Natural Analogue Studies Research Articles

Spectroscopic studies on natural fluorapatites irradiated with 10 MeV electrons

Fluorapatites are one of the candidate matrices for hosting the nuclear waste from molten salt reactors. To assess their radiation stability and long-term performance, natural analogue study approach was undertaken. Naturally occurring fluorapatites containing with carbonate substitutions were irradiated with 10 MeV electron beam radiation for doses 20 MGy. X-ray diffraction, Raman and Fourier Transform infrared spectroscopy show no evidence of structural degradation or phosphate condensation. However, a change in the intensity of ν3 Phosphate Raman bands was observed indicating that the phosphate tetrahedra is affected by the electron beam consistent with the displacement cross-section calculations for each constituent element. Overall, the study confirmed that fluorapatite possess good structural stability against electron radiation upto 20 MGy.

Review of secondary phases formed under natural alkaline conditions at low temperatures and implications for cement–bentonite interactions in radioactive waste repositories

Abstract The alteration of bentonite under alkaline conditions and the subsequent changes in properties such as permeability and self-sealing ability should be evaluated for the performance assessment of radioactive waste repositories. As the period of evaluation for alterations is extremely long, natural analog (NA) studies that can observe long-term phenomena similar to the system of radioactive waste repositories have significant advantages. However, locations that can be set up as NA study sites with significant similarity are limited and should be pursued by localizing analog systems. This literature review summarized studies reporting secondary phases formed at low temperatures (<100°C) under a broader range of natural sites which are chemically similar to the alkaline conditions expected at bentonite in radioactive waste repositories, including near pyrometamorphic rocks, near ophiolites, and in alkaline saline lakes. This review provides insights into the species, formation conditions, and stability of secondary phases that could be formed during cement–bentonite interactions and the timescale for mineralogical transitions from a metastable to a stable phase. The findings could be useful for selecting secondary phases to be considered in reactive transport modeling for predicting cement–bentonite interactions in radioactive waste repositories.

Water-rock interactions of uranium deposits: A field investigation and laboratory batch experiment

Interactions between bedrock and groundwater in the far-field of a deep geological repository (DGR) for high-level radioactive waste significantly affect the transport of uranium, which is the major radionuclide in a DGR. Therefore, the present study evaluated the geochemical behavior of uranium by assessing the hydrogeochemical characteristics of groundwater, surface water, mine water, and quarry runoff water in the Okcheon metamorphic belt, which represents a natural analogue study site in Korea. A batch experiment was also conducted to further elucidate the interactions between the uranium-containing rock and groundwater in the study area. The results of the field investigation indicated that uranium in groundwater formed aqueous complexes in the form of calcium uranyl tricarbonate. The concentrations of uranium in groundwater were low, at less than 1 μg L−1, which seems to be attributable to the dissolutions of uraninite, coffinite, UO2(am), and U4O9(c) under the moderately reduced condition and subsequent control by co-precipitation with iron (hydr)oxides. The results of the batch experiment showed that uranium concentrations may be controlled by adsorption or surface complexation with iron oxides. The field study demonstrates the equilibrium state maintained in the current geochemical conditions at the study site, while the batch experiment provides implications regarding the reaction processes over time. Overall, this study showed that uranium forms complexes with carbonate and sulfate under the geochemical conditions of the study site, and that its mobility could be restricted through co-precipitation or adsorption/surface complexation. This study is expected to contribute to a comprehensive understanding of how the behavior of uranium is affected by the evolution of geochemical conditions around the DGR.

Natural Analogue Study on the Disposal of Radioactive Waste Using Uranium Deposits and Geochemical Behaviors of Uranium

Natural Analogue Study on the Disposal of Radioactive Waste Using Uranium Deposits and Geochemical Behaviors of Uranium

Natural Analogue Studies in Support of Post-Closure Safety Assessment of Deep Geological Disposal

Natural analogues are systems that have evolved over geological timescales with features similar to one or several components of a deep geological repository (DGR). Natural analogues complement short-duration laboratory studies since they are existing reflections of many long-term processes that might affect the performance of a repository. Mathematical models are often used for the post-closure safety assessment of a DGR. Confidence in the models’ predictions is enhanced when the models successfully simulate the past evolution of a natural analogue. This paper summarizes the Canadian Nuclear Safety Commission’s (CNSC’s) recent research on natural analogues to inform on (1) glacial erosion, (2) engineered barrier system, and (3) uranium reactive transport in the context of DGRs for radioactive wastes. Glaciation and its erosion are prominent factors impacting the performance of future DGRs at high latitudes in the northern hemisphere. The authors have reviewed the field data from the Greenland Analogue Project, developed a conceptual and mathematical model for the simulation of the thermal conditions within the Greenland ice sheet, as well as the thermal-hydraulic conditions at its base and the ice sheet velocity, and eventually estimated the erosion rate at the site. The Cigar Lake Analogue demonstrates the long-term radionuclide containment capability of the illite clay zone enveloping the ore body, serving as an analogy to the engineered clay barriers. The CNSC and University of Ottawa analyzed 129I in the Cigar Lake core samples, and modeled and correlated the diffusion-dominated transport of radionuclides over the geological evolution of the Cigar Lake deposit. The results provide information on the mobility of fission products and significant radionuclides in conditions analogous to the source, engineered barriers, and near-field host rock of a DGR. The reactive transport and geochemistry of the Kiggavik-Andrew Lake uranium deposit mineralization and remobilization was another natural uranium deposit analogue studied by the CNSC. A reactive transport model was established according to the conceptualized geochemical processes and run under specified boundary and initial conditions to validate the geochemical processes. The geometry, timing, geochemistry, and fluid composition were used as model constraints.

Hydrothermal-activity stage classification and power-generation potential evaluation of geothermal wells based on a natural analog study on epithermal deposits, in Japan

In this study, we prepare guidelines for hydrothermal-activity stage classification and evaluate the power-generation potential of geothermal wells based on a natural analog study on the hydrogeological and thermal structures and hydrothermal-alteration minerals in a low-sulfidation epithermal deposit. As such, many high-temperature geothermal wells in Japan were classified into four hydrothermal-activity stages (early, middle, late-1, and late-2) based on the developed guidelines. In conclusion, the late-1-stage well is evaluated to supply fluids for power generation with the least economic and environmental risks. In contrast, the geothermal wells in other active stages indicate some of the concerns.

Hydrothermal-Activity Stage Classification and Power-Generation Potential Evaluation of Geothermal Wells Based on a Natural Analog Study on Epithermal Deposits, in Japan

Hydrothermal-Activity Stage Classification and Power-Generation Potential Evaluation of Geothermal Wells Based on a Natural Analog Study on Epithermal Deposits, in Japan

Potential Pb 2+ mobilization, transport, and sequestration in shallow aquifers impacted by multiphase CO 2 leakage: a natural analogue study from the Virgin River Basin in SW Utah

Geological carbon sequestration (GCS) is necessary to help meet goals for emissions reduction, but groundwater contamination may occur if CO 2 and/or brine were to leak out of deep storage formations into the shallow subsurface. For this study, a natural analogue was investigated: in the Virgin River Basin of SW Utah, water with moderate salinity and high CO 2 concentrations is leaking upwards into shallow aquifers that contain heavy-metal-bearing concretions. The aquifer system is comprised of the Navajo and Kayenta formations, which are pervasive across southern Utah and have been considered as a potential GCS injection unit where they are sufficiently deep. Numerical models of the site were constructed based on measured water chemistry and head distributions from previous studies. Simulations were used to improve understanding of the rate and distribution of the upwelling flow into the aquifers, and to assess the reactive transport processes that may occur if the upwelling fluids were to interact with a zone of iron oxide and other heavy metals, representing the concretions that are common in the area. Various mineralogies were tested, including one in which Pb 2+ was adsorbed onto ferrihydrite, and another in which it was bound within a solid mixture of litharge (PbO) and hematite (Fe 2 O 3 ). Results indicate that metal mobilization depends strongly on the source-zone composition and that Pb 2+ transport can be naturally attenuated by gas-phase formation and carbonate-mineral precipitation. These findings could be used to improve risk assessment and mitigation strategies at geological carbon sequestration sites. Thematic collection: This article is part of the Geoscience for CO 2 storage collection available at: https://www.lyellcollection.org/cc/geoscience-for-co2-storage

A study of natural analogues for predicting the performance of a CO2 geological storage: the experience from a natural CO2 reservoir (Gañuelas-Mazarrón Tertiary Basin, SE Spain)

In the framework of a Spanish project focused on carbon capture and storage technologies, the Ganuelas-Mazarron Tertiary Basin (SE Spain) was studied as a natural analogue of a CO2 reservoir affected by anthropogenic leakages. It has been accepted that the main objective of natural analogue studies is to predict the long-term performance of a natural CO2 reservoir to be extrapolated to the operation of a CO2 deep geological storage, but these studies can also provide valuable information to select a site for CO2 storage. Thus, the comprehensive study performed in this Spanish basin has allowed the establishment of a guide to be applied to other similar natural systems with deep saline aquifers that are able to store CO2. This guide comprises 5 phases: (1) the compilation of existing information from the site; (2) the geological and structural study of the natural CO2 reservoir; (3) the characterisation of the main components (waters–rocks–gases) of the natural CO2 reservoir; (4) the identification of analogies between the natural CO2 reservoir and a potential site for CO2 geological storage; and (5) the implications for the long-term behaviour and safety of a CO2 storage system. Whilst the three first stages are well known since they are exclusively focused on the site characterisation, the latter two are poorly developed. For this reason, it has been considered convenient to go deeper into both the identification of analogies and the assessment of their performance in storing CO2. The main results of this study are aimed at elaborating a practical guide for regulatory agencies that are responsible for making decisions about sites that have been selected for anthropogenic CO2 geological storage.

Long term reactivity of CO2 in a low salinity reservoir-seal complex

An understanding of the long-term reactivity of different rock types to injected CO2 is needed for sequestration site assessment. Relative to saline aquifer studies, the long term reactivity of CO2 in low salinity aquifers has received little attention. Currently in Australia, the Surat Basin is being appraised for its large-scale CO2 storage potential within low salinity aquifers. Sixteen core samples from the Precipice Sandstone and Evergreen Formation – the notional target reservoir and seal complex – were characterized for mineral content; helium, mercury-injection and micro CT porosities; air permeability; and, imaged with SEM-EDS. Samples consisted of quartz rich reservoir sandstones, feldspar and clay rich or calcite cemented sandstones (secondary reservoir), mudstones (sealing complex), and oolitic ironstones (sealing complex) derived from braided river, fluvial-deltaic, and restricted marine shoal depositional environments, respectively. The reservoir sandstone samples characterized here had measured total porosity that ranged from 11 to 23% with pore throats mainly between 90 and 100 μm, and core air permeability from 558 to 3397 mD. In the Precipice Sandstone reservoir sample μCT plugs, 98% of the pore space was connected with calculated vertical permeability 145–4611 mD and horizontal 4291–8200 mD. Feldspar and clay rich sandstone and mudstone samples from the overlying Evergreen Formation had porosity that ranged between 0.2 and 22.9%, with a wide range of pore throat sizes from ~0.005 to 30 μm, and permeability from 0.2 to 28.1 mD, respectively. Ironstone and mudstone samples from the Westgrove Ironstone Member (Evergreen Formation) had porosity from 0.7 to 9.7% and a low permeability of 0.04 mD.Kinetic geochemical CO2 reactivity models made predictions over two time-scales: 30 or 1000 years. Selected models also accounted for the potential presence of 10 ppm SO2 gas. The Precipice Sandstone quartz-rich reservoir sandstones had consistently small amounts of reactive minerals and mineral trapping or scaling of the reservoir was not predicted over 30 years, with the pH approximately 4.5 after 30 years. Samples from the Evergreen Formation included feldspar and clay rich sandstones and mudstones, several contained variable amounts of carbonate cement. Their response to CO2 was more influenced by mineral content than rock type. Plagioclase feldspars and Fe-rich chlorite were the main silicate minerals that reacted to produce siderite and ankerite mineral trapping up to 2.57 kg/m3 CO2. In the very unlikely event that CO2 rich fluids migrated upwards as far as the Westgrove Ironstone Member, chlorite is predicted to alter to siderite. This study indicates that the Precipice Sandstone reservoir in the study region has a low likelihood of mineral scaling which is favorable to avoid CO2 injectivity issues. Mineral trapping as ankerite and siderite could be expected to trap CO2 in the chlorite and plagioclase rich Evergreen Formation seal lithologies. Further work is suggested on validating long term predictions with observation data from natural analogue studies.

Understanding of Long-Term CO2-Brine-Rock Geochemical Reactions Using Numerical Modeling and Natural Analogue Study

To further understand the interactions of CO2-brine-rock at geological time scales, in this study, a 1D reactive transport model of CO2 intrusion into sandstone of the Longtan Formation (P2l) in the Huangqiao area, China, was constructed based on site-specific data. The simulation time is consistent with the retention time of CO2 in the Longtan sandstone Formation and is set to 20 Ma. The reactive transport model is calibrated and revised using the measured data for sandstone samples from Well X3 (i.e., the natural analogue). By comparing the simulation results with measured data for the natural analogue, the long-term geochemical reactions are investigated. The simulation results indicate that the brine-rock interactions induced by CO2 can be roughly divided into two stages. First, susceptible minerals (e.g., chlorite, ankerite, calcite, and feldspar minerals) dissolve rapidly under acidic conditions formed by the dissolution of CO2. The precipitation of siderite is facilitated by the dissolution of ankerite and chlorite. Smectite-Ca and dawsonite precipitate due to the dissolution of anorthite and albite, respectively. Dawsonite begins to convert into smectite-Na when albite is completely dissolved. As the reactions continue, intermediate products (i.e., illite, smectite-Na, and smectite-Ca) generated in the first stage become the reactants and subsequently react with CO2 and brine. These three clay minerals are not stable under acidic conditions and transform into kaolinite and paragenetic quartz in the later stage of reaction. Comparing the simulation results of the Base Case with the measured data for the natural analogue and inspired by previous studies, the scour of kaolinite is supposed to have occurred in this region and is considered in the revised model by introducing a coefficient of the scour of kaolinite (i.e., Case 2). The simulation results of Case 2 fit well with the measured data on mineral assemblage, and the trend of the sandstone porosity growth caused by the CO2-brine-rock reaction is captured by our simulation results. The combination of numerical simulation and natural analogue study indicates that the joint effects of long-term CO2-brine-rock reactions and scour of kaolinite increase the pore space of the host rock and result in an increase in quartz content in the sandstone.

Brief communication: Understanding solar geoengineering's potential to limit sea level rise requires attention from cryosphere experts

Abstract. Stratospheric aerosol geoengineering, a form of solar geoengineering, is a proposal to add a reflective layer of aerosol to the stratosphere to reduce net radiative forcing and so to reduce the risks of climate change. The efficacy of solar geoengineering at reducing changes to the cryosphere is uncertain; solar geoengineering could reduce temperatures and so slow melt, but its ability to reverse ice sheet collapse once initiated may be limited. Here we review the literature on solar geoengineering and the cryosphere and identify the key uncertainties that research could address. Solar geoengineering may be more effective at reducing surface melt than a reduction in greenhouse forcing that produces the same global-average temperature response. Studies of natural analogues and model simulations support this conclusion. However, changes below the surfaces of the ocean and ice sheets may strongly limit the potential of solar geoengineering to reduce the retreat of marine glaciers. High-quality process model studies may illuminate these issues. Solar geoengineering is a contentious emerging issue in climate policy and it is critical that the potential, limits, and risks of these proposals are made clear for policy makers.

Microscale Research on Effective Geosequestration of CO2 in Coal Reservoir: A Natural Analogue Study in Haishiwan Coalfield, China

A natural analogue study in CO2-rich coalfield (Haishiwan, China) provides a strong support for safe, reliable, and long-term storage by analyzing the mechanism of CO2 migration, entrapment, and storage in coal reservoir. Thus, effects of geological tectonism on reservoir properties were investigated. Simultaneously, coal and oil shale samples before and after supercritical CO2 (SCCO2) treatment via geochemical reactor were collected to analyze changes in pore structure, functional group distributions, and SCCO2 extraction. Observations from in situ properties of coal seam indicate that there is a positive relationship with CH4 contents and F19 fault whereas CO2 and carbonate contents decrease as the distance from F19 increases. Analysis of pore properties reveals that SCCO2 enlarges the development of coal pore and facilitates the diffusion and seepage channel of coal reservoir, while no changes in larger pores are found in oil shale, which may restrain fluids from passing through. Then, oxygen-containing functional groups are mobilized by SCCO2 from oil shale, associated with a decrease in sorption sites. The sealing capacity of cap rock (oil shale) and geological tectonism (F19 fault), as the major contributors to CO2 enrichment and accumulation, provides insights into the suitable selection of CCGS site for long geological time.

A Natural Analogue Approach for Discriminating Leaks of CO2 Stored Underground Using Groundwater Geochemistry Statistical Methods, South Korea

Carbon capture and storage (CCS) is one of several useful strategies for capturing greenhouse gases to counter global climate change. In CCS, greenhouse gases such as CO2 that are emitted from stacks are isolated in underground geological storage. Natural analogue studies that can provide insights into possible geological CO2 storage sites, can deliver crucial information about the safety and security of geological sequestration, the long-term impact of CO2 storage on the environment, and the field operation and monitoring requirements for geological sequestration. This study adopted a probability density function (PDF) approach for CO2 leakage monitoring by characterizing naturally occurring CO2-rich groundwater as an analogue that can occur around a CO2 storage site due to CO2 dissolving into fresh groundwater. Two quantitative indices, (QItail and QIshift), were estimated from the PDF test and were used to compare CO2-rich and ordinary groundwaters. Key geochemical parameters (pH, electrical conductance, total dissolved solids, HCO3−, Ca2+, Mg2+, and SiO2) in different geological regions of South Korea were determined through a comparison of quantitative indices and the respective distribution patterns of the CO2-rich and ordinary groundwaters.

Reactivity of supercritical sulfur dioxide and carbon dioxide in a carbonate reservoir: An experimental investigation of supercritical fluid-brine-rock interactions relevant to the Madison Limestone of Southwest Wyoming

Managing impure carbon dioxide produced by fossil fuel-based generation of electricity is required for successful implementation of carbon capture, utilization, and storage. Impurities in carbon dioxide, particularly [Formula: see text] and [Formula: see text], are geochemically more reactive than the carbon dioxide and may adversely impact a carbon dioxide storage reservoir by generating additional acidity. Hydrothermal experiments are performed to evaluate geochemical and mineralogic effects of injecting [Formula: see text]-[Formula: see text] fluid into a carbonate reservoir. The experimental design is based on a natural carbon dioxide reservoir, the Madison Limestone on the Moxa Arch of Southwest Wyoming, which serves as a natural analog for geologic cosequestration of sulfur dioxide and carbon dioxide. Idealized Madison Limestone ([Formula: see text]) and [Formula: see text] brine ([Formula: see text], initial [Formula: see text]) reacted at reservoir conditions (110°C and 25 MPa) for approximately 165 days (3960 h). Carbon dioxide fluid containing 500 ppmv sulfur dioxide was injected and the experiment continued for approximately 55 days (1326 h). Sulfur dioxide partitions out of the supercritical carbon dioxide phase and dissolves into coexisting brine on the time scale of the experiments (55 days). Injecting supercritical [Formula: see text]-[Formula: see text] or pure supercritical carbon dioxide into a brine-limestone system produces the same in situ pH (4.6) and ex situ pH (6.4–6.5), as measured 28 h after injection because dissolution of calcite buffers in situ pH. Precipitation of anhydrite sequesters injected sulfur and, coupled with dissolution of calcite, effectively buffers the amount of dissolved calcium to the same concentrations measured in limestone-brine experiments injected with pure carbon dioxide. Supercritical [Formula: see text]-[Formula: see text] does not enhance the sequestration potential of a carbonate reservoir relative to pure supercritical carbon dioxide. Our results substantiate predictions from natural analog studies of the Madison Limestone that anhydrite traps sulfur and carbonate minerals ultimately reprecipitate and mineralize carbon in carbonate reservoirs.

Hydrochemical and Isotopic Characteristics of CO2-rich Groundwater in the Gyeongsang Sedimentary Basin, South Korea: A Natural Analogue Study on the Potential Leakage of Geologically-stored CO2

The potential of geologic carbon storage has been considered in the Gyeongsang sedimentary basin (GSB) at the southeastern part of South Korea. In order to understand the long-term behaviors of geologically-stored CO2, hydrochemical and multi-isotopic data (δ18O-δD of water and δ13C of dissolved inorganic carbon) of groundwater samples were collected from naturally seeping CO2-rich springs and ambient shallow groundwater wells in the GSB. The collected samples were classified into three hydrochemical groups: 1) dilute and acidic, CO2-rich springs, 2) high TDS, CO2-rich springs, and 3) CO2-poor groundwater. CO2-rich springs (i.e., Groups 1 and 2) were differentiated from Group 3 by their high carbon isotope values and partial pressure of CO2, suggesting that the CO2 in Groups 1 and 2 originates from a deep-seated (magmatic) source. Compared to the CO2-rich springs of Group 1, major cations and HCO3-, together with Fe, Mn and Sr, are enriched in CO2-rich springs of Group 2 and these constituents are highly correlated with TDS. This indicates that, during the ascent of CO2-rich fluids via fractures, CO2-rich springs of Group 2 experienced substantial CO2-water-rock interactions, possibly through longer or restricted pathways, whereas CO2-rich springs of Group 1 acquired the chemistry through lower degrees of water-rock interaction via the rapid ascent through more permeable pathways. The results of principal component analysis (PCA) with compositional data demonstrated that pH can be used as a prior monitoring parameter to detect the direct leakage of CO2 as represented by Group 1. In addition, the changes of ionic composition can be used as a supplementary tool to monitor the indirect leakage of CO2 accompanying a substantial CO2-water-rock interaction.

Natural CO 2 sites in Italy show the importance of overburden geopressure, fractures and faults for CO 2 storage performance and risk management

Abstract The study of natural analogues can inform the long-term performance security of engineered CO 2 storage. There are natural CO 2 reservoirs and CO 2 seeps in Italy. Here, we study nine reservoirs and establish which are sealed or are leaking CO 2 to surface. Their characteristics are compared to elucidate which conditions control CO 2 leakage. All of the case studies would fail current CO 2 storage site selection criteria, although only two leak CO 2 to surface. The factors found to systematically affect seal performance are overburden geopressure and proximity to modern extensional faults. Amongst our case studies, the sealing reservoirs show elevated overburden geopressure whereas the leaking reservoirs do not. Since the leaking reservoirs are located within <10 km of modern extensional faults, pressure equilibration within the overburden may be facilitated by enhanced crustal permeability related to faulting. Modelling of the properties that could enable the observed CO 2 leakage rates finds that high-permeability pathways (such as transmissive faults or fractures) become increasingly necessary to sustain leak rates as CO 2 density decreases during ascent to surface, regardless of the leakage mechanism into the overburden. This work illustrates the value of characterizing the overburden geology during CO 2 storage site selection to inform screening criterion, risk assessment and monitoring strategy.

A natural cement analogue study to understand the long-term behaviour of cements in nuclear waste repositories: Maqarin (Jordan)

The geological storage of nuclear waste includes multibarrier engineered systems where a large amount of cement-based material is used. Predicting the long term behaviour of cement is approached by reactive transport modelling, where some of the boundary conditions can be defined through studying natural cement analogues (e.g. at the Maqarin natural analogue site). At Maqarin, pyrometamorphism of clay biomicrites and siliceous chalks, caused by the in-situ combustion of organic matter, produced various clinker minerals. The interaction of infiltrating groundwater with these clinker phases resulted in a portlandite-buffered hyperalkaline leachate plume, which migrated into the adjacent biomicrite host rock, resulting in the precipitation of hydrated cement minerals.In this study, rock samples with different degrees of interaction with the hyperalkaline plume were investigated by various methods (mostly SEM-EDS). The observations have identified a paragenetic sequence of hydrous cement minerals, and reveal how the fractures and porosity in the biomicrite have become sequentially filled. In the alkaline disturbed zone, C-A-S-H (an unstoichiometric gel of Ca, Al, Si and OH) is observed to fill the pores of the biomicrite wallrock, as a consequence of reaction with a high pH Ca-rich fluid circulating in fractures. Porosity profiles indicate that in some cases the pores of the rock adjacent to the fractures became tightly sealed, whereas in the veins some porosity is preserved. Later pulses of sulphate-rich groundwater precipitated ettringite and occasionally thaumasite in the veins, whereas downstream in the lower pH distal regions of the hyperalkaline plume, zeolite was precipitated.Comparing our observations with the reactive transport modelling results reveals two major discrepancies: firstly, the models predict that ettringite is precipitated before C-A-S-H, whereas the C-A-S-H is observed as the earlier phase in Maqarin; and, secondly, the models predict that ettringite acts as the principal pore-filling phase in contrast to the C-A-S-H observed in the natural system. These discrepancies are related to the fact that our data were not available at the time the modelling studies were performed. However, all models succeeded in reproducing the porosity reduction observed at the fracture–rock interface in the natural analogue system.

Monitoring of CO2-rich waters with low pH and low EC: an analogue study of CO2 leakage into shallow aquifers

The geochemistry of CO2-rich springs and wells was monitored as a natural analogue study of CO2 leakage into shallow aquifers. In result, within the relatively small study area, diluted CO2-rich waters (DCWs), concentrated CW (CCW), and ordinary groundwaters were observed. DCWs showed an exceptionally low pH (mean 4.8) and low EC (mean 150 μS/cm). The low pH and EC as well as the time-invariant geochemistry of DCWs were probably due to continuous CO2 inputs into the open system, which had a short reaction time and rarely consisted of reactive minerals. DCWs showed the low concentrations of SiO2 (mean 20.4 mg/L) and the average tritium concentration of 3.4 TU, which indicates the low CO2–H2O–rock interaction. In addition, \(\delta^{13} {\text{C}}_{{{\text{CO}}_{ 2} {\text{g}}}}\) in equilibrium with water was estimated using the mass balance equation and δ13CDIC measured in water samples. The results of the stable carbon isotope analysis showed that the CO2 originated from a deep-seated source to the shallow DCW aquifer (<80 m deep below the surface), whereas the deeper CCW aquifer was affected by soil organic CO2 near the surface. To detect the CO2 leakage from CO2 storage sites, the geochemistry of shallow aquifers should be monitored. This study result suggests that at least pH, EC, DIC, and carbon isotopes should be monitored because the monitoring of pH is helpful in an aquifer with low buffering capacity; while EC can be low despite CO2 leakage and the subsequently low pH at early stages, depending on the subsurface environment. Above all, this present study indicates that understanding the characteristics of aquifer conditions is of great importance for CO2 leakage detection.

Does the nucleation of clay minerals control the rate of diagenesis in sandstones?

AbstractNucleation is much more important for clay minerals than for other authigenic cements as clay crystals are very small, so that a very large number of clay crystals must be nucleated. The role of this difficult kinetic step in the diagenesis of sandstones has not been considered adequately as a ratedetermining process. The relationship between pore-fluid supersaturation and the rate of nucleation of a mineral is very different from the relationship between supersaturation and the rate of crystal enlargement; thus the two processes will act at very different rates. A diagenetic model that predicts claymineral formation but omits the nucleation stage may make unreliable predictions. This may account partially for the discrepancy between numerical simulations of CO2injection that predict high degrees of reaction between the CO2and the host rock, and the results of studies of natural analogues that have much lower degrees of reaction.