A reactive transport model for geochemical mitigation of CO2 leaking into a confined aquifer

Long-term storage of anthropogenic CO2 in the subsurface generally assumes that caprock formations will serve as physical barriers to upward migration of CO2. However, as a precaution and to provide assurances to regulators and the public, monitoring is used detect any unexpected leakage from the storage reservoir. If a leak is found, the ability to rapidly deploy mitigation measures is needed. Here we use the TOUGHREACT code to develop a series of two-dimensional reactive transport simulations of the hydrogeochemical characteristics of a newly formed CO2 leak into an overlying aquifer. Using this model, we consider: (1) geochemical shifts in formation water indicative of a leak; (2) hydrodynamics of pumping wells in the vicinity of a leak; and (3) delivery of a sealant to a leak through an adjacent well bore.Our results demonstrate that characteristic shifts in pH and dissolved inorganic carbon can be detected in the aquifer prior to the breakthrough of supercritical CO2, and could offer a potential means of identifying small and newly formed leaks. Pumping water into the aquifer in the vicinity of the leak provides a hydrodynamic control that can temporarily mitigate the flux rate of CO2 and facilitate delivery of a sealant to the location of the caprock defect. Injection of a fluid-phase sealant through the pumping well is demonstrated by introduction of a silica-bearing alkaline flood, resulting in precipitation of amorphous silica in areas of neutral to acidic pH. Results show that a decrease in permeability of several orders of magnitude can be achieved with a high molar volume sealant, such that CO2 flux rate is decreased. However, individual simulation results are highly contingent upon both the properties of the sealant, the porosity-permeability relationship employed in the model, and the relative flux rates of CO2 and alkaline flood introduced into the aquifer. These conclusions highlight the need for both experimental data and controlled field tests to constrain modelling predictions

On the mobilization of metals by CO2leakage into shallow aquifers: exploring release mechanisms by modeling field and laboratory experiments

The dissolution of CO2 in water leads to a pH decrease and a carbonate content increase in affected groundwater, which in turn can drive the mobilization of metals from sediments. The mechanisms of metal release postulated in various field and laboratory studies often differ. Drawing primarily on previously published results, we examine contrasting metal mobilization behaviors at two field tests and in one laboratory study, to investigate whether the same mechanisms could explain metal releases in these different experiments. Numerical modeling of the two field tests reveals that fast Ca-driven cation exchange (from calcite dissolution) can explain the release of most major and trace metal cations at both sites, and their parallel concentration trends. The dissolution of other minerals reacting more slowly (superimposed on cation exchange) also contributes to metal release over longer time frames, but can be masked by fast ambient groundwater velocities. Therefore, the magnitude and extent of mobilization depends not only on metal-mineral associations and sediment pH buffering characteristics, but also on groundwater flow rates, thus on the residence time of CO2-impacted groundwater relative to the rates of metal-release reactions. Sequential leaching laboratory tests modeled using the same metal-release concept as postulated from field experiments show that both field and laboratory data can be explained by the same processes. The reversibility of metal release upon CO2 degassing by de-pressurization is also explored using simple geochemical models, and shows that the sequestration of metals by resorption and re-precipitation upon CO2 exsolution is quite plausible and may warrant further attentio

On the buffer capacity of CO2-charged seawater used for carbonation and subsequent mineral sequestration

Successful mineral trapping of carbon dioxide faces the challenge of effectively titrating a CO2-charged acidic injection solution to pH conditions favorable to carbonate precipitation -using the rock as primary alkalinity source. To illustrate the magnitude of this task, buffer capacities of seawater solutions equilibrated with different partial pressure of CO2 are presented, under open and closed conditions. A number of mechanisms can be evoked to overcome the large buffer intensity of the injection fluid, including dilution, dissolution kinetic catalysis and increasing reaction temperature. Buffer capacity – pH plots are presented to aid in understanding how buffer capacity changes as a function of the presence and concentration of key solutes, like fluoride

Water Challenges for Geologic Carbon Capture and Sequestration

Carbon capture and sequestration (CCS) has been proposed as a means to dramatically reduce greenhouse gas emissions with the continued use of fossil fuels. For geologic sequestration, the carbon dioxide is captured from large point sources (e.g., power plants or other industrial sources), transported to the injection site and injected into deep geological formations for storage. This will produce new water challenges, such as the amount of water used in energy resource development and utilization and the “capture penalty” for water use. At depth, brine displacement within formations, storage reservoir pressure increases resulting from injection, and leakage are potential concerns. Potential impacts range from increasing water demand for capture to contamination of groundwater through leakage or brine displacement. Understanding these potential impacts and the conditions under which they arise informs the design and implementation of appropriate monitoring and controls, important both for assurance of environmental safety and for accounting purposes. Potential benefits also exist, such as co-production and treatment of water to both offset reservoir pressure increase and to provide local water for beneficial use

Reactive transport modeling to study changes in water chemistry induced by CO2 injection at the Frio-I brine pilot

To demonstrate the potential for geologic storage of CO{sub 2} in saline aquifers, the Frio-I Brine Pilot was conducted, during which 1600 tons of CO{sub 2} were injected into a high-permeability sandstone and the resulting subsurface plume of CO{sub 2} was monitored using a variety of hydrogeological, geophysical, and geochemical techniques. Fluid samples were obtained before CO{sub 2} injection for baseline geochemical characterization, during the CO{sub 2} injection to track its breakthrough at a nearby observation well, and after injection to investigate changes in fluid composition and potential leakage into an overlying zone. Following CO{sub 2} breakthrough at the observation well, brine samples showed sharp drops in pH, pronounced increases in HCO{sub 3}{sup -} and aqueous Fe, and significant shifts in the isotopic compositions of H{sub 2}O and dissolved inorganic carbon. Based on a calibrated 1-D radial flow model, reactive transport modeling was performed for the Frio-I Brine Pilot. A simple kinetic model of Fe release from the solid to aqueous phase was developed, which can reproduce the observed increases in aqueous Fe concentration. Brine samples collected after half a year had lower Fe concentrations due to carbonate precipitation, and this trend can be also captured by our modeling. The paper provides a method for estimating potential mobile Fe inventory, and its bounding concentration in the storage formation from limited observation data. Long-term simulations show that the CO{sub 2} plume gradually spreads outward due to capillary forces, and the gas saturation gradually decreases due to its dissolution and precipitation of carbonates. The gas phase is predicted to disappear after 500 years. Elevated aqueous CO{sub 2} concentrations remain for a longer time, but eventually decrease due to carbonate precipitation. For the Frio-I Brine Pilot, all injected CO{sub 2} could ultimately be sequestered as carbonate minerals

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

Transport of Pb and Zn by carboxylate complexes in basinal ore fluids and related petroleum-field brines at 100°C: the influence of pH and oxygen fugacity

It is well established through field observations, experiments, and chemical models that oxidation (redox) state and pH exert a strong influence on the speciation of dissolved components and the solubility of minerals in hydrothermal fluids. log [Image: see text] –pH diagrams were used to depict the influence of oxygen fugacity and pH on monocarboxylate- and dicarboxylate-transport of Pb and Zn in low-temperature (100°C) hydrothermal ore fluids that are related to diagenetic processes in deep sedimentary basins, and allow a first-order comparison of Pb and Zn transport among proposed model fluids for Mississippi Valley-type (MVT) and red-bed related base metal (RBRBM) deposits in terms of their approximate pH and [Image: see text] conditions. To construct these diagrams, total Pb and Zn concentrations and Pb and Zn speciation were calculated as a function of log [Image: see text] and pH for a composite ore-brine with concentrations of major elements, total sulfur, and total carbonate that approximate the composition of MVT and RBRBM model ore fluids and modern basinal brines. In addition to acetate and malonate complexation, complexes involving the ligands Cl(-), HS(-), H(2)S, and OH(- )were included in the model of calculated total metal concentration and metal speciation. Also, in the model, Zn and Pb are competing with the common-rock forming metals Ca, Mg, Na, Fe, and Al for the same ligands. Calculated total Pb concentration and calculated total Zn concentration are constrained by galena and sphalerite solubility, respectively. Isopleths, in log [Image: see text] –pH space, of the concentration of Pb and concentration of Zn in carboxylate (acetate + malonate) complexes illustrate that the oxidized model fluids of T. H. Giordano (in Organic Acids in Geological Processes, ed. E. D. Pittman and M. D. Lewan, Springer-Verlag, New York, 1994, pp. 319–354) and G. M. Anderson (Econ. Geol., 1975, 70, 937–942) are capable of transporting sufficient amounts of Pb (up to 10 ppm) and Zn (up to 100 ppm) in the form of carboxylate complexes to form economic deposits of these metals. On the other hand, the reduced ore fluid models of D. A. Sverjensky (Econ. Geol., 1984, 79, 23–37) and T. H. Giordano and H. L. Barnes (Econ. Geol., 1981, 76, 2200–2211) can at best transport amounts of Pb and Zn, as carboxylate complexes, that are many orders of magnitude below the 1 to 10 ppm minimum required to form economic deposits. Lead and zinc speciation (mol% of total Pb or Zn) in the model ore fluid was calculated at specific log [Image: see text] –pH conditions along the 100, 0.01, and 0.001 ppm total Pb and total Zn isopleths. Along the 100 ppm isopleth conditions are oxidized (∑SO(4 )>> ∑H(2)S) with Pb and Zn predominantly in the form of chloride complexes under acid to mildly alkaline conditions (pH from 3 to approximately 7.5), while hydroxide complexes dominate Pb and Zn speciation under more alkaline conditions. Sulfide complexes are insignificant under these oxidized conditions. For more reduced conditions along the 0.01 and 0.001 ppm isopleths chloride complexes dominate Pb and Zn speciation in the SO(4)(2- )field and near the SO(4)(2-)-reduced sulfur boundary from pH = 4 to approximately 7.5, while hydroxide complexes dominate Pb and Zn speciation under alkaline conditions above pH = 7.5 in the SO(4)(2- )field. In the most reduced fluids (∑H(2)S >> ∑SO(4)) along the 0.01 and 0.001 isopleths, sulfide complexes account for almost 100% of the Pb and Zn in the model fluid. Acetate (monocarboxylate) complexation is significant only under conditions of chloride and hydroxide complex dominance and its effect is maximized in the pH range 5 to 7, where it complexes 2 to 2.6% of the total Pb and 1 to 1.25% of the total Zn. Malonate (dicarboxylate) complexes are insignificant along all isopleths. The speciation results from this study show that deep formation waters characterized by temperatures near 100°C, high oxidation states and ∑H(2)S < 0.03 mg L(-1 )([Image: see text] < 10(-6)), high chlorinities (~ 100000 mg L(-1)), and high but reasonable concentrations of carboxylate anions can mobilize up to 3% of the total Pb and up to 1.3% of the total Zn as carboxylate complexes. Furthermore, these percentages, under the most favorable conditions, correspond to approximately 1 to 100 ppm of these metals in solution; concentrations that are adequate to form economic deposits of these metals. However, the field evidence suggests that all of these optimum conditions for carboxylate complexation are rarely met at the same time. A comparison of the composite ore fluid compositions from this study and modern brine data shows that the ore brines, corresponding to log [Image: see text] –pH conditions based on the Anderson (1975) and Giordano (1994) model fluids, are similar in many respects to modern, high trace-metal petroleum-field brines. The principal differences between modern high trace-metal brines and the composite ore fluids of Anderson (1975) and Giordano (1994) relate to their carboxylate anion content. The reported concentrations of monocarboxylate anions (∑monocbx) and dicarboxylate anions (Edicbx) in high trace-metal petroleum-field brines (< 1 to 300 mg L(-1 )and < 1 mg L(-1), respectively) are significantly lower than the concentrations assumed in the modelled brines of this study (∑monocbx = 7 700 mg L(-1 )and ∑dicbx = 300 mg L(-1)). There are also major differences in the corresponding total chloride to carboxylate ratio (∑m(Cl)/∑m(cbx)) and monocarboxylate to dicarboxylate ratio (∑m(monocbx)/∑m(dicbx)). Modern high trace-metal brines have much higher ∑m(Cl)/∑m(cbx )values and, therefore, the contribution of carboxylate complexes to the total Pb and Zn content in these modern brines is likely to be significantly less than the 1 to 3 percent for the composite ore fluids of Anderson (1975) and Giordano (1994). The composite ore-brine based on the Giordano and Barnes (1981) MVT ore fluid is comparable to the high salinity (> 170 000 mg L(-1 )TDS) subset of modern brines characterized by low trace-metal content and high total reduced sulfur (∑H(2)S). A comparison of the Sverjensky (1984) composite ore-brine with modern petroleum-field brines in terms of ∑H(2)S and Zn content, reveals that this ore fluid corresponds to a "border-type" brine, between modern high trace-metal brines and those with low trace-metal content and high ∑H(2)S. A brine of this type is characterized by values of ∑H(2)S, ∑Zn, and/or ∑Pb within or near the 1 to 10 mg L(-1 )range. Based on brine-composition data from numerous references cited in this paper, border-type brines do exist but are rare. The model results and field evidence presented in this study are consistent with other chemical simulation studies of carboxylate complexation in modern petroleum-field brines. Thus, it appears that carboxylate complexation plays a minor, if not insignificant, role as a transport mechanism for Pb and Zn in high salinity Na–Cl and Na–Ca–Cl basinal brines and related ore fluids

The Inherent Tracer Fingerprint of Captured CO2.

Carbon capture and storage (CCS) is the only currently available technology that can directly reduce anthropogenic CO2 emissions arising from fossil fuel combustion. Monitoring and verification of CO2 stored in geological reservoirs will be a regulatory requirement and so the development of reliable monitoring techniques is essential. The isotopic and trace gas composition - the inherent fingerprint - of captured CO2 streams is a potentially powerful, low cost geochemical technique for tracking the fate of injected gas in CCS projects; carbon and oxygen isotopes, in particular, have been used as geochemical tracers in a number of pilot CO2 storage sites, and noble gases are known to be powerful tracers of natural CO2 migration. However, the inherent tracer fingerprint in captured CO2 streams has yet to be robustly investigated and documented and key questions remain, including how consistent is the fingerprint, what controls it, and will it be retained en route to and within the storage reservoir? Here we present the first systematic measurements of the carbon and oxygen isotopes and the trace noble gas composition of anthropogenic CO2 captured from combustion power stations and fertiliser plants. The analysed CO2 is derived from coal, biomass and natural gas feedstocks, using amine capture, oxyfuel and gasification processes, from six different CO2 capture plants spanning four different countries. We find that δ13C values are primarily controlled by the δ13C of the feedstock while δ18O values are predominantly similar to atmospheric O2. Noble gases are of low concentration and exhibit relative element abundances different to expected reservoir baselines and air, with isotopic compositions that are similar to air or fractionated air. The use of inherent tracers for monitoring and verification was provisionally assessed by analysing CO2 samples produced from two field storage sites after CO2 injection. These experiments at Otway, Australia, and Aquistore, Canada, highlight the need for reliable baseline data. Noble gas data indicates noble gas stripping of the formation water and entrainment of Kr and Xe from an earlier injection experiment at Otway, and inheritance of a distinctive crustal radiogenic noble gas fingerprint at Aquistore. This fingerprint can be used to identify unplanned migration of the CO2 to the shallow subsurface or surface

A preliminary study of the chemistry of pore water extracted from tuff by one-dimensional compression

A specially designed and fabricated one-dimensional compression cell is being used to extract water from nonwelded and densely welded tuffs having degrees of saturation greater than 16 and 37 percent respectively. Chemical analyses of pore water obtained at increasing pressures are used to evaluate possible changes in chemistry caused by compression. The extracted pore water varies form a calcium chloride type to a sodium bicarbonate type. The mean concentration of dissolved ions generally decreases during compression. The relative abundance of the major cations varies little with increasing pressure. Possible causes of the pore-water-chemistry changes include: (1) dilution of pore water by low ionic strength adsorbed water from zeolites and clays; (2) dissolution reactions caused by the increase in dissolved carbon dioxide concentrations that may result from pressurization; (3) membrane filtration by zeolites and clays; and (4) ion exchange with the zeolites and clays