Mineralogical controls on porosity and water chemistry during O2-SO2-CO2 reaction of CO2 storage reservoir and cap-rock core

Reservoir and cap-rock core samples with variable lithology's representative of siliciclastic reservoirs used for CO storage have been characterized and reacted at reservoir conditions with an impure CO stream and low salinity brine. Cores from a target CO storage site in Queensland, Australia were tested. Mineralogical controls on the resulting changes to porosity and water chemistry have been identified. The tested siliciclastic reservoir core samples can be grouped generally into three responses to impure CO-brine reaction, dependent on mineralogy. The mineralogically clean quartzose reservoir cores had high porosities, with negligible change after reaction, in resolvable porosity or mineralogy, calculated using X-ray micro computed tomography and QEMSCAN. However, strong brine acidification and a high concentration of dissolved sulphate were generated in experiments owing to minimal mineral buffering. Also, the movement of kaolin has the potential to block pore throats and reduce permeability. The reaction of the impure CO-brine with calcite-cemented cap-rock core samples caused the largest porosity changes after reaction through calcite dissolution; to the extent that one sample developed a connection of open pores that extended into the core sub-plug. This has the potential to both favor injectivity but also affect CO migration. The dissolution of calcite caused the buffering of acidity resulting in no significant observable silicate dissolution. Clay-rich cap-rock core samples with minor amounts of carbonate minerals had only small changes after reaction. Created porosity appeared mainly disconnected. Changes were instead associated with decreases in density from Fe-leaching of chlorite or dissolution of minor amounts of carbonates and plagioclase. The interbedded sandstone and shale core also developed increased porosity parallel to bedding through dissolution of carbonates and reactive silicates in the sandy layers. Tight interbedded cap-rocks could be expected to act as baffles to fluids preventing vertical fluid migration. Concentrations of dissolved elements including Ca, Fe, Mn, and Ni increased during reactions of several core samples, with Mn, Mg, Co, and Zn correlated with Ca from cap-rock cores. Precipitation of gypsum, Fe-oxides and clays on seal core samples sequestered dissolved elements including Fe through co-precipitation or adsorption. A conceptual model of impure CO-water-rock interactions for a siliciclastic reservoir is discussed

Understanding decay in marine calcifiers: Micro-CT analysis of skeletal structures provides insight into the impacts of a changing climate in marine ecosystems

Calcifying organisms and their exoskeletons support some of the most diverse and economically important ecosystems in our oceans. Under a changing climate, we are beginning to see alterations to the structure and properties of these exoskeletons due to ocean acidification, warming and accelerated rates of bioerosion. Our understanding has grown as a result of using micro‐computed tomography (μCT) but its applications in marine biology have not taken full advantage of the technological development in this methodology. We present a significant advancement in the use of this method to studying decalcification in a marine calcifier. We present a detailed workflow on best practice for μCT image processing and analysis of marine calcifiers, designed using coral skeletons subjected to acute, short‐term microbial bioerosion. This includes estimating subresolution microporosity and describing pore space morphological characteristics of macroporosity, in perforate and imperforate exoskeletons. These metrics are compared between control and bieroded samples, and are correlated with skeletal hardness as measured by nanoindentation. Our results suggest that using subresolution microporosity analysis improves the spatiotemporal resolution of μCT data and can detect changes not seen in macroporosity, in both perforate and imperforate skeletons. In imperforate samples, the mean size and relative number of pores in the macroporous portion of the images changed significantly where total macroporosity did not. The increased number of pores and higher microporosity are both directly related to a physical weakening of the calcareous exoskeletons of imperforate corals only. In perforate corals, increased macroporosity was accompanied by an overall widening of pore spaces though this did not correlate with sample hardness. These novel techniques complement traditional approaches and in combination demonstrate the potential for using μCT scanning to sensitively track the process of decalcification from a structural and morphological perspective. Importantly, these approaches do not necessarily rely on ultra‐high resolution (i.e. single micron) scans and so maintain the accessibility of this technology. The continued optimization of these tools for a variety of marine calcifiers will advance our understanding of the effect of climate change on marine biogenic calcified structures.Australian Research Council, Grant/Award Number: DP180103199; International Coral Reef Societ

Fractal Analysis Methods for Solid Alkane Monolayer Domains at SiO 2 /Air Interfaces

A systematic evaluation of various fractal analysis methods is essential for studying morphologies of finite and noisy experimental patterns such as domains of long chain alkanes at SiO2/air interfaces. The derivation of trustworthy fractal dimensions crucially relies on the definition of confidence intervals for the assumed scaling range. We demonstrate that the determination of the intervals can be improved largely by comparing the scaling behavior of different morphological measures (area, boundary, curvature). We show that the combination of area and boundary data from coarse-grained structures obtained with the box-counting method reveals clear confidence limits and thus credible morphological data. This also holds for the Minkowski density method. It also reveals the confidence range. Its main drawback, the larger swing-in period at the lower cutoff compared to the box-counting method, is compensated by more details on the scaling behavior of area, boundary, and curvature. The sandbox method is less recommendable. It essentially delivers the same data as box-counting, but it is more susceptible to finite size effects at the lower cutoff. It is found that the domain morphology depends on the surface coverage of alkanes. The individual domains at low surface coverage have a fractal dimension of ≈ whereas at coverages well above ≈the scaling dimension is 2 with a large margin of uncertainty at ≈coverage. This change in morphology is attributed to a crossover from a growth regime dominated by diffusion-limited aggregation of individual domains to a regime where the growth is increasingly affected by annealing and the interaction of solid growth fronts which approach each other and thus compete for the alkane supply

Influence of wood's anatomical and resin traits on the radial permeability of the hybrid pine (Pinus elliottii x Pinus caribaea) wood in Australia

Wood permeability has a major effect on industrial wood processing and utilization. Wood anatomy and resin influence the permeability of wood. Understanding and manipulating these influences is important to optimize the manufacture and use of forest products. This study investigated the relationships between wood anatomical traits, radial permeability, and resin content of samples collected from 19-year-old hybrid pines (Pinus elliottii var. elliottii x Pinus caribaea var. hondurensis) from Queensland, Australia. The earlywood tracheid tangential lumen diameter and axial resin canal diameter were statistically positively correlated with radial permeability. The heartwood proportion and the frequency of axial resin canals were statistically negatively correlated with radial permeability and positively correlated with resin content. The axial resin canal diameter, sapwood proportion, latewood content, ray frequency, and earlywood tracheid lumen diameter increased from pith to bark, whereas the axial resin canal frequency decreased. Resin was found distributed throughout the wood microstructure, from pith to bark in many samples, and in both heartwood and sapwood. However, there was a much greater quantity of resin in heartwood and wood from the middle (inner radius) of the tree, with widespread occurrence of resin impregnation in the axial tracheids

Maximising the value of digital core analysis for carbon sequestration site assessment: final report on geochemical reactivitiy studies of core material using ScCO2. Technical report for Project 7-0311-0128, Sub-project 5: undertake time series (4D) imaging and conventional experimental studies to measure geochemical reactivity and dissolution trapping capacity of core material using supercritical CO2

Performed time-step 3D imaging before and after geochemical reaction with CO2:brine Performed pore-scale 3D imaging before and after reaction of the reservoir, seal and over-lying formation. Pure CO2 and mixed gas containing SO2 and O2 were tested. The images show some localised changes including the dissolution of some carbonate minerals, degradation of some minerals and precipitation of others

Influence of Wood’s Anatomical and Resin Traits on the Radial Permeability of the Hybrid Pine (Pinus elliottii× Pinus caribaea) Wood in Australia

Wood permeability has a major effect on industrial wood processing and utilization. Wood anatomy and resin influence the permeability of wood. Understanding and manipulating these influences is important to optimize the manufacture and use of forest products. This study investigated the relationships between wood anatomical traits, radial permeability, and resin content of samples collected from 19-year-old hybrid pines (Pinus elliottii var. elliottii × Pinus caribaea var. hondurensis) from Queensland, Australia. The earlywood tracheid tangential lumen diameter and axial resin canal diameter were statistically positively correlated with radial permeability. The heartwood proportion and the frequency of axial resin canals were statistically negatively correlated with radial permeability and positively correlated with resin content. The axial resin canal diameter, sapwood proportion, latewood content, ray frequency, and earlywood tracheid lumen diameter increased from pith to bark, whereas the axial resin canal frequency decreased. Resin was found distributed throughout the wood microstructure, from pith to bark in many samples, and in both heartwood and sapwood. However, there was a much greater quantity of resin in heartwood and wood from the middle (inner radius) of the tree, with widespread occurrence of resin impregnation in the axial tracheids

Potassium silicate alteration in porphyry copper-gold deposits: a case study at the giant maar-diatreme hosted Grasberg deposit, Indonesia

Potassium silicate alteration is a hallmark of the porphyry copper deposits that supply two thirds of the world's annual copper demand. These deposits formed in the cores of calc-alkaline to alkaline volcanic systems from the flux of magmatic gas that transported copper and other metals from source to the surface. The giant 3.2 Ma Grasberg Cu[sbnd]Au deposit formed within a maar-diatreme complex following a resurgence in magmatism. The defined resources of this deposit occur from a few hundred metres depth to 1.7 km below the paleosurface which, uniquely in this deposit, is partially preserved as a section of maar tuffs. Potassium silicate alteration has commonly been interpreted as being the result of the addition of potassium to the porphyry copper host rocks via pervasive interaction with a large volume of a potassium-rich brine that is commonly presumed to be of magmatic origin. However, the data reported here show that alteration at the deposit scale is essentially isochemical with respect to the major rock-forming components and that only sulphur and the economic metals (Cu, Mo, Au, etc.) are added by flux of reactive magmatic gas containing SO2 and HCl from source intrusions at depth. Silicate solubilities are very low so that only a minor fraction of the total alkalis in the host rock are extracted by alteration reactions and then discharged at the paleo-surface. Reaction of the magmatic gas phase with plagioclase results in the coupled deposition of anhydrite (CaSO4) and disproportionation of SO2 to release H2S. The in-situ release of H2S immediately scavenges Cu and other chalcophile metals from the continuing magmatic gas flux to form the Cu-, Fe- and other sulphides that, in sufficient concentration, make up the economic reserve available to mining. The sequestration of Ca into anhydrite, along with deposition of silica into early quartz veins, increases the concentration of the other major components (K2O, Na2O, MgO, etc) in the remaining silicate assemblage within the porous host rock. The result is the development of intermingled potassium-enriched silicate and sulphur-rich (anhydrite-sulphide) sub-assemblages that constitute the mineralised phyllic or potassic alteration zones. These crystallise according to their pressure and depth into alteration assemblages dominated by potassic phyllosilicates, quartz and pyrite in the phyllic alteration zone, and alkali feldspar and phlogopitic-biotite plus minor andalusite and corundum in the central potassic zone. Dissolution and recrystallisation of primary magmatic biotite in the host rock releases K as well as Fe, the latter (along with amphibole and feldspar) providing iron for the formation of chalcopyrite, bornite and pyrite. The in-situ release of H2S through anhydrite formation, immediately scavenges Cu and other chalcophile metals from the continuing magmatic gas flux to form the Cu[sbnd]Fe[sbnd] sulphides that, in sufficient concentration, make up the economic reserve available to mining. Understanding of the alteration processes during porphyry copper formation also provides insights into gas-solid reactions processes inside active magmatic arc volcanoes but the magnitude of copper mineralisation is dependent on the original metal content of the source of the magmatic gas phase

Three-dimensional Imaging of Multiphase Flow in Porous Media

This paper reports progress in the 3D pore-scale micro-CT imaging of multiple fluid phases during drainage experiments in porous materials. Experiments performed on a sintered monodisperse bead pack and a Berea sandstone sample are described. It is observed that the residual (trapped) wetting phase in the sintered bead pack is present as pendular rings, bridges between adjacent grains and lenses within pore throats. Estimates of the residual wetting phase saturation are in accord with previous experiments and predictions on model bead packs. Relative permeabilities computed directly on the digitised images of the fluid phases are in good agreement with experimentally measured values for Berea sandstone. Two simple numerical methods for estimating two phase drainage saturation distributions directly from images are compared. Both methods give good agreement with the bead pack experiment. The match for Berea sandstone is poorer; differences may be due to variable wettability