Feasibility of geoelectrical monitoring and multiphase modeling for process understanding of gaseous CO2 injection into a shallow aquifer

Potential pathways in the subsurface may allow upwardly migrating gaseous CO₂ from deep geological storage formations to be released into near surface aquifers. Consequently, the availability of adequate methods for monitoring potential CO₂ releases in both deep geological formations and the shallow subsurface is a prerequisite for the deployment of Carbon Capture and Storage technology. Geoelectrical surveys are carried out for monitoring a small-scale and temporally limited CO₂ injection experiment in a pristine shallow aquifer system. Additionally, the feasibility of multiphase modeling was tested in order to describe both complex non-linear multiphase flow processes and the electrical behavior of partially saturated heterogeneous porous media. The suitability of geoelectrical methods for monitoring injected CO₂ and geochemically altered groundwater was proven. At the test site, geoelectrical measurements reveal significant variations in electrical conductivity in the order of 15?C30?%. However, site-specific conditions (e.g., geological settings, groundwater composition) significantly influence variations in subsurface electrical conductivity and consequently, the feasibility of geoelectrical monitoring. The monitoring results provided initial information concerning gaseous CO₂ migration and accumulation processes. Geoelectrical monitoring, in combination with multiphase modeling, was identified as a useful tool for understanding gas phase migration and mass transfer processes that occur due to CO₂ intrusions in shallow aquifer systems.     

Assessing the potential consequences of CO2 leakage to freshwater resources: A batch-reaction experiment towards an isotopic tracing tool

The assessment of the environmental impacts of CO₂ geological storage requires the investigation of potential CO₂ leakages into fresh groundwater, particularly with respect to protected groundwater resources. The geochemical processes and perturbations associated with a CO₂ leak into fresh groundwater could alter groundwater quality: indeed, some of the reacting minerals may contain hazardous constituents, which might be released into groundwater. Since the geochemical reactions may occult direct evidence of intruding CO₂, it is necessary to characterize these processes and identify possible indirect indicators for monitoring CO₂ intrusion. The present study focuses on open questions: Can changes in water quality provide evidence of CO₂ leakage? Which parameters can be used to assess impact on freshwater aquifers? What is the time scale of water chemistry degradation in the presence of CO₂? The results of an experimental approach allow selecting pertinent isotope tracers as possible indirect indicators of CO₂ presence, opening the way to devise an isotopic tracing tool.The study area is located in the Paris Basin (France), which contains deep saline formations identified as targets by French national programs for CO₂ geological storage. The study focuses on the multi-layered Albian fresh water aquifer, confined in the central part of the Paris Basin a major strategic potable groundwater overlying the potential CO₂ storage formations. An experimental approach (batch reactors) was carried out in order to better understand the rock–water–CO₂ interactions with two main objectives. The first was to assess the evolution of the formation water chemistry and mineralogy of the solid phase over time during the interaction. The second concerned the design of an isotopic monitoring program for freshwater resources potentially affected by CO₂ leakage. The main focus was to select suitable environmental isotope tracers to track water rock interaction associated with small quantities of CO₂ leaking into freshwater aquifers.In order to improve knowledge on the Albian aquifer, and to provide representative samples for the experiments, solid and fluid sampling campaigns were performed throughout the Paris Basin. Albian groundwater is anoxic with high concentrations of Fe, a pH around 7 and a mineral content of 0.3 g L⁻¹. Macroscopic and microscopic solid analyses showed a quartz-rich sand with the presence of illite/smectite, microcline, apatite and glauconite. A water–mineral–CO₂ interaction batch experiment was used to investigate the geochemical evolution of the groundwater and the potential release of hazardous trace elements. It was complemented by a multi-isotope approach including δ¹³C_DIC and ⁸⁷Sr/⁸⁶Sr. Here the evolution of the concentrations of major and trace elements and isotopic ratios over batch durations from 1 day to 1 month are discussed. Three types of ion behavior are observed: Type I features Ca, SiO₂, HCO₃, F, PO₄, Na, Al, B, Co, K, Li, Mg, Mn, Ni, Pb, Sr, Zn which increased after initial CO₂ influx. Type II comprises Be and Fe declining at the start of CO₂ injection. Then, type III groups element with no variation during the experiments like Cl and SO₄. The results of the multi-isotope approach show significant changes in isotopic ratios with time. The contribution of isotope and chemical data helps in understanding geochemical processes involved in the system. The isotopic systems used in this study are potential indirect indicators of CO₂–water–rock interaction and could serve as monitoring tools of CO₂ leakage into an aquifer overlying deep saline formations used for C sequestration and storage.     

CO2 leakage impacts on shallow groundwater: Field-scale reactive-transport simulations informed by observations at a natural analog site

It is challenging to predict the degree to which shallow groundwater might be affected by leaks from a CO₂ sequestration reservoir, particularly over long time scales and large spatial scales. In this study observations at a CO₂ enriched shallow aquifer natural analog were used to develop a predictive model which is then used to simulate leakage scenarios. This natural analog provides the opportunity to make direct field observations of groundwater chemistry in the presence of elevated CO₂, to collect aquifer samples and expose them to CO₂ under controlled conditions in the laboratory, and to test the ability of multi-phase reactive transport models to reproduce measured geochemical trends at the field-scale. The field observations suggest that brackish water entrained with the upwelling CO₂ are a more significant source of trace metals than in situ mobilization of metals due to exposure to CO₂. The study focuses on a single trace metal of concern at this site: U. Experimental results indicate that cation exchange/adsorption and dissolution/precipitation of calcite containing trace amounts of U are important reactions controlling U in groundwater at this site, and that the amount of U associated with calcite is fairly well constrained. Simulations incorporating these results into a 3-D multi-phase reactive transport model are able to reproduce the measured ranges and trends between pH, pCO₂, Ca, total C, U and Cl⁻ at the field site. Although the true fluxes at the natural analog site are unknown, the cumulative CO₂ flux inferred from these simulations are approximately equivalent to 37.8E−3 MT, approximately corresponding to a .001% leak rate for injection at a large (750 MW) power plant. The leakage scenario simulations suggest that if the leak only persists for a short time the volume of aquifer contaminated by CO₂-induced mobilization of U will be relatively small, yet persistent over 100 a.     

Changes in the chemistry of shallow groundwater related to the 2008 injection of CO2 at the ZERT field site, Bozeman, Montana

Approximately 300 kg/day of food-grade CO₂ was injected through a perforated pipe placed horizontally 2–2.3 m deep during July 9–August 7, 2008 at the MSU-ZERT field test to evaluate atmospheric and near-surface monitoring and detection techniques applicable to the subsurface storage and potential leakage of CO₂. As part of this multidisciplinary research project, 80 samples of water were collected from 10 shallow monitoring wells (1.5 or 3.0 m deep) installed 1–6 m from the injection pipe, at the southwestern end of the slotted section (zone VI), and from two distant monitoring wells. The samples were collected before, during, and following CO₂ injection. The main objective of study was to investigate changes in the concentrations of major, minor, and trace inorganic and organic compounds during and following CO₂ injection. The ultimate goals were (1) to better understand the potential of groundwater quality impacts related to CO₂ leakage from deep storage operations, (2) to develop geochemical tools that could provide early detection of CO₂ intrusion into underground sources of drinking water (USDW), and (3) to test the predictive capabilities of geochemical codes against field data. Field determinations showed rapid and systematic changes in pH (7.0–5.6), alkalinity (400–1,330 mg/l as HCO₃), and electrical conductance (600–1,800 μS/cm) following CO₂ injection in samples collected from the 1.5 m-deep wells. Laboratory results show major increases in the concentrations of Ca (90–240 mg/l), Mg (25–70 mg/l), Fe (5–1,200 ppb), and Mn (5–1,400 ppb) following CO₂ injection. These chemical changes could provide early detection of CO₂ leakage into shallow groundwater from deep storage operations. Dissolution of observed carbonate minerals and desorption-ion exchange resulting from lowered pH values following CO₂ injection are the likely geochemical processes responsible for the observed increases in the concentrations of solutes; concentrations generally decreased temporarily following four significant precipitation events. The DOC values obtained are 5 ± 2 mg/l, and the variations do not correlate with CO₂ injection. CO₂ injection, however, is responsible for detection of BTEX (e.g. benzene, 0–0.8 ppb), mobilization of metals, the lowered pH values, and increases in the concentrations of other solutes in groundwater. The trace metal and BTEX concentrations are all significantly below the maximum contaminant levels (MCLs). Sequential leaching of core samples is being carried out to investigate the source of metals and other solutes.     

Analyses of pre-injection reservoir data for stable carbon isotope trend predictions in CO2 monitoring: preparing for CO2 injection

Baseline monitoring at the proposed enhanced gas recovery site in Altmark (Germany) was carried out in combination with theoretical and laboratory investigations to describe and predict the principles of expected stable carbon isotope and dissolved inorganic carbon (DIC) trends during CO₂ injection in reservoirs. This provides fundamental data for site-specific characterisation for monitoring purposes. Baseline ??¹³C values at the Altmark site ranged between ?1.8 and ?11.5??? and DIC values were about 2?mmol?L^?1. These baseline values form the basis for a theoretical study on the influences of the ambient reservoir conditions on the state of geochemical and isotope equilibrium of the reservoir fluids. Transferring this theoretical study to the Altmark site enables predictions on geochemical trends during potential injection. Assuming that CO₂ would be injected at the Altmark site to pCO₂?=?100?bar and with a ??¹³C of ?30???, at isotopic and geochemical equilibrium, ??¹³C_DIC values would approach this end-member, and DIC concentrations of 1,000?mmol L^?1 would be expected. Laboratory experiments were conducted at low pCO₂ levels (4?C35?bars) to mimic the approach of a CO₂ plume at a monitoring well. These results support field investigations from other sites: that ??¹³C_DIC is a sensitive tool for monitoring CO₂ migration in the subsurface and simultaneously allows quantification of geochemical trapping of CO₂.     

The impact of CO<Subscript>2</Subscript> on shallow groundwater chemistry: observations at a natural analog site and implications for carbon sequestration

In a natural analog study of risks associated with carbon sequestration, impacts of CO₂ on shallow groundwater quality have been measured in a sandstone aquifer in New Mexico, USA. Despite relatively high levels of dissolved CO₂, originating from depth and producing geysering at one well, pH depression and consequent trace element mobility are relatively minor effects due to the buffering capacity of the aquifer. However, local contamination due to influx of brackish waters in a subset of wells is significant. Geochemical modeling of major ion concentrations suggests that high alkalinity and carbonate mineral dissolution buffers pH changes due to CO₂ influx. Analysis of trends in dissolved trace elements, chloride, and CO₂ reveal no evidence of in situ trace element mobilization. There is clear evidence, however, that As, U, and Pb are locally co-transported into the aquifer with CO₂-rich brackish water. This study illustrates the role that local geochemical conditions will play in determining the effectiveness of monitoring strategies for CO₂ leakage. For example, if buffering is significant, pH monitoring may not effectively detect CO₂ leakage. This study also highlights potential complications that CO₂ carrier fluids, such as brackish waters, pose in monitoring impacts of geologic sequestration.     

Effect of NO2 in exhaust gas from an oxyfuel combustion system on the cap rock of a proposed CO2 injection site

A laboratory geochemical study was conducted using a drill core sample of cap rock from the Surat Basin, Australia, to investigate the effect of NO₂ contained in the CO₂ gas exhausted from the oxyfuel combustion process (oxyfuel combustion CO₂) on the cap rock. A gas (CO₂ containing NO₂) was prepared to simulate the exhaust gas produced from the oxyfuel combustion process. Two types of gases (pure CO₂ and CO₂ containing SO₂) were also prepared as reference gases. The effect of NO₂ on cap rock was studied experimentally using these gases. No differences in the amounts of leached ions and pH changes for CO₂ containing NO₂ (36 ppmv), pure CO₂, and CO₂ containing SO₂ (35 ppmv) existed. The pH values decreased immediately after CO₂ gas injection but increased with time as a result of mineral buffering. Leaching of Fe, Mg, Ca, and K was suggested to have occurred as the result of dissolution of Fe-chlorite, prehnite and illite-smectite mixed layer clay in the shale sample. The amounts of Ca, Fe, and Mg leached with CO₂ containing NO₂ (318 ppmv) were higher than those for pure CO₂. For the mixture containing 318 ppmv NO₂, the pH increased more than that for the other gas conditions immediately after the pH fall at the start of the experiment, because oxidation-reduction reactions occurred between Fe²⁺ and NO₃⁻. Moreover, the results indicated that some of the leached Ca and Fe were deposited on the shale sample because of the pH increase. Therefore, we concluded that the effects of NO₂ on mineral dissolution and pH changes of formation water are negligible when oxyfuel combustion CO₂ containing about 30 ppmv of NO₂ is injected into an underground aquifer. In addition, even if about 300 ppmv NO₂ is accidentally injected into the underground aquifer, mineral dissolution is suppressed due to the buffering of pH decrease after gas injection.     

Potential risks to freshwater resources as a result of leakage from CO<Subscript>2</Subscript> geological storage: a batch-reaction experiment

In assessing the feasibility of widespread deployment of CO₂ geological storage, it is prudent to first assess potential consequences of an error or accident that could lead to CO₂ leakage into groundwater resources above a sequestration interval. Information about the sensitivity of the groundwater system to introduction of CO₂ is needed in order to design groundwater monitoring program. A laboratory-batch experiment was conducted to explore the range of CO₂ impact on groundwater quality of a spectrum of representative aquifers, in the Gulf Coast region, USA. Results show that CO₂ elevated concentrations of many cations within hours or days. Two types of cations were recognized according to their concentration trends. Type I cations—Ca, Mg, Si, K, Sr, Mn, Ba, Co, B, Zn—rapidly increased following initial CO₂ flux and reached stable concentrations before the end of the experiment. Type II cations—Fe, Al, Mo, U, V, As, Cr, Cs, Rb, Ni and Cu—increased at the start of CO₂ flux, but declined, in most cases, to levels lower than pre-CO₂ concentrations. Dissolution of dolomite and calcite caused the largest increase in concentrations for Ca, Mg, Mn, Ba and Sr. Cation release rates decreased linearly as pH increased during mineral buffering. Experiment results suggest that carbonate minerals are the dominant contributor of changes in groundwater quality. Risk assessments of potential degradation of groundwater and monitoring strategies should focus on these fast-reacting minerals. Mobilization risk of Type II cations, however, may be self-mitigated because adsorption occurs when pH rebounds.     

Monitoring of fluid–rock interaction and CO2 storage through produced fluid sampling at the Weyburn CO2-injection enhanced oil recovery site,Saskatchewan, Canada

The Weyburn Oil Field is a carbonate reservoir in south central Saskatchewan, Canada and is the site of a large CO₂ injection project for purposes of enhanced oil recovery. The Weyburn Field, in the Mississippian Midale Formation, was discovered in 1954 and was under primary production until secondary recovery by water flood began in 1964. The reservoir comprises two units, the Vuggy and the Marly, and primary and secondary recovery are thought to only have significantly depleted the Vuggy zone, leaving the Marly with higher oil saturations. In 2000, PanCanadian Resources (now EnCana), the operator of the field, began tertiary recovery by injection of CO₂ and water, primarily into the Marly. The advent of this project was an opportunity to study the potential for geological storage of CO₂.Using 43 Baseline samples collected in August 2000, before CO₂ injection at Weyburn, and 44 monitoring samples collected in March 2001, changes in the fluid chemistry and isotope composition have been tracked. The initial fluid distribution showed water from discovery through water flood in the Midale Formation with Cl ranging from 25,000 to 60,000 mg/L, from the NW to the SE across the Phase 1A area. By the time of Baseline sampling the produced water had been diluted to Cl of 25,000–50,000 mg/L as a result of the addition of make up water from the low TDS Blairmore Formation, but the pattern of distribution was still present. The Cl distribution is mimicked by the distribution of other dissolved ions and variables, with Ca (1250–1500 mg/L) and NH_{3 (aq)} increasing from NW to SE, and alkalinity (700–300 mg/L), resistivity, and H₂S (300–100 mg/L) decreasing. Based on chemical and isotopic data, the H₂S is interpreted to result from bacterial SO₄ reduction. After 6 months of injection of CO₂, the general patterns are changed very little, except that the pH has decreased by 0.5 units and alkalinity has increased, with values over 1400 mg/L in the NW, decreasing to 500 mg/L in the SE. Calcium has increased to range from 1250 to 1750 mg/L, but the pattern of NW–SE distribution is altered. Chemical and isotopic data suggest this change in distribution is caused by the dissolution of calcite due to water–rock reactions driven by CO₂. The Baseline samples varied from −22 to −12‰ δ¹³C (V-PDB) for CO₂ gas. The injected CO₂ has an isotope ratio of −20‰. The Monitor-1 samples of produced CO₂ ranged from −18 to −13‰, requiring a heavy source of C, most easily attributed to dissolution of carbonate minerals. Field measured pH had increased and alkalinity had decreased by the second monitoring trip (July 2001) to near Baseline values, suggesting continued reaction with reservoir minerals.Addition of CO₂ to water–rock mixtures comprising carbonate minerals causes dissolution of carbonates and production of alkalinity. Geochemical modeling suggests dissolution is taking place, however more detail on water–oil–gas ratios needs to be gathered to obtain more accurate estimates of pH at the formation level. Geological storage of CO₂ relies on the potential that, over the longer term, silicate minerals will buffer the pH, causing any added CO₂ to be precipitated as calcite. Some initial modeling of water–rock reactions suggests that silica sources are available to the water resident in the Midale Formation, and that clay minerals may well be capable of acting as pH buffers, allowing injected CO₂ to be stored as carbonate minerals. Further work is underway to document the mineralogy of the Midale Formation and associated units so as to define more accurately the potential for geological storage.     

Well-based hydraulic and geochemical monitoring of the above zone of the CO2 reservoir at Ketzin, Germany

In order to detect hydraulic and geochemical impact on the groundwater directly above the CO₂ storage reservoir at the Ketzin pilot site continuous monitoring using an observation well is carried out. The target depth (446 m below ground level, bgl.) of the well is the Exter formation (Upper Triassic, Rhaetian) which is the closest permeable stratigraphic overlying formation to the CO₂ storage reservoir (630–636 m bgl. at well location). The monitoring concept comprises evaluation of hydraulic conditions, temperature, water chemistry, gas geochemistry and δ¹³C values. This is achieved by a tubing inserted inside the well with installed pressure sensors and a U-tube sampling system so that pumping tests or additional wireline logging can be carried out simultaneously with monitoring. The aquifer was examined using a pump test. The observation well is hydraulically connected to the regional aquifer system and the permeability of about 1.8 D is comparatively high. Between Sept. 2011 and Oct. 2012, a pressure increase of 7.4 kPa is observed during monitoring under environmental conditions. Drilling was carried out with drilling mud on carbonate basis. The concentration of residual drilling mud decreases during the pump test, but all samples show a residual concentration of drilling mud. The formation fluid composition is recalculated with PHREEQC and is comparable to the literature values for the Exter formation. The gas partial pressure is below saturation at standard conditions and the composition is dominated by N₂ similar to the underlying storage reservoir prior to CO₂ injection. The impact of residual drilling mud on dissolved inorganic carbon and the respective δ¹³C values decreases during the monitoring period. The pristine isotopic composition cannot be determined due to calcite precipitation. No conclusive results indicate a leakage from the underlying CO₂ storage reservoir.     

Laboratory experiments and field study for the detection and monitoring of potential seepage from CO2 storage sites

Potential CO₂ seepages from geological storage sites or from the injection rig may affect the surrounding environment. To develop reliable detection techniques for such seepages a laboratory rig was designed that is composed of three vertical Plexiglas columns. The columns can be filled with sediments and water; CO₂ can be injected from the bottom. Two columns are used to simulate the impact of CO₂ on soils; while the third one, which is larger in size, simulates CO₂ seepage in aquatic environments. The main results of the laboratory experiments indicate that increased levels of CO₂ generate a quick drop in pH. Once the seepage is stopped, a partial recovery towards the initial values of pH is recorded. The outcomes of the laboratory experiments on the aquatic seepage are compared with observations from a submarine natural emission of CO₂. In this natural underwater seepage multi-parametric probes and laboratory analysis were used to analyze the composition and the chemical effects of the emitted gas; basic acoustic techniques were tested as tools for the prompt detection of CO₂ bubbles in water.     

Stable isotope (2H, 18O and 87Sr/86Sr) and hydrochemistry monitoring for groundwater hydrodynamics analysis in a karst aquifer (Gran Sasso,Central Italy)

This paper deals with chemical and isotope analyses of 21 springs, which were monitored 3 times in the course of 2001; the monitoring program was focused on the groundwater of the Gran Sasso carbonate karst aquifer (Central Italy), typical of the mountainous Mediterranean area.Based on the hydrogeological setting of the study area, 6 groups of springs with different groundwater circulation patterns were distinguished. The hydrogeochemistry of their main components provided additional information about groundwater flowpaths, confirming the proposed classification. The spatial distribution of their ion concentrations validated the assumptions underlying the hydrogeological conceptual model, showing diverging groundwater flowpaths from the core to the boundaries of the aquifer. Geochemical modelling and saturation index computation elucidated water–carbonate rock interaction, contribution by alluvial aquifers at the karst aquifer boundaries, as well as impacts of human activities.The analysis of ¹⁸O/¹⁶O and ²H/H values and their spatial distribution in the aquifer substantiated the hydrogeology-based classification of 6 groups of springs, making it possible to trace back groundwater recharge areas based on mean isotope elevations; the latter were calculated by using two rain monitoring stations. ⁸⁷Sr/⁸⁶Sr analyses showed seasonal changes in many springs: in winter–spring, the changes are due to inflow of new recharge water, infiltrating into younger rocks and thus increasing ⁸⁷Sr/⁸⁶Sr values; in summer–autumn, when there is no recharge and spring discharge declines, changes are due to base flow groundwater circulating in more ancient rocks, with a subsequent drop in ⁸⁷Sr/⁸⁶Sr values.The results of this study stress the contribution that spatio-temporal isotope monitoring can give to the definition of groundwater flowpaths and hydrodynamics in fissured and karst aquifers, taking into account their hydrogeological and hydrogeochemical setting.     

Potential environmental issues of CO2 storage in deep saline aquifers: Geochemical results from the Frio-I Brine Pilot test,Texas, USA

Sedimentary basins in general, and deep saline aquifers in particular, are being investigated as possible repositories for large volumes of anthropogenic CO₂ that must be sequestered to mitigate global warming and related climate changes. To investigate the potential for the long-term storage of CO₂ in such aquifers, 1600 t of CO₂ were injected at 1500 m depth into a 24-m-thick “C” sandstone unit of the Frio Formation, a regional aquifer in the US Gulf Coast. Fluid samples obtained before CO₂ injection from the injection well and an observation well 30 m updip showed a Na–Ca–Cl type brine with ∼93,000 mg/L TDS at saturation with CH₄ at reservoir conditions; gas analyses showed that CH₄ comprised ∼95% of dissolved gas, but CO₂ was low at 0.3%. Following CO₂ breakthrough, 51 h after injection, samples showed sharp drops in pH (6.5–5.7), pronounced increases in alkalinity (100–3000 mg/L as HCO₃) and in Fe (30–1100 mg/L), a slug of very high DOC values, and significant shifts in the isotopic compositions of H₂O, DIC, and CH₄. These data, coupled with geochemical modeling, indicate corrosion of pipe and well casing as well as rapid dissolution of minerals, especially calcite and iron oxyhydroxides, both caused by lowered pH (initially ∼3.0 at subsurface conditions) of the brine in contact with supercritical CO₂.     

Modeling, parameterization and evaluation of monitoring methods for CO2 storage in deep saline formations: the CO2-MoPa project

Capture and geological sequestration of CO₂ from large industrial sources is considered a measure for reducing anthropogenic emissions of CO₂ and thus mitigating climate change. One of the main storage options proposed are deep saline formations, as they provide the largest potential storage capacities among the geologic options. A thorough assessment of this type of storage site therefore is required. The CO₂-MoPa project aims at contributing to the dimensioning of CO₂ storage projects and to evaluating monitoring methods for CO₂ injection by an integrated approach. For this, virtual, but realistic test sites are designed geometrically and fully parameterized. Numerical process models are developed and then used to simulate the effects of a CO₂ injection into the virtual test sites. Because the parameterization of the virtual sites is known completely, investigation as well as monitoring methods can be closely examined and evaluated by comparing the virtual monitoring result with the simulation. To this end, the monitoring or investigation method is also simulated, and the (virtual) measurements are recorded and evaluated like real data. Application to a synthetic site typical for the north German basin showed that pressure response has to be evaluated taking into account the layered structure of the storage system. Microgravimetric measurements are found to be promising for detecting the CO₂ phase distribution. A combination of seismic and geoelectric measurements can be used to constrain the CO₂ phase distribution for the anticline system used in the synthetic site.     

High-resolution stable carbon isotope monitoring indicates variable flow dynamic patterns in a deep saline aquifer at the Ketzin pilot site (Germany)

Stable isotopes of injected CO₂ act as useful tracers in carbon capture and storage (CCS) because the CO₂ itself is the carrier of the tracer signal and remains unaffected by sorption or partitioning effects. At the Ketzin pilot site (Germany), carbon stable isotope composition (δ¹³C) of injected CO₂ at the injection well was analyzed over a time period of 4 months. Occurring isotope variances resulted from the injection of CO₂ from two different sources (an oil refinery and a natural gas-reservoir). The two gases differed in their carbon isotope composition by more than 27‰. In order to find identifiable patterns of these variances in the reservoir, more than 250 CO₂-samples were collected and analyzed for their carbon isotope ratios at an observation well 100 m distant from the injection well. An isotope ratio mass spectrometer connected to a modified Thermo Gasbench system allowed quick and cost effective isotope analyses of a high number of CO₂ gas specimens. CO₂ gas from the oil refinery (δ¹³C = −30.9‰, source A) was most frequently injected and dominated the reservoir δ¹³C values at the injection site. Sporadic injection of the CO₂ from the natural gas-reservoir (δ¹³C = −3.5‰, source B) caused isotope shifts of up to +5‰ at the injection well. These variances provided a potential ideal tracer for CO₂ migration behavior. Based on these findings, tracer input signals that were injected during the last 2 years of injection could be reconstructed with the aid of an isotope mixing model and CO₂ delivery schedules. However, in contrast to the injection well, δ¹³C values at the observation well showed no variances and a constant value of −28.5‰ was measured at 600 m depth. This is in disagreement with signals that would be expected if the input signals from the injection would arrive at the observation well. The lack of isotope signals at the observation well suggests that parts of the reservoir are filled with CO₂ that is immobilized.     

Suitability of Existing Numerical Model Codes and Thermodynamic Databases for the Prognosis of Calcite Dissolution Processes in Near-Surface Sediments Due to a CO2 Leakage Investigated by Column Experiments

Among the risks of CO₂ storage is the potential of CO₂ leakage into overlaying formations and near-surface potable aquifers. Through a leakage, the CO₂ can intrude into protected groundwater resources, which can lead to groundwater acidification followed by potential mobilisation of heavy metals and other trace metals through mineral dissolution or ion exchange processes. The prediction of pH buffer reactions in the formations overlaying a CO₂ storage site is essential for assessing the impact of CO₂ leakages in terms of trace metal mobilisation. For buffering the pH-value, calcite dissolution is one of the most important mechanisms. Although calcite dissolution has been studied for decades, experiments conducted under elevated CO₂ partial pressures are rare. Here, the first study for column experiments is presented applying CO₂ partial pressures from 6 to 43 bars and realising a near-natural flow regime. Geochemical calculations of calcite dissolution kinetics were conducted using PHREEQC together with different thermodynamic databases. Applying calcite surface areas, which were previously acquired by N₂-BET or calculated based on grain diameters, respectively, to the rate laws according to Plummer et al. (Am J Sci 278:179–216, doi:10.2475/ajs.278.2.179, 1978) or Palandri and Kharaka (US Geol Surv Open file Rep 2004–1068:71, 2004) in the numerical simulations led to an overestimation of the calcite dissolution rate by up to three orders of magnitude compared to the results of the column experiments. Only reduction of the calcite surface area in the simulations as a fitting procedure allowed reproducing the experimental results. A reason may be that the diffusion boundary layer (DBL), which depends on the groundwater flow velocity and develops at the calcite grain surface separating it from the bulk of the solution, has to be regarded: The DBL leads to a decrease in the calcite dissolution rate under natural laminar flow conditions compared to turbulent mixing in traditional batch experiments. However, varying the rate constants by three orders of magnitudes in a field scale PHREEQC model simulating a CO₂ leakage produced minor variations in the pH buffering through calcite dissolution. This justifies the use of equilibrium models when calculating the calcite dissolution in CO₂ leakage scenarios for porous aquifers and slow or moderate groundwater flow velocities. However, the selection of the thermodynamic database has an impact on the dissolved calcium concentration, leading to an uncertainty in the simulation results. The resulting uncertainty, which applies also to the calculated propagation of an aquifer zone depleted in calcite through dissolution, seems negligible for shallow aquifers of approximately 60 m depth, but amounts to 35 % of the calcium concentration for aquifers at a depth of approximately 400 m.     

Monitoring above-zone temperature variations associated with CO2 and brine leakage from a storage aquifer

CO₂ injection in saline aquifers induces temperature changes owing to processes such as Joule–Thomson cooling, endothermic water vaporization, exothermic CO₂ dissolution besides the temperature discrepancy between injected and native fluids. CO₂ leaking from the injection zone, in addition to initial temperature contrast due to the geothermal gradient, undergoes similar processes, causing temperature changes in the above zone. Numerical simulation tools were used to evaluate temperature changes associated with CO₂ leakage from the storage aquifer to an above-zone monitoring interval and to assess the monitorability of CO₂ leakage on the basis of temperature data. The impact of both CO₂ and brine leakage on temperature response is considered for three cases (1) a leaky well co-located with the injection well, (2) a leaky well distant from the injector, and (3) a leaky fault. A sensitivity analysis was performed to determine key operational and reservoir parameters that control the temperature signal in the above zone. Throughout the analysis injection-zone parameters remain unchanged. Significant pressure drop upon leakage causes expansion of CO₂ associated with Joule–Thomson cooling. However, brine may begin leaking before CO₂ breakthrough at the leakage pathway, causing heating in the above zone. Thus, unlike the pressure which increases in response to both CO₂ and brine leakage, the temperature signal may differentiate between the leaking fluids. In addition, the strength of the temperature signal correlates with leakage velocity unlike pressure signal whose strength depends on leakage rate. Increasing leakage conduit cross-sectional area increases leakage rate and thus increases pressure change in the above zone. However, it decreases leakage velocity, and therefore, reduces temperature cooling and signal. It is also shown that the leakage-induced temperature change covers a small area around the leakage pathway. Thus, temperature data will be most useful if collected along potential leaky wells and/or wells intersecting potential leaky faults.     

Natural Gas Hazard (CO2, 222 Rn) within a Quiescent Volcanic Region and Its Relations with Tectonics: The Case of the Ciampino-Marino Area, Alban Hills Volcano, Italy

Groundwater surveys were performed by detailed(around 300 sites) grid-analysis of water temperature, pH, redox potential, electrical conductivity, ²²²Rn, alkalinity and by calculating the pCO₂, throughout the Ciampino and Marino towns in the Alban Hills quiescent volcano (Central Italy). Following several episodes of dangerous CO₂ exhalation from soils during the last 20 years and earlier ashistorically recorded, the work aimed at assessing the Natural Gas Hazard (NGH) including the indoor-Rn hazard. The NGH was defined as the probability of an area to become a site of poisonous peri-volcanic gas exhalations from soils to the lower atmosphere (comprising buildings). CO₂ was found to be a ``carrier' for the other poisonous minor and in trace components (H<sub>s</sub>S, CH<sub>4</sub>, <sup>222</sup>Rn, etc.). This assessment was performed by extrapolating in the aquifer CO<sub>2</sub> and <sup>222</sup>Rn conditions, and discriminating sectors where future CO<sub>2</sub> flux in soils as well as indoor-Rn measurements have to be noted. A preliminary indoor-Rn survey was performed at about 200 sites. The highest values were found in the highest pCO<sub>2</sub> and high <sup>222</sup>Rn values in groundwater. This indicates convection and enhanced permeability in certain sectors of the main aquifer, i.e., along the bordering faults and inside the gas-trap of the Ciampino Horst., where ``continuous gas-phase micro-macro seepage mechanism' is invoked to explain the high peri-volcanic gases flux.     

Mixing of magmatic CO2 into volcano groundwater flow at Aso volcano assessed combining carbon and water stable isotopes

To understand deep groundwater flow systems and their interaction with CO₂ emanated from magma at depth in a volcanic edifice, deep groundwater samples were collected from hot spring wells in the Aso volcanic area for hydrogen, oxygen and carbon isotope analyses and measurements of the stable carbon isotope ratios and concentrations of dissolved inorganic carbon (DIC). Relations between the stable carbon isotope ratio (δ¹³C_DIC) and DIC concentrations of the sampled waters show that magma-derived CO₂ mixed into the deep groundwater. Furthermore, groundwaters of deeper areas, except samples from fumarolic areas, show higher δ¹³C_DIC values. The waters' stable hydrogen and oxygen isotope ratios (δD and δ¹⁸O) reflect the meteoric-water origin of that region's deep groundwater. A negative correlation was found between the altitude of the well bottom and the altitude of groundwater recharge as calculated using the equation of the recharge-water line and δD value. This applies especially in the Aso-dani area, where deeper groundwater correlates with higher recharge. Groundwater recharged at high altitude has higher δ¹³C_DIC of than groundwater recharged at low altitude, strongly suggesting that magmatic CO₂ is present to a much greater degree in deeper groundwater. These results indicate that magmatic CO₂ mixes into deeper groundwater flowing nearer the magma conduit or chamber.     

Interaction between deep and shallow groundwater systems in areas affected by Quaternary tectonics (Central Italy): a geochemical and isotope approach

Hydro- and isotope geochemistry are used to refine groundwater conceptual models in two areas of central Italy (Acque Albule Basin and Velino River Valley) affected by extensional Quaternary tectonics, where deep and shallow groundwater flow systems are interacting. The role of geology, of recent deposits filling the plains and of main tectonic features controlling groundwater flowpaths and deep-seated fluids emergences are investigated and discussed. Environmental isotopes (²H and ¹⁸O) confirm recharge in the surrounding carbonate aquifers, and meteoric origin of both shallow and deep groundwater. Major ion chemistry indicates a mixing between shallow Ca-HCO₃ groundwater from carbonate aquifers and deep Ca-HCO₃-SO₄ groundwater, characterised by higher salinity and temperature and high concentration in sulphates. Isotopic composition of dissolved sulphates (δ ³⁴S and δ ¹⁸O) and dissolved inorganic carbon (δ ¹³C), henceforth indicated as DIC, are used to verify the presence of different sources of groundwater, and to validate the mixing model suggested by the major ion analyses. Sulphate isotope composition suggests a marine origin for the groundwater characterised by elevated sulphate concentration, whose source is present in the deep buried sequences. Carbon isotope composition confirms the role of a DIC source associated to CO₂ degassing of a deep reservoir. Groundwater conceptual models are improved underlining the importance of Plio-Pleistocene sequences filling the tectonic depression. In the Acque Albule area, the travertine plateau represents a mixing stratified aquifer, where deep groundwater contribution is spread into the shallow aquifer. The alluvial–clastic–lacustrine leaky aquifer of Velino Valley enables a complete mixing of shallow and deep groundwater allowing spot-located discharge of deep groundwater along tectonic patterns and facilitating sulphate reduction in the lacustrine sediments, explaining locally the presence of H₂S.