Fluid-rock interactions in a carbon storage site analogue, Green River, Utah

Pagination differs from hardbound copy deposited in Cambridge University Library.Reactions between CO2-charged brines and reservoir minerals might either enhance the long-term storage of CO2 in geological reservoirs or facilitate leakage by corroding cap rocks and fault seals. Modelling the progress of such reactions is frustrated by uncertainties in the absolute mineral surface reaction rates and the significance of other rate limiting steps in natural systems. This study uses the chemical evolution of groundwater from the Jurassic Navajo Sandstone, part of a leaking natural accumulation of CO2 at Green River, Utah, in the Colorado Plateau, USA, to place constraints on the rates and potential controlling mechanisms of the mineral-fluid reactions,under elevated CO2 pressures, in a natural system. The progress of individual reactions, inferred from changes in groundwater chemistry is modelled using mass balance techniques. The mineral reactions are close to stoichiometric with plagioclase and K-feldspar dissolution largely balanced by precipitation of clay minerals and carbonate. Mineral modes, in conjunction with published surface area measurements and flow rates estimated from hydraulic head measurements, are then used to quantify the kinetics of feldspar dissolution. Maximum estimated dissolution rates for plagioclase and K-feldspar are 2x10-14 and 4x10-16 mol·m-2·s-1, respectively. Fluid ion-activity products are close to equilibrium (e.g. DGr for plagioclase between -2 and -10 kJ/mol) and lie in the region in which mineral surface reaction rates show a strong dependence on DGr. Local variation in DGr is attributed to the injection and disassociation of CO2 which initially depresses silicate mineral saturation in the fluid, promoting feldspar dissolution. With progressive flow through the aquifer, feldspar hydrolysis reactions consume H+ and liberate solutes to solution which increase mineral saturation in the fluid and rates slow as a consequence. The measured plagioclase dissolution rates at low DGr would be compatible with far-from-quilibrium rates of ~1x10-13 mol·m-2·s-1 as observed in some experimental studies. This suggests that the discrepancy between field and laboratory reaction rates may in part be explained by the differences in the thermodynamic state of natural and experimental fluids, with field-scale reactions occurring close to equilibrium whereas most laboratory experiments are run far-from-equilibrium. Surface carbonate deposits and cementation within the footwall of the local fault systems record multiple injections of CO2 into the Navajo Aquifer and leakage of CO2 from the site over ca. 400,000 years. The d18O, d13C and 87Sr/86Sr of these deposits record rapid rates of CO2 leakage (up to ~1000 tonnes/a) following injection of CO2, but rates differ by an order of magnitude between each fault, due to differences in the fault architecture. Elevated pCO2 enhances rates of feldspar dissolution in the host aquifer and carbonate precipitation in fracture conduits. Silicate mineral dissolution rates decline and carbonate precipitation rates increase as pH and the CO2 charge dissipate. The Sr/Ca of calcite cements record average precipitation rates of ~2x10-6 mol/m2/s, comparable to laboratory derived calcite precipitation rates in fluids with elevated Mn/Ca and Fe/Ca, at cc of ~1 to 3. This suggests that far-from-equilibrium carbonate precipitation, which blocks fracture conduits and causes the leaking system to self-seal, driven by CO2 degassing in the shallow subsurface, can be accurately modeled with laboratory derived rates. Sandstones altered in CO2 leakage conduits exhibit extensive dissolution of hematite grain coatings and are chemically bleached as a result. Measurements of Eh-pH conditions in the modern fluid, and modeling of paleo-Eh-pH conditions using calcite Fe and Mn concentrations, suggests that the CO2-charged groundwaters are reducing, due to their low dissolved O2 content and that pH suppression due to high pCO2 is capable of dissolving and transporting large concentrations of metals. Exhumed paleo-CO2 reservoirs along the crest of the Green River anticline have been identified using volatile hosting fluid inclusions. Paleo-CO2-charged fluids mobilized hydrocarbons and CH4 from deeper formations, enhancing the reductive dissolution of hematite, which produced spectacular km-scale bleached patterns in these sediment.This work was funded by a post-graduate research grant from Shell Global Solutions International awarded to Niko Kampman

Fluid flow and CO2–fluid–mineral interactions during CO2-storage in sedimentary basins

Modelling the progress of geochemical processes in CO2 storage sites is frustrated by uncertainties in the rates of CO2 flow and dissolution, and in the rates and controlling mechanisms of fluid–mineral reactions that stabilise the CO2 in geological reservoirs. Dissolution of CO2 must be controlled by the complexities of 2-phase flow of CO2 and formation brines and the smaller-scale heterogeneities in the permeability in the reservoirs which increase the fluid contact areas. The subsequent fluid mineral reactions may increase storage security by precipitating CO2 in carbonate minerals but the consequences of fluid–mineral reactions on caprock rocks or potential leakage pathways up fault zones are less certain as the CO2-charged brines may either corrode minerals or decrease permeabilities by precipitating carbonates. Observations from CO2-injection experiments and natural analogues provide important constraints on the rates of CO2 and brine flow and on the progress of CO2 dissolution and mineral–fluid reactions. In these experiments brines in contact with the propagating plume appear to rapidly saturate with CO2. Dissolution of the CO2 drives the dissolution of oxide and carbonate minerals, on times scales of days to weeks. These reactions buffer fluid pH and produce alkalinity such that carbonate dissolution moves to carbonate precipitation over time-scales of weeks to months. The dissolution of Fe-oxide grain coatings and the release of Fe to solution is important in stabilising insoluble Fe–Mg–Ca carbonate minerals but the rate limiting step for carbonate mineral precipitation is the transport of CO2-charged brines and silicate mineral dissolution rates. Observations from CO2-EOR experiments and natural analogues suggest that the silicate mineral dissolution reactions are initially fast in the low pH fluids surrounding the CO2 plume but that reaction progress over months to years drives minerals towards thermodynamic equilibrium and dissolution rates slow over 2–5 orders of magnitude as equilibrium is approached. The sluggish dissolution of silicate minerals is likely to preside over the long-term fate of the CO2 in geological reservoirs. Observations from injection experiments and natural analogues suggest that the potentially harmful trace elements mobilised by the drop in pH are immobilised as adsorbed and precipitated phases as fluid pH is buffered across mineral reaction fronts. There are very few observations of caprock exposed to CO2-rich brines. Preliminary examination of core recently recovered from scientific drilling of a natural CO2 accumulation in Utah suggests that the diffusion of CO2 into reservoir caprocks drives dissolution of Fe-oxides but subsequent precipitation of carbonate minerals likely retards the diffusion distance of the CO2. At this site thin siltstone layers are shown to be effective seals to the CO2-charged fluids, which has significant implications for the long term security of CO2 in geological reservoirs

Kinetics of CO2-fluid-rock reactions in a basalt aquifer, Soda Springs, Idaho

The dissolution of silicate minerals by CO2-rich fluids and the subsequent precipitation of CO2 as carbonate minerals represent a means of permanently storing anthropogenic CO2 waste products in a solid and secure form. Modelling the progression of these reactions is hindered by our poor understanding of the rates of mineral dissolution–precipitation reactions and mineral surface properties in natural systems. This study evaluates the chemical evolution of groundwater flowing through a basalt aquifer, which forms part of the leaking CO2-charged system of the Blackfoot Volcanic Field in south-eastern Idaho, USA. Reaction progress is modelled using changes in groundwater chemistry by inverse mass balance techniques. The CO2-promoted fluid–mineral reactions include the dissolution of primary plagioclase, orthoclase, pyroxene and gypsum which is balanced by the precipitation of secondary albite, calcite, zeolite, kaolinite and silica. Mineral mole transfers and groundwater flow rates estimated from hydraulic head data are used to determine the kinetics of plagioclase and orthoclase feldspar dissolution. Plagioclase surface area measurements were determined using the evolution of the U-series isotope ratios in the groundwater and are compared to published surface area measurements. Calculated rates of dissolution for plagioclase range from 2.4 × 10−12 to 4.6 × 10−16 mol/m2/s and orthoclase from 2.0 × 10−13 to 6.8 × 10−16 mol/m2/s respectively. These feldspar reaction rates, correlate with the degree of mineral–fluid disequilibrium and are similar to the dissolution rates for these mineral measured in other natural CO2-charged groundwater systems

Estimating carbon dioxide residence time scales through noble gas and stable isotope diffusion profiles

The study of natural carbon dioxide reservoirs provides fundamental insight into processes involved in carbon capture and storage. However, the calculations of process rates such as dissolution of CO2 into formation water remain uncertain due to indirectly determined ages of the CO2 influx. The proposed ages for the Bravo Dome gas field in New Mexico, USA, vary from 56 ka to 1.5 Ma. Here we demonstrate that residence times can be estimated from simple modeling of noble gas and stable isotope diffusion profiles from the gas-water contact through the gas column. The Bravo Dome gas field shows a gradient in noble gas concentrations and isotopic ratios from east to west across the 70-km-wide field. A mantle-like end member with a 3He/4He (R/RA) ratio of up to 4.7 is found in the west in contrast to a groundwater end member with high concentrations of air- and crustal-derived noble gases in the east. The air- and crustal-derived noble gases decrease gradually toward the west. Stable isotope compositions (C and O) also vary across the field. Diffusion modeling of He, Ne, Ar, Kr, Xe, and δ13C data yield residence times for the CO2 between 14.1 ± 0.2 ka and 16.9 +1.1/–0.5 ka. This is far less than the previous estimates of 1.2–1.5 Ma based on apatite (U-Th)/He thermochronology, leading to a dissolution rate of 29,900 +11,800/–10,700 t/a to 35,900 ± 12,300 t/a, implying that 28% of the total emplaced CO2 dissolved. This new method can be applied to a wide variety of gas fields with variation in the concentration of groundwater-derived noble gases and allow a better assessment of the time scale of other diffusive fluid-fluid interactions

Validating reactive transport models of CO2-brine-rock reactions in caprocks using observations from a natural CO2 reservoir

Storage of anthropogenic CO2 in geological formations relies on impermeable caprocks as the primary seal preventing buoyant super-critical CO2 escaping. Although natural CO2 reservoirs demonstrate that CO2 may be stored safely for millions of years, uncertainty remains in predicting how caprocks will react with acid CO2-bearing brines. This uncertainty poses a challenge to the assessment of carbon capture and storage schemes. Prediction of caprock behaviour is based primarily on theoretical modelling and laboratory experiments. However, the reactive transport phenomena cannot be reproduced in laboratory experiments over sufficient timescales, theoretical models need calibration against observational data and existing studies on natural caprocks have not resolved mineral reactions. Here we report a detailed description of a stacked sequence of CO2 reservoir-caprock systems exposed to CO2-rich fluids over ∼ 105 years, a time-scale comparable with that needed for effective geological carbon storage. Fluid-mineral reactions in the base of multiple caprocks is driven by diffusion of CO2 and minor H2S from the underlying reservoirs. The reactions include dissolution of hematite, dolomite and K-feldspar and precipitation of Fe-bearing dolomite, gypsum, pyrite and illite over centimetre length-scales. The mineral dissolution reactions generate transient increases in porosity, as determined by neutron scattering measurements, but the propagation of mineral reaction fronts is retarded by the reaction stoichiometry and mineral precipitation. Modelling of the mineral reaction fronts shows that the alteration is sluggish, developing over a >104 year period. The results attest to the significance of transport-limited reactions to the long-term integrity of sealing behaviour in caprocks exposed to CO2

Kinetics of CO2-fluid-rock reactions in a basalt aquifer, Soda Springs, Idaho

The dissolution of silicate minerals by CO2-rich fluids and the subsequent precipitation of CO2 as carbonate minerals represent a means of permanently storing anthropogenic CO2 waste products in a solid and secure form. Modelling the progression of these reactions is hindered by our poor understanding of the rates of mineral dissolution–precipitation reactions and mineral surface properties in natural systems. This study evaluates the chemical evolution of groundwater flowing through a basalt aquifer, which forms part of the leaking CO2-charged system of the Blackfoot Volcanic Field in south-eastern Idaho, USA. Reaction progress is modelled using changes in groundwater chemistry by inverse mass balance techniques. The CO2-promoted fluid–mineral reactions include the dissolution of primary plagioclase, orthoclase, pyroxene and gypsum which is balanced by the precipitation of secondary albite, calcite, zeolite, kaolinite and silica. Mineral mole transfers and groundwater flow rates estimated from hydraulic head data are used to determine the kinetics of plagioclase and orthoclase feldspar dissolution. Plagioclase surface area measurements were determined using the evolution of the U-series isotope ratios in the groundwater and are compared to published surface area measurements. Calculated rates of dissolution for plagioclase range from 2.4 × 10−12 to 4.6 × 10−16 mol/m2/s and orthoclase from 2.0 × 10−13 to 6.8 × 10−16 mol/m2/s respectively. These feldspar reaction rates, correlate with the degree of mineral–fluid disequilibrium and are similar to the dissolution rates for these mineral measured in other natural CO2-charged groundwater systems

Mechanical weakening of a mudrock seal by reaction with CO2-charged fluids

The long-term interaction of CO2-charged fluids with low permeability cap rocks is important for seal integrity assessment. To address this potential risk, we studied long-term geomechanical changes in a reservoir seal due to fluid-rock interactions with CO2-charged fluids, focusing on a natural CO2 analogue near Green River, Utah, USA. The observed chemo-mechanical changes are on the millimeter scale, which required small-scale petrophysical, mineralogical, and micromechanical analyses. Results showed that over the 7 cm thick reaction front, the low permeability cap rock underwent mechanical weakening, as indicated by indentation tests. This weakening is inferred to be due to dissolution of dolomite and hematite, with the former leading to porosity increase, as shown by small-angle neutron scattering, while the latter likely led to loss of electrostatic forces between the clay particles. This resulted in loss of cohesion, compaction, and formation of bedding-parallel fractures. Microfracturing occurred in situ, as evidenced by fractures infilled with pyrite and gypsum. This study demonstrates that mechanical weakening of cap rocks might occur, but only over time scales of ∼100,000 yr and over small distances. Considering the thickness of cap rocks above CO2 storage reservoirs, we do not anticipate a considerable threat of losing containment integrity over time scales of hundreds to thousands of years as a result of these small-scale fluid-rock interactions

CYP1A2 polymorphism −1545C > T (rs2470890) is associated with increased side effects to clozapine

Background Cytochrome P450 1A2 gene (CYP1A2) polymorphisms have been suggested to be associated with increased side effects to antipsychotics. However, studies on this are scarce and have been conducted with either various antipsychotics or only in small samples of patients receiving clozapine. The aim of the present study was to test for an association between the CYP1A2 −1545C > T (rs2470890) polymorphism and side effects in a larger sample of patients during long-term clozapine treatment. Methods A total of 237 patients receiving clozapine treatment completed the Liverpool University Neuroleptic Side-Effect Rating Scale (LUNSERS) assessing clozapine-induced side effects. Of these patients, 180 completed the questionnaire satisfactorily, agreed to provide a blood sample, and were successfully genotyped for the polymorphism. Results The TT genotype of CYP1A2 polymorphism −1545C > T (rs2470890) was associated with significantly more severe side effects during clozapine treatment (p = 0.011). In a subanalysis, all seven types of side effects (sympathicotonia–tension; depression–anxiety; sedation; orthostatic hypotension; dermal side effects; urinary side effects; and sexual side effects) appeared numerically (but insignificantly) more severely among TT carriers. In addition, use of mood stabilizers was more common among patients with the TT genotype (OR = 2.63, p = 0.004). Conclusions This study has identified an association between the CYP1A2 polymorphism −1545C > T (rs2470890) and the occurrence of more severe clozapine side effects. However, these results should be regarded as tentative and more studies of larger sample sizes will be required to confirm the result.BioMed Central opean acces

Modelling of long-term along-fault flow of CO2 from a natural reservoir

Geological sequestration of CO2 requires the presence of at least one competent seal above the storage reservoir to ensure containment of the stored CO2. Most of the considered storage sites are overlain by low-permeability evaporites or mudrocks that form competent seals in the absence of defects. Potential defects are formed by man-made well penetrations (necessary for exploration and appraisal, and injection) as well as (for mudrocks) natural or injection-induced fracture systems through the caprock. These defects need to be de-risked during site selection and characterisation. A European ACT-sponsored research consortium, DETECT, developed an integrated characterisation and risk assessment toolkit for natural fault/fracture pathways. In this paper we describe the DETECT experimental-modelling workflow, which aims to be predictive for fault-related leakage quantification, and its application to a field case example for validation. The workflow combines laboratory experiments to obtain single-fracture stress-sensitive permeabilities; single-fracture modelling for stress-sensitive relative permeabilities and capillary pressures; fracture network characterisation and modelling for the caprock(s); upscaling of properties and constitutive functions in fracture networks; and full compositional flow modelling at field scale. We focus the paper on the application of the workflow to the Green River Site in Utah. This is a rare case of leakage from a natural CO2 reservoir, where CO2 (dissolved or gaseous) migrates along two fault zones to the surface. This site provides a unique opportunity to understand CO2 leakage mechanisms and volumes along faults, because of its extensive characterisation including a large dataset of present-day CO2 surface flux measurements as well as historical records of CO2 leakage in the form of travertine mounds. When applied to this site, our methodology predicts leakage locations accurately and, within an order of magnitude, leakage rates correctly without extensive history matching. Subsequent history matching achieves accurate leak rate matches within a-priori uncertainty ranges for model input parameters

A systematic investigation of the intrinsic flow properties of fractures using a combined 3D printing and micro-computed tomography approach

Geological storage operations spanning energy, nuclear material and carbon dioxide (CO2) storage, require meticulous understanding of the integrity of geological seals over a range of temporal and spatial scales. Fluid-conductive fault and fracture systems in otherwise low-permeability rocks may threaten seal performance and compromise subsurface storage projects. The understanding of these systems is complicated by the occurrence of anisotropic aperture distribution caused by inherent surface roughness. Difficulties predicting fluid flow through fractures stems from our limited understanding of the fundamental controls on their intrinsic permeabilities, and the prevalence, severity and complexity of hydromechanical responses arising from the coupling of multiphase flow, pore pressure and effective stress. In this study, we systematically investigated the effect of surface roughness on the transport properties of 3D-printed (Acrylonitrile Butadiene Styrene resin) fracture surfaces with micrometre surface roughness distributions. We printed 11 separate fractures, 7 of which are synthetically generated self-affine surfaces encompassing a range of fractal dimensions (Df = 1.2 to 2.4) observed in nature. The remaining 4 are acquired from micrometre-scale surface scans from natural fractures within the Carmel mudrock, a caprock from a natural CO2 leakage site in Utah, USA. Fluid flow experiments using single (brine) and multiple fluids (decane and brine) are undertaken to investigate the fluid pathways and interactions between each phase across a range of effective stresses (5 to 25 bar). We investigate the interplay between multiphase flow dynamics, surface roughness and hydraulic aperture distribution to gain insight into the intrinsic transport properties of fractures with different origins of roughness. Experiments are performed and imaged using a micro-computed tomography scanner (EMCT; (Bultreys et al., 2016)), where the results can be used to further the understanding of the governing parameters influencing fracture transmissivity, while also constraining surface roughness inputs for single- and multiphase fracture flow models