Mineral Saturation State and the Implications for Reaction Rates in Reactive Transport Modeling of CO2 Storage

AbstractThe injection of CO2 results in a decrease in the pH and a corresponding change from conditions at or near saturation between the aqueous and mineral phases to one of undersaturation. With growing evidence that many mineral dissolution reaction rates are dependent on the proximity to equilibrium, we seek to address the extent to which a fluid becomes undersaturated with respect to the mineral phases present through the addition of CO2. It turns out, for many minerals with a dissolution reaction that is pH dependent, that the saturation index changes little from the initially saturated condition. This indicates that reaction rates commonly used in reaction path and reactive transport models of carbon storage are not sufficiently representative of the dissolution mechanism that dominates and tend to overestimate the amount of reaction with time

Anomalous magnetic noise in an imperfectly flat landscape in the topological magnet Dy2Ti2O7.

Noise generated by motion of charge and spin provides a unique window into materials at the atomic scale. From temperature of resistors to electrons breaking into fractional quasiparticles, "listening" to the noise spectrum is a powerful way to decode underlying dynamics. Here, we use ultrasensitive superconducting quantum interference device (SQUIDs) to probe the puzzling noise in a frustrated magnet, the spin-ice compound Dy2Ti2O7 (DTO), revealing cooperative and memory effects. DTO is a topological magnet in three dimensions-characterized by emergent magnetostatics and telltale fractionalized magnetic monopole quasiparticles-whose real-time dynamical properties have been an enigma from the very beginning. We show that DTO exhibits highly anomalous noise spectra, differing significantly from the expected Brownian noise of monopole random walks, in three qualitatively different regimes: equilibrium spin ice, a "frozen" regime extending to ultralow temperatures, and a high-temperature "anomalous" paramagnet. We present several distinct mechanisms that give rise to varied colored noise spectra. In addition, we identify the structure of the local spin-flip dynamics as a crucial ingredient for any modeling. Thus, the dynamics of spin ice reflects the interplay of local dynamics with emergent topological degrees of freedom and a frustration-generated imperfectly flat energy landscape, and as such, it points to intriguing cooperative and memory effects for a broad class of magnetic materials

A fresh approach to investigating CO2 storage: Experimental CO2-water-rock interactions in a low-salinity reservoir system

The interactions between CO2, water and rock in low-salinity host formations remain largely unexplored for conditions relevant to CO2 injection and storage. Core samples and sub-plugs from five Jurassic-aged Surat Basin sandstones and siltstones of varying mineralogy have been experimentally reacted in low-salinity water with supercritical CO2 at simulated in situ reservoir conditions (P=12MPa and T=60°C) for 16days (384h), with a view to characterising potential CO2-water-rock interactions in fresh or low-salinity potential siliclastic CO2 storage targets located in Queensland, Australia. CO2-water-rock reactions were coupled with detailed mineral and porosity characterisation, obtained prior to and following reaction, to identify changes in the mineralogy and porosity of selected reservoir and seal rocks during simulated CO2 injection. Aqueous element concentrations were measured from fluid extracts obtained periodically throughout the experiments to infer fluid-rock reactions over time. Fluid analyses show an evolution of dissolved concentration over time, with most major (e.g. Ca, Fe, Si, Mg, Mn) and minor (e.g. S, Sr, Ba, Zn) components increasing in concentration during reaction with CO2. Similar trends between elements reflect shared sources and/or similar release mechanisms, such as dissolution and desorption with decreasing pH. Small decreases in concentration of selected elements were observed towards the end of some experiments; however, no precipitation of minerals was directly observed in petrography. Sample characterisation on a fine scale allowed direct scrutiny of mineralogical and porosity changes by comparing pre- and post-reaction observations. Scanning electron microscopy and registered 3D images from micro-computed tomography (micro-CT) indicate dissolution of minerals, including carbonates, chlorite, biotite members, and, to a lesser extent, feldspars. Quantitative mineral mapping of sub-plugs identified dissolution of calcite from carbonate cemented core, with a decrease in calcite content from 17vol.% to 15vol.% following reaction, and a subsequent increase in porosity of 1.1vol.%. Kinetic geochemical modelling of the CO2-water-rock experiments successfully reproduced the general trends observed in aqueous geochemistry for the investigated major elements. After coupling experimental geochemistry with detailed sample characterisation and numerical modelling, expected initial reactions in the near-well region include partial dissolution and desorption of calcite, mixed carbonates, chloritic clays and annite due to pH decrease, followed in the longer-term by dissolution of additional silicates, such as feldspars. Dissolution of carbonates is predicted to improve injectivity in the near-well environment and contribute to the eventual re-precipitation of carbonates in the far field

A Real Space Description of Field Induced Melting in the Charge Ordered Manganites: II. the Disordered Case

We study the effect of A site disorder on magnetic field induced melting of charge order (CO) in half doped manganites using a Monte-Carlo technique. Strong A-site disorder destroys CO even without an applied field. At moderate disorder, the zero field CO state survives but has several intriguing features in its field response. Our spatially resolved results track the broadening of the field melting transition due to disorder and explain the unusual dependence of the melting scales on bandwidth and disorder. In combination with our companion paper on field melting of charge order in clean systems we provide an unified understanding of CO melting across all half doped manganites.Comment: 9 pages, pdflatex, 10 embedded png fig

Impact of actin filament stabilization on adult hippocampal and olfactory bulb neurogenesis

Rearrangement of the actin cytoskeleton is essential for dynamic cellular processes. Decreased actin turnover and rigidity of cytoskeletal structures have been associated with aging and cell death. Gelsolin is a Ca(2+)-activated actin-severing protein that is widely expressed throughout the adult mammalian brain. Here, we used gelsolin-deficient (Gsn(-/-)) mice as a model system for actin filament stabilization. In Gsn(-/-) mice, emigration of newly generated cells from the subventricular zone into the olfactory bulb was slowed. In vitro, gelsolin deficiency did not affect proliferation or neuronal differentiation of adult neural progenitors cells (NPCs) but resulted in retarded migration. Surprisingly, hippocampal neurogenesis was robustly induced by gelsolin deficiency. The ability of NPCs to intrinsically sense excitatory activity and thereby implement coupling between network activity and neurogenesis has recently been established. Depolarization-induced [Ca(2+)](i) increases and exocytotic neurotransmitter release were enhanced in Gsn(-/-) synaptosomes. Importantly, treatment of Gsn(-/-) synaptosomes with mycotoxin cytochalasin D, which, like gelsolin, produces actin disassembly, decreased enhanced Ca(2+) influx and subsequent exocytotic norepinephrine release to wild-type levels. Similarly, depolarization-induced glutamate release from Gsn(-/-) brain slices was increased. Furthermore, increased hippocampal neurogenesis in Gsn(-/-) mice was associated with a special microenvironment characterized by enhanced density of perfused vessels, increased regional cerebral blood flow, and increased endothelial nitric oxide synthase (NOS-III) expression in hippocampus. Together, reduced filamentous actin turnover in presynaptic terminals causes increased Ca(2+) influx and, subsequently, elevated exocytotic neurotransmitter release acting on neural progenitors. Increased neurogenesis in Gsn(-/-) hippocampus is associated with a special vascular niche for neurogenesis