calcium carbonate speleothems from Ca-HCO3-type groundwaters and degassing of CO2. Stalagmites within the Peak Dale tunnel have grown rapidly (averaging 33 mm y-1), following the closure of the tunnel 70 years ago. They have an unusual morphology comprising a central sub-horizontally-laminated column of micro- to nano-crystalline calcium carbonate encompassed by an outer sub-vertical assymetric ripple laminated layer. The stalagmites are largely composed of secondary calcite forming pseudomorphs (<1 mm) which we believe to be predominantly after the ‘cold climate’ calcium carbonate polymorph, ikaite (calcium carbonate hexahydrate: CaCO3•6H2O), with minor volumes of small (<5 μm) pseudomorphs after vaterite. The tunnel has a near constant temperature of 8-9°C which is slightly above the previously published crystallisation temperatures for ikaite (<6°C). Analysis of a stalagmite actively growing at the time of sampling, and preserved immediately within a dry nitrogen cryogenic vessel, indicates that following crystallisation of ikaite, decomposition to calcite occurs rapidly, if not instantaneously. We believe this is the first occurrence of this calcium carbonate polymorph observed within speleothem

Mineral reaction kinetics constrain the length scale of rock matrix diffusion

Mass transport by aqueous fluids is a dynamic process in shallow crustal systems, redistributing nutrients as well as contaminants. Rock matrix diffusion into fractures (void space) within crystalline rock has been postulated to play an important role in the transient storage of solutes. The reacted volume of host rock involved, however, will be controlled by fluid-rock reactions. Here we present the results of a study which focusses on defining the length scale over which rock matrix diffusion operates within crystalline rock over timescales that are relevant to safety assessment of radioactive and other long-lived wastes. Through detailed chemical and structural analysis of natural specimens sampled at depth from an active system (Toki Granite, Japan), we show that, contrary to commonly proposed models, the length scale of rock matrix diffusion may be extremely small, on the order of centimetres, even over timescales of millions of years. This implies that in many cases the importance of rock matrix diffusion will be minimal. Additional analyses of a contrasting crystalline rock system (Carnmenellis Granite, UK) corroborate these results

Interactions between Simulant Vitrified Nuclear Wastes and high pH solutions: A Natural Analogue Approach

This study details the characterization of a glass sample exposed to hyperalkaline water and calcium-rich sediment for an extended time period (estimated as 2-70 years) at a lime (CaO) waste site in the UK. We introduce this site, known as Peak Dale, in reference to its use as a natural analogue for nuclear waste glass dissolution in the high pH environment of a cementitious engineered barrier of a geological disposal facility. In particular, a preliminary assessment of alteration layer chemistry and morphology is described and the initiation of a long-term durability assessment is outlined

Non Linear Current Response of a Many-Level Tunneling System: Higher Harmonics Generation

The fully nonlinear response of a many-level tunneling system to a strong alternating field of high frequency $\omega$ is studied in terms of the Schwinger-Keldysh nonequilibrium Green functions. The nonlinear time dependent tunneling current $I(t)$ is calculated exactly and its resonance structure is elucidated. In particular, it is shown that under certain reasonable conditions on the physical parameters, the Fourier component $I_{n}$ is sharply peaked at $n=\frac {\Delta E} {\hbar \omega}$, where $\Delta E$ is the spacing between two levels. This frequency multiplication results from the highly nonlinear process of $n$ photon absorption (or emission) by the tunneling system. It is also conjectured that this effect (which so far is studied mainly in the context of nonlinear optics) might be experimentally feasible.Comment: 28 pages, LaTex, 7 figures are available upon request from [email protected], submitted to Phys.Rev.

Three-dimensional coherent X-ray diffraction imaging of a ceramic nanofoam: determination of structural deformation mechanisms

Ultra-low density polymers, metals, and ceramic nanofoams are valued for their high strength-to-weight ratio, high surface area and insulating properties ascribed to their structural geometry. We obtain the labrynthine internal structure of a tantalum oxide nanofoam by X-ray diffractive imaging. Finite element analysis from the structure reveals mechanical properties consistent with bulk samples and with a diffusion limited cluster aggregation model, while excess mass on the nodes discounts the dangling fragments hypothesis of percolation theory.Comment: 8 pages, 5 figures, 30 reference

Determining constraints imposed by salt fabrics on the morphology of solution-mined energy storage cavities, through dissolution experiments using brine and seawater in halite

Large-scale compressed air energy storage facilities offer one solution to the UK's energy demands, using solution-mined caverns in salt lithologies. For optimum gas storage efficiency, cavern geometry should ideally be smooth: spherical to cylindrical with a circular cross-section. However, such caverns are often irregular with marked asymmetry or ellipticity, and although the reasons for non-circular cross-sections developing during solution mining in some caverns can be related to, for example, the presence of interbedded lithologies, in other instances they are not fully understood. Cavities from dissolution experiments using five main end-member salt facies fabrics from the Triassic Preesall and Northwich Halite formations have been assessed to determine factors affecting cavity geometry, formation and variability in dissolution behaviour. Identical sets of experiments were performed on each fabric type, using two solution concentration strengths: brine and synthetic seawater. Comparison of experimental results using a combination of analytical and imaging techniques shows the extent to which the salt fabric and enhancement of features within the salt influence the resulting dissolution cavity. Observations show a visible increase in micropores within the adjacent halite matrix following dissolution. Smaller-scale features provide further insights into the dissolution processes, and salt fabric behaviour under different dissolution conditions. Supplementary material: A detailed description of methods is available at https://doi.org/10.6084/m9.figshare.c.428245