Mineral Precipitation Reactions Research Articles

Kinetics of In-Situ Calcium Magnesium Carbonate Precipitation and the Need for Desulfation in Seawater-Flooded Carbonate Reservoirs

Summary Mixing of incompatible injection and formation brines leads to the deposition of inorganic sulfate scales such as barite, celestite, and anhydrite in and around production wells. This process is well documented in seawater-flooded clastic reservoirs. One technique to avoid the resulting formation damage is to remove sulfate from seawater before injection using nanofiltration; however, this process is costly. We identify in this paper that it may not always be necessary in higher-temperature carbonate reservoirs. In this paper, we describe the use of reactive transport reservoir simulation to investigate the impact of carbon dioxide (CO2) partitioning and changes in pH, ionic concentrations, and temperature on carbonate reactivity and the sulfate scaling risk in waterflooded carbonate reservoirs. Dissolution and precipitation of calcite, dolomite, gypsum, anhydrite, barite, and celestite are all modeled and found to be coupled through (various) common ion effects. The produced brine compositions are used to calculate the saturation ratios (SRs) and mass of precipitate that may form in the production system. Sensitivity to mineral reaction kinetics, particularly for the dolomite reactions, is accounted for. Results identify that there is a strong relationship between calcite dissolution and dolomite (or other calcium/magnesium carbonate mineral) precipitation reactions, which drive each other and are affected by the availability of CO2 in the residual oil phase. This evolves over time, and as the thermal front propagates, impacts the concentration of calcium and magnesium in the brines traversing the reservoir. Temperature changes around the injection wellbore impact CO2 and mineral solubilities. The concentration of calcium in the displaced brine mix is thus determined more by contact with rock and temperature than by mixing between injection and formation brines. Depending on location relative to the thermal front, this may lead to gypsum or anhydrite precipitation, thereby stripping sulfate out of the injection brine. Thus, the sulfate scaling risk at the production wells is significantly reduced by this sulfate depletion process: The sulfate is stripped out of the seawater as it warms up in the reservoir before it mixes extensively with the formation water and significantly before any mixture of the two brines reaches the production zone. Thus, any loss of permeability is restricted to deep within the reservoir, where the pore volume (PV) that can accommodate mineral precipitation is very large. In this work, we identify that for carbonate reservoirs above 90–100°C, stripping of sulfate due to coupled mineral reactions may reduce or eliminate the need for use of a sulfate reduction plant (SRP). The process is modeled for the first time, accounting for the impact of CO2 partitioning and thermal front propagation. Knowledge of the kinetics of calcium/magnesium carbonate precipitation is shown to be critical in predicting the extent of sulfate depletion.

Geochemical evaluation of Washita-Fredericksburg formation as a carbon storage reservoir

Geological carbon sequestration is a promising technique to reduce atmospheric greenhouse gas emissions. The Washita-Fredericksburg formation in the southeastern United States is being considered as a prospective storage formation. This requires understanding the geochemical impact of CO2 injection on the formation, which is the focus of this work. Here, sandstone samples from the Washita-Fredericksburg formation are analyzed to understand their overall mineralogical composition and the potential geochemical processes that might occur following CO2 injection. Powder X-ray diffraction (XRD) analysis, Scanning Electron Microscopy (SEM) imaging, and image analysis were used to identify mineral phases. SEM images were processed to create a segmented mineral map, which was then used to calculate mineral volume fractions and porosity. Results show that the sample has a porosity of 20% and is mainly composed of quartz, K-feldspar, muscovite, and clays. Accessory minerals such as titanite were also found. Reactive transport models were constructed to assess potential CO2-brine-mineral interactions following CO2 injection. Simulation results suggest that the overall extent of mineral dissolution and precipitation reactions over 10,000 days is limited, with muscovite dissolution increasing porosity to 22%. Limited mineral reactions suggest more injected CO2 will exist in free and dissolved forms, which may require more extensive long-term monitoring.

An emulation-based approach for interrogating reactive transport models

Abstract. We present an emulation-based approach to understand the interactions among different chemical and biological processes modelled in environmental reactive transport models (RTMs) and explore how the parameterisation of these processes influences the results of multi-component RTMs. We utilise a previously published RTM consisting of 20 primary species, 20 secondary complexes, 17 mineral reactions, and 2 biologically mediated reactions; this RTM describes bio-stimulation using sediment from a contaminated aquifer. We choose a subset of the input parameters to vary over a range of values. The result is the construction of a new dataset that describes the model behaviour over a range of environmental conditions. Using this dataset to train a statistical model creates an emulator of the underlying RTM. This is a condensed representation of the original RTM that facilitates rapid exploration of a broad range of environmental conditions and sensitivities. As an illustration of this approach, we use the emulator to explore how varying the boundary conditions in the RTM describing the aquifer impacts the rates and volumes of mineral precipitation. A key result of this work is the recognition of an unanticipated dependency of pyrite precipitation on pCO2 in the injection fluid due to the stoichiometry of the microbially mediated sulfate reduction reaction. This complex relationship was made apparent by the emulator, while the underlying RTM was not specifically constructed to create such a feedback. We argue that this emulation approach to sensitivity analysis for RTMs may be useful in discovering such new coupled sensitives in geochemical systems and for designing experiments to optimise environmental remediation. Finally, we demonstrate that this approach can maximise specific mineral precipitation or dissolution reactions by using the emulator to find local maxima, which can be widely applied in environmental systems.

Evolution of Mineral-Accessible Surface Area Induced by Geochemical Reactions

Mineral dissolution and precipitation reactions occur in a wide range of porous media systems, driven by deviations from an equilibrium between solid and fluid phases. Reactions occur at mineral surfaces in contact with reactive fluids or accessible mineral surface areas. These mineral surface areas can be determined using a multiscale imaging approach and have been shown to improve the simulation of mineral reaction rates in porous media compared to other estimates of reactive surface area. As reactions progress, mineral surface area evolves, and reactive transport simulations often use a simplified model assuming spherical grains to estimate mineral surface area evolution. This, however, does not depict the evolution of reactive surfaces in porous media systems with varying mineral accessibility. This work aims to quantitatively assess the evolution of accessible mineral surface area in porous media for a multimineralic system undergoing mineral dissolution reactions induced by acid exposure. Before and after the reaction, accessible mineral surface areas are determined from 2D scanning electron microscopy, and 3D X-ray computed tomography imaging of a sandstone sample. The quantified evolution of accessible surface area is compared to the calculated mineral surface area evolution using current approaches. Results show an overall increase in total surface area due to the reaction; however, individual mineral surface areas may increase or decrease. Variation is observed in mineral surface area values measured from imaging and equations used in models. The evolution of mineral surface area is largely impacted by the total surface area as well as the pore connectivity rather than porosity and volume fraction evolution.

Comparison study of phase-field and level-set method for three-phase systems including two minerals

We investigate reactive flow and transport in evolving porous media. Solute species that are transported within the fluid phase are taking part in mineral precipitation and dissolution reactions for two competing mineral phases. The evolution of the three phases is not known a-priori but depends on the concentration of the dissolved solute species. To model the coupled behavior, phase-field and level-set models are formulated. These formulations are compared in three increasingly challenging setups including significant mineral overgrowth. Simulation outcomes are examined with respect to mineral volumes and surface areas as well as derived effective quantities such as diffusion and permeability tensors. In doing so, we extend the results of current benchmarks for mineral dissolution/precipitation at the pore-scale to the multiphasic solid case. Both approaches are found to be able to simulate the evolution of the three-phase system, but the phase-field model is influenced by curvature-driven motion.

The transformation of U(VI) and V(V) in carnotite group minerals during dissimilatory respiration by a metal reducing bacterium

Recent results from laboratory and field studies support that dissimilatory metal reducing (DMR) bacteria influence the fate and transport of uranium in anaerobic subsurface environments. To date, most research efforts have focused on the reduction of soluble U(VI) by DMR bacteria to form insoluble uraninite (UO2). Subsurface environments harbor, however, large reservoirs of U(VI) in solid or mineral form. Uranium that is structure-bound in minerals is expected to be more refractory to microbial reduction than soluble U, based on analogy with Fe respiration. The reducibility of U(VI) could impact the fate of U(IV) by controlling mineral precipitation reactions, which has implications for the long-term immobilization of U in subsurface environments. We studied anoxic cultures of Shewanella putrefaciens CN32 incubated with natural carnotite-group minerals by X-ray diffraction, electron microscopy, scanning transmission X-ray microscopy (STXM). Near-edge X-ray absorption fine structure (NEXAFS) spectroscopy measurements at U-N4,5, V-L2,3, and O-K edges on cultures incubated up to 10 months show that V(V) was reduced to V(IV), whereas U was not reduced. In contrast, V(V) and U(VI) in solution were both completely reduced to lower oxidation states by CN32, as precipitates within the exopolymer surrounding the bacteria. Assays for the toxicity of U and V to CN32 showed that biofilm formation was stimulated at 0.001 M U(VI), and growth was inhibited at concentrations of U(VI) greater than 0.001 M. Vanadium did not inhibit growth or stimulate biofilm formation at any concentration tested. Investigations of the bacteria-mineral and bacteria-metal interface at the nanometer and molecular scales provide new insights into the co-respiration of V and U that help explain their biogeochemical cycling and have implications for subsurface bioremediation of these elements.

Influence of Storage Period on the Geochemical Evolution of a Compressed Energy Storage System

Subsurface porous aquifers are being considered for use as reservoirs for compressed energy storage of renewable energy. In these systems, a gas is injected during times in which production exceeds demand and extracted for energy generation during periods of peak demand or scarcity in production. Current operational subsurface energy facilities use salt caverns for storage and air as the working gas. CO2 is potentially a more favorable choice of working gas where under storage conditions CO2 has high compressibility which can improve operational efficiency. However, the interaction of CO2 and brine at the boundary of the storage zone can produce a chemically active fluid which can result in mineral dissolution and precipitation reactions and alter the properties of the storage zone. This study seeks to understand the geochemical implications of utilization of CO2 as a working gas during injection, storage and extraction flow cycles. Here, reactive transport simulations are developed based on 7 h of injection, 11 h of withdrawal and 6 h of reservoir closure, corresponding to the schedule of the Pittsfield field test, for 15 years of operational life span to assess the geochemical evolution of the reservoir. The evolution in the storage system is compared to a continuously cyclic system of 12 h injection and extraction. The result of the study on operational schedule show that mineral reactivity occurs at the inlet of the domain. Furthermore, the porosity of the inner domain is preserved during the cycling of CO2 acidified brine for both systems.

Jacobian Free Methods for Coupling Transport with Chemistry in Heterogenous Porous Media

Reactive transport plays an important role in various subsurface applications, including carbon dioxide sequestration, nuclear waste storage, biogeochemistry and the simulation of hydro–thermal reservoirs. The model couples a set of partial differential equations, describing the transport of chemical species, to nonlinear algebraic or differential equations, describing the chemical reactions. Solution methods for the resulting large nonlinear system can be either fully coupled or can iterate between transport and chemistry. This paper extends previous work by the authors where an approach based on the Newton–Krylov method applied to a reduced system has been developed. The main feature of the approach is to solve the nonlinear system in a fully coupled manner while keeping transport and chemistry modules separate. Here we extend the method in two directions. First, we take into account mineral precipitation and dissolution reactions by using an interior point Newton method, so as to avoid the usual combinatorial approach. Second, we study two-dimensional heterogeneous geometries. We show how the method can make use of an existing transport solver, used as a black box. We detail the methods and algorithms for the individual modules, and for the coupling step. We show the performance of the method on synthetic examples.

Mineral dissolution and precipitation reactions and their net balance controlled by mineral surface area: An experimental study on the interactions between continental flood basalts and CO2-saturated water at 80 bars and 60 °C

Continental flood basalts are currently considered as unconventional CO2 storage reservoirs given several knowledge gaps remain. This study addresses the question whether subvertical fractures and joints in the storage complex and its overburden may lead to long-term CO2 leakage or whether commencement of self-sealing can be expected at an early stage of geochemical reactions. The latter occurs when mineral precipitation outcompetes mineral dissolution. The nature of secondary mineral precipitation and the change of ion concentrations over time were studied in a batch reactor experiment where basalt wafers with a low surface area were exposed to CO2-saturated formation water at a pressure of 80 bars and 60 °C. Primarily stilbite (a zeolite) and montmorillionite (a smectite) were observed in suspension and kaolinite, Fe-oxide and Na-nontronite were additionally identified as authigenic minerals on the surface of the basalt wafers at the end of the incubation. These observations are in agreement with the state of mineral saturation based on the water composition throughout the incubation. Carbonate minerals were undersaturated throughout the incubation suggesting limited carbon mineral trapping capacity under the given conditions. A mineral nucleation phase (day 1 to 6) dominated by cation release due to dissolution and a mineral growth phase (day 8 to 44) dominated by cation uptake due to precipitation were identified. The latter resulted in the formation of considerable mineral mass, which was deposited almost completely on the wafer surface.

Aqueous chemistry of anthropogenically contaminated Bengaluru lakes

Anthropogenic activities impact the major ion composition of fresh water sources. The inorganic species are likely to be influenced by mineral dissolution, mineral precipitation, redox and ion-exchange reactions in the contaminated lakes. Owing to paucity of research, this study examines the influence of bio-geochemical reactions on the major ion composition of sewage contaminated Bengaluru lakes. The selected lakes represent water bodies in the major valley systems of the city that are polluted by partly treated sewage and stormwater runoffs. Hydrogeochemical facies of the lake samples showed that enrichment of Mg2+, Na+, Cl− and SO42− ions from anthropogenic contamination altered the chemical type of the lake-water. Examination of processes influencing the major ion composition of surface waters indicated that evaporation than rock-weathering tends to influence the chemical composition of the Bengaluru lakes. Precipitation of carbonate minerals in the alkaline pH contributed to the deficiency of alkaline earth ions, while dissolution of anthropogenic gypsum enhanced the SO42− ion concentration of the lakes. Solute diffusion from lake water into the pore solutions of sediments and ion-exchange reactions between monovalent ions of sediments and divalent cations in lake water are additional pathways that influence the major ion composition of the contaminated lakes. Besides alterations in major ion composition, organic contamination, biochemical reactions associated with photosynthesis activity of algae and release of toxic Al3+ ions from mineral dissolution are consequences of the lake contamination.

Kinetic fractionation of carbon and oxygen isotopes during BaCO3 precipitation

Disequilibrium isotopic compositions in carbonate minerals often reflect the integration of several different kinetic isotope effects (KIEs), whose relative contribution to the overall composition depends on the specific mineral formation process and environment. Thus, potential environmental reconstructions from disequilibrium compositions in natural carbonates require (i) quantification of KIEs associated with reactions involved in mineral formation, and (ii) a theoretical framework linking physical properties of natural environments to the expression and preservation of these KIEs in carbonates.To constrain KIEs associated with carbonate mineral precipitation reactions, we performed a series of rapid witherite (BaCO3) precipitation experiments over a range of pH (8.7–13.0), temperature (15–40 °C) and fractional yield of the dissolved inorganic carbon (DIC; a few percent to quantitative precipitation). Our experiments extend the range of pH and temperature explored in previous studies, and include measurements of both carbon and oxygen isotopes. We developed a dynamic model of the DIC system, with which we simulated the experiments. The model results identify isotopic distillation due to formation of aqueous CO2 and mineral precipitation by either CO32– or HCO3– as the main determinants of the carbon and oxygen isotopic evolution of the solid and of the solution.We estimate that the carbon kinetic fractionation factor (KFF) associated with unidirectional precipitation of witherite via CO32–, 1000ln13αCO32-→BaCO3k+1, is 0.5 ± 0.1‰ (15–40 °C), whereas the oxygen KFF, 1000ln18αCO32-→BaCO3k+1, is –1.0 ± 0.3‰ (15 °C) and –0.5 ± 0.2‰ (25–40 °C). The carbon KFF associated with unidirectional HCO3– precipitation pathways, 1000ln13αHCO3-→BaCO3k+2,+3, is –0.2 ± 1.0‰ (15–40 °C), whereas the oxygen KFF, 1000ln18αHCO3-→BaCO3k+2,+3, is –6.7 ± 1.1‰ (15 °C), –4.5 ± 1.1‰ (25 °C) and –4.0 ± 1.1‰ (40 °C). Our oxygen KFF of witherite precipitation from CO32– agrees well with the available literature estimates at 25 °C. In addition, our carbon and oxygen KFFs are comparable to literature KFFs associated with calcite precipitation, possibly suggesting a similarity of precipitation KFFs among carbonate minerals. Importantly, the relative magnitudes and uncertainties of the precipitation KFFs and the equilibrium fractionation between CO32– and HCO3–, leads to the expectation that in many natural settings, the isotopic composition of carbonate minerals be an insensitive probe of the precipitation pathway.

Effect of brine salinity on the geological sequestration of CO2 in a deep saline carbonate formation

AbstractWhen supercritical CO2 is injected into a deep saline aquifer, the salinity of the brine can influence both the solubility of the injected CO2 in the brine and the subsequent aqueous geochemical reactions that occur. The objective of this study is to assess the effect of brine salinity on CO2 storage in deep saline carbonate formations. Specifically, the study aims to quantitatively assess the effect of brine salinity on (a) the amount of CO2 that can be sequestered in the aqueous phase, (b) the storage efficiency of the repository, (c) the change in pH of the residual brine after dissolution of CO2, and (d) changes in the mineralogy and porosity of the rock matrix that result from mineral dissolution and precipitation reactions induced by CO2 injection. Injection of CO2 into a model layered carbonate formation was simulated using the reactive‐transport code TOUGHREACT 3.3. The simulations consisted of 50 years of injection into a partially completed injection well, followed by 50 years of equilibration (no injection). Salinity of the brine was varied between 1% and 15% to determine the effects of salinity. Because the solubility of CO2 decreases as the salinity of the brine increases, an increase in brine salinity from 1% to 15% resulted in a 19% decrease in storage efficiency and a 25% decrease in the mass of CO2 dissolved in the aqueous phase. However, despite the strong effect of brine salinity on CO2 dissolution, there was almost no effect of salinity on the pH change in the residual brine: the chemical activity coefficient of the dissolved CO2 increases with brine salinity, counteracting the effects of decreased solubility. Consequently, brine salinity had little effect on mineral dissolution or precipitation, or on changes in formation porosity. The study therefore helps to choose sequestration sites depending upon the salinity of the brine: lower salinity results in more solubility trapping and better storage efficiency without noticeable differences in pH drop or mineral dissolution. © 2020 Society of Chemical Industry and John Wiley & Sons, Ltd.

A lattice-Boltzmann study of permeability-porosity relationships and mineral precipitation patterns in fractured porous media

Mineral precipitation can drastically alter a reservoir’s ability to transmit mass and energy during various engineering/natural subsurface processes, such as geothermal energy extraction and geological carbon dioxide sequestration. However, it is still challenging to explain the relationships among permeability, porosity, and precipitation patterns in reservoirs, particularly in fracture-dominated reservoirs. Here, we investigate the pore-scale behavior of single-species mineral precipitation reactions in a fractured porous medium, using a phase field lattice-Boltzmann method. Parallel to the main flow direction, the medium is divided into two halves, one with a low-permeability matrix and one with a high-permeability matrix. Each matrix contains one flow-through and one dead-end fracture. A wide range of species diffusivity and reaction rates is explored to cover regimes from advection- to diffusion-dominated, and from transport- to reaction-limited. By employing the ratio of the Damkohler (Da) and the Peclet (Pe) number, four distinct precipitation patterns can be identified, namely (1) no precipitation (Da/Pe 100), (3) fracture isolation (1 1), and (4) diffusive precipitation (1 < Da/Pe < 100 and Pe < 0.1). Using moment analyses, we discuss in detail the development of the species (i.e., reactant) concentration and mineral precipitation fields for various species transport regimes. Finally, we establish a general relationship among mineral precipitation pattern, porosity, and permeability. Our study provides insights into the feedback loop of fluid flow, species transport, mineral precipitation, pore space geometry changes, and permeability in fractured porous media.

Phosphorus and nitrogen loading to Lake Huron from septic systems at Grand Bend, ON

Groundwater nutrient loading to L. Huron was assessed along a 1.7 km section of beach at Grand Bend, ON, Canada, where septic systems are used for wastewater disposal. The artificial sweetener acesulfame (ACE) was detected in all groundwater samples (7–842 ng/L, n = 78), revealing that the entire surficial aquifer was impacted by septic system wastewater. Nitrate concentrations (3.5 ± 1.4 mg/L, n = 78) were correlated with ACE (r2 = 0.54), indicating that septic systems contribute to nitrate loading in the aquifer. Chloride was also elevated (37 ± 11 mg/L, n = 78), but was not correlated with ACE (r2 = 0.008), indicating a non wastewater source was dominant, likely road salt. Soluble reactive phosphorus (SRP) values were low (5.3 ± 9.3 μg/L, n = 77) and were not correlated with ACE (r2 = 0.006). Sediment profiling below two of the septic system drain-fields, showed that the sand grains had distinct secondary coatings containing P, indicating that mineral precipitation reactions played a role in limiting P concentrations present in the aquifer. Groundwater nutrient loading to the lake was estimated at 13,000 kg N/year from NO3− and 1.9 kg P/year from SRP. These amounts are insignificant compared to nutrient loading from a stream that drains an agricultural catchment and discharges to the lake at the north end of the study site (Parkhill Creek). This calls into question, in some cases, the rationale of decommissioning properly functioning septic systems as a mitigation measure for reducing nutrient loading to nearby water courses.

Underground hydrogen storage: application of geochemical modelling in a case study in the Molasse Basin, Upper Austria

Hydrogen storage in depleted gas fields is a promising option for the large-scale storage of excess renewable energy. In the framework of the hydrogen storage assessment for the “Underground Sun Storage” project, we conduct a multi-step geochemical modelling approach to study fluid–rock interactions by means of equilibrium and kinetic batch simulations. With the equilibrium approach, we estimate the long-term consequences of hydrogen storage, whereas kinetic models are used to investigate the interactions between hydrogen and the formation on the time scales of typical storage cycles. The kinetic approach suggests that reactions of hydrogen with minerals become only relevant over timescales much longer than the considered storage cycles. The final kinetic model considers both mineral reactions and hydrogen dissolution to be kinetically controlled. Interactions among hydrogen and aqueous-phase components seem to be dominant within the storage-relevant time span. Additionally, sensitivity analyses of hydrogen dissolution kinetics, which we consider to be the controlling parameter of the overall reaction system, were performed. Reliable data on the kinetic rates of mineral dissolution and precipitation reactions, specifically in the presence of hydrogen, are scarce and often not representative of the studied conditions. These uncertainties in the kinetic rates for minerals such as pyrite and pyrrhotite were investigated and are discussed in the present work. The proposed geochemical workflow provides valuable insight into controlling mechanisms and risk evaluation of hydrogen storage projects and may serve as a guideline for future investigations.

Advanced biofilm staining techniques for TEM and SEM in geomicrobiology: Implications for visualizing EPS architecture, mineral nucleation, and microfossil generation

Microbial biofilms and mats have long been studied for their role in mineral precipitation reactions in natural environments. Scanning electron microscopy (SEM) is often used to characterize biofilms and their associated precipitates, however, conventional SEM sample preparation methods do not typically preserve the structure of the extracellular polymeric substances (EPS), which account for a large portion of biofilm material and play crucial roles in biofilm function and mineral nucleation. In the present investigation, EPS preservation and visualization using transmission electron microscopy (TEM) was explored using three biofilm fixation and staining protocols. Although aspects of these protocols were developed for preserving complex eukaryotic tissue samples, the heterogeneous, three-dimensional nature of biofilms make them suitable candidates for these sample processing techniques. The results suggest that cryofixation provides the best preservation of cyanobacteria-dominated biofilm structures. A staining protocol including six different pre-embedding stains allowed for TEM visualization of the EPS matrix that encompasses biofilm cells and precipitates. Of the stains used, uranyl acetate appears to be important in avoiding biofilm deformation during sample processing. Using these staining protocols, cell-EPS-mineral relationships were observed, including the precipitation of hydromagnesite [Mg5(CO3)4(OH)2·4H2O] on the EPS adjacent to the exterior of cyanobacteria filaments. Beachrock-associated biofilms were characterized using both TEM of ultrathin sections, as well as SEM of resin embedded osmium stained biofilms prepared as petrographic thin sections. Combining these two approaches enabled characterization of both the micrometer-scale cell-carbonate mineral contacts, as well as the larger scale microbial colony-mineral cement relationships. These results suggest that sample preparation techniques developed for rapid preservation of eukaryotic tissue samples can be used to preserve and characterize biofilm architecture. These findings have applications to understanding mineral nucleation in biofilms, and the preservation of biofilms as microfossils in the rock record.

Role of water−rock interaction in the geochemical evolution of Marcellus Shale produced waters

Knowledge of geochemical processes that occur during hydraulic fracturing of shale resources for natural gas recovery can provide insight into in situ mineral precipitation and dissolution reactions that affect shale pore and fracture networks, and ultimately the ability to recover natural gas. Measurement of dissolved chemical species in produced waters, which serve as indicators of water-rock reactions in the reservoir, is one approach for monitoring subsurface geochemistry. However, an ability to distinguish effects of water-rock reactions versus reservoir fluid mixing on chemical concentration and speciation in produced waters requires experimental investigation to better understand natural geochemical tracer behavior.In this study, we explored Li, Sr, and U as geochemical tracers of ion−exchange and mineral dissolution reactions occurring during a series of flow-through laboratory experiments designed to evaluate mineral reactions occurring in shale reacted with hydraulic fracturing fluid (HFF). The experiments, reported in detail in a separate study (Paukert Vankeuren et al., 2017), were designed to emulate shut-in conditions (period after hydraulic fracturing but before production when HFF remains in the reservoir to allow for opening of new fractures for hydrocarbon recovery) for Marcellus Shale undergoing hydraulic fracturing in southwestern Pennsylvania, USA. In the companion study presented here, effluent samples from the core flood experiments were analyzed for changes in Li isotopes (δ7Li), radiogenic Sr isotopes (εSrSW), and U concentration as possible unique geochemical tracers to indicate water-rock reaction. Experimental and reactive transport modeling results demonstrated that the peak of U in experimental effluents is derived from dissolution of U-containing calcite, which may explain the pulse of U observed in produced water collected from hydraulically fractured Marcellus Shale on the first day of flowback. Experimental results also showed that changes in δ7Li values and εSrSW from the flow-through experiments differ from values measured in a time series of produced waters from Marcellus Shale gas wells. Thus, although ion−exchange and mineral dissolution and precipitation reactions result in an observable change in Sr isotope signals in laboratory experiments, this change may not be identifiable in produced waters in the field due to complications associated with geologic heterogeneity and overprinting of other signals such as fluid mixing and transport. While U shows some promise as a tracer of HFF-shale reactions, particularly carbonate dissolution, it may be necessary to continue searching for other tracers present in produced waters to aid in elucidating in situ water-rock reactions of interest.

Determination of Geochemical Bio-Signatures in Mars-Like Basaltic Environments.

Bio-signatures play a central role in determining whether life existed on early Mars. Using a terrestrial basalt as a compositional analog for the martian surface, we applied a combination of experimental microbiology and thermochemical modeling techniques to identify potential geochemical bio-signatures for life on early Mars. Laboratory experiments were used to determine the short-term effects of biota on the dissolution of terrestrial basalt, and the formation of secondary alteration minerals. The chemoorganoheterotrophic bacterium, Burkholderia sp. strain B_33, was grown in a minimal growth medium with and without terrestrial basalt as the sole nutrient source. No growth was detected in the absence of the basalt. In the presence of basalt, during exponential growth, the pH decreased rapidly from pH 7.0 to 3.6 and then gradually increased to a steady-state of equilibrium of between 6.8 and 7.1. Microbial growth coincided with an increase in key elements in the growth medium (Si, K, Ca, Mg, and Fe). Experimental results were compared with theoretical thermochemical modeling to predict growth of secondary alteration minerals, which can be used as bio-signatures, over a geological timescale. We thermochemically modeled the dissolution of the basalt (in the absence of biota) in very dilute brine at 25°C, 1 bar; the pH was buffered by the mineral dissolution and precipitation reactions. Preliminary results suggested that at the water to rock ratio of 1 × 107, zeolite, hematite, chlorite, kaolinite, and apatite formed abiotically. The biotic weathering processes were modeled by varying the pH conditions within the model to adjust for biologic influence. The results suggested that, for a basaltic system, the microbially-mediated dissolution of basalt would result in “simpler” secondary alteration, consisting of Fe-hydroxide and kaolinite, under conditions where the abiotic system would also form chlorite. The results from this study demonstrate that, by using laboratory-based experiments and thermochemical modeling, it is possible to identify secondary alteration minerals that could potentially be used to distinguish between abiotic and biotic weathering processes on early Mars. This work will contribute to the interpretation of data from past, present, and future life detection missions to Mars.

Numerical investigation of Lower Tuscaloosa Sandstone and Selma Chalk caprock under geological CO2 sequestration conditions: mineral precipitation and permeability evolution

AbstractA numerical model was developed using CrunchFlow to simulate reactive transport and porosity and permeability changes of sandstone and carbonate rock samples taken from the Lower Tuscaloosa Formation and the Selma Chalk Formation, Jackson County, MS, USA. The model predicted a permeability decrease from 2190 mD to 2038 mD for the Lower Tuscaloosa Sandstone sample in a static batch reactor after 180 days of exposure to CO2‐saturated brine, which is consistent with measured permeability results. The model predicted a negligible permeability change from 2.00 mD to 2.08 mD for the Selma Chalk carbonate sample after 180 days of exposure to CO2‐saturated brine. Based on model prediction, key mineral dissolution and precipitation reactions in the Lower Tuscaloosa Sandstone sample include dissolution of quartz, chlorite, and feldspar, as well as precipitation of amorphous silica and kaolinite. For the Selma Chalk carbonate sample, key predicted reactions include dissolution of calcite, quartz and chlorite, and precipitation of kaolinite and amorphous silica. Initial porosity, initial feldspar content and the exponent n value (related to pore structure and tortuosity) used in permeability calculations were three important factors affecting permeability evolution of sandstone samples under CO2 sequestration conditions. The small permeability change predicted for both the Lower Tuscaloosa Sandstone and the Selma Chalk caprock after exposure to CO2‐saturated brine suggests that poro‐permeability changes during CO2 injection into the Lower Tuscaloosa Formation are not likely to significantly affect reservoir and seal quality. © 2017 Society of Chemical Industry and John Wiley &amp; Sons, Ltd.

The influence of oxygen isotope exchange between CO2 and H2O in natural CO2-rich spring waters: Implications for geothermometry

Oxygen isotope ratio (δ18O) value deviations from the Meteoric Water Line with no significant change in the hydrogen isotope (δ2H) composition have been reported in naturally occurring CO2-rich waters from around the world. Here we review the effects of oxygen isotope exchange with CO2, high temperature equilibration with bedrock minerals and mineral dissolution and precipitation reactions on the CO2-rich water isotopic composition. We present two case studies from Daylesford (Australia) and Pah Tempe (Utah, USA) mineral springs, where we use a numerical geochemical modelling approach to resolve the influence of low temperature water-rock interactions and CO2 equilibration to the oxygen isotope ranges observed in the mineral waters. In both cases, we find that mineral dissolution – precipitation reactions are unlikely to have a significant effect on the groundwater isotopic compositions, and that the observed δ18O values in natural CO2 springs can be simply explained by equilibrium fractionation between water and free phase CO2. Traditionally, the interaction of CO2 and water in a natural CO2-rich groundwater setting has only been associated with water 18O depletion and this is the first study to consider 18O enrichment. We establish that in a natural setting, CO2 and water equilibration can result in water 18O depletion or enrichment, and that the change in the oxygen isotope composition ultimately depends on the initial CO2 and water δ18O values. Our new conceptual model therefore provides a mechanism to explain water 18O enrichment at ambient temperatures. This finding is critical for the use of δ18O in groundwater geothermometry and for the interpretation of natural water circulation depths: we argue that in some cases, natural waters previously interpreted as geothermal based on their oxygen isotope composition may actually have acquired their isotopic signature through interaction with CO2 at ambient temperatures.