Experimental identification of CO2–oil–brine–rock interactions: Implications for CO2 sequestration after termination of a CO2-EOR project

Carbon dioxide enhanced oil recovery (CO₂-EOR) has been widely applied to the process of carbon capture, utilization, and storage (CCUS). Here, we investigate CO₂–oil–water–rock interactions under reservoir conditions (100 °C and 24 MPa) in order to understand the fluid–rock interactions following termination of a CO₂-EOR project. Our experimental results show that CO₂-rich fluid remained the active fluid controlling the dissolution–precipitation processes in an oil-undersaturated sandstone reservoir; e.g., the dissolution of feldspar and calcite, and the precipitation of kaolinite as well as solid phases comprising O, Si, Al, Na, C, and Ti. Mineral dissolution rates were reduced in the case that mineral surfaces were coated by oil. Mineral wettability and composition, and oil saturation were the main controls on the exposed surface area of grains, and mineral wettability in particular led to selective dissolution. In addition, the permeability of the reservoir decreased substantially due to the precipitation of kaolinite and solid-phase particles, and due to the clogging of less soluble mineral particles released by the dissolution of K-feldspar and carbonate cement, whereas porosity increased. The results provide insight into potential formation damage resulting from CO₂-EOR projects.     

Geochemical modelling of CO2–water–rock interactions in a potential storage formation of the North German sedimentary basin

The lower Triassic/Bunter sandstone and lower Jurassic/Rhät formations of the Northern Germany sedimentary basin constitute feasible reservoirs for the storage of CO₂ from combustion of fossil fuels or industrial production processes. This study presents analyses of geochemical interactions between CO₂, formation fluid and rock of these potential reservoirs using geochemical modelling in order to assess the short and long term impact of CO₂ sequestration. Batch equilibrium modelling was performed first for assessing the consistency of fluid and mineralogy field data and for identifying potential secondary minerals under the influence of injected CO₂. Inclusion of reaction kinetics in the batch models allowed an observation of reaction paths and to estimate the time frame of geochemical reactions. Finally, one-dimensional equilibrium reactive transport modelling was used in order to investigate the direction of reactions under conditions of fluid flow and mass transport and to quantify feedbacks of reactions on transport processes.Results of the simulations performed show that dawsonite may act as the main CO₂ storage mineral in both formations, while the carbonates calcite and dolomite dissolve over time. Also, changes in porosity and permeability are significant in the equilibrium reactive transport simulations. The time scale of kinetically controlled reactions observed in the kinetic batch modeling, however, suggests that CO₂ mineral trapping in both formations requires very long time frames, and hence other mechanisms such as structural or solubility trapping seem to be more relevant within the injection or early post-injection phase for the studied formations.     

Modeling of water–rock interactions in an aquitard of sandy clay in the coastal area near Beihai,China

Unconsolidated sand, gravel and clay deposits near Beihai and in the Leizhou Peninsula in southern China form an unconfined aquifer, aquitard and a confined aquifer. Water and soil samples were collected from the two aquifers in the coastal Beihai area for the determination of chemical compositions, minerals and soluble ions. Hydrogeochemical modeling of three flow paths through the aquitard are carried out using PHREEQC to determine water–rock interactions along the flow paths. The results indicate that the dissolution of anorthite, fluorite, halite, rhodochrosite and CO₂, and precipitation of potash feldspar and kaolinite may be occurring when groundwater leaks through the aquitard from the unconfined aquifer to the confined aquifer. Cation exchanges between Na and Ca can also happen along the flow paths.     

Water–rock–CO2 interactions in saline aquifers aimed for carbon dioxide storage: Experimental and numerical modeling studies of the Rio Bonito Formation (Permian), southern Brazil

Mineral trapping is one of the safest ways to store CO₂ underground as C will be immobilized in a solid phase. Carbon dioxide will be, therefore, sequestered for geological periods of time, helping to diminish greenhouse gas emissions and mitigate global warming. Although mineral trapping is considered a fairly long process, owing to the existence of kinetic barriers for mineral precipitation, it has been demonstrated both experimentally and by numerical modeling. Here the results of experimental and numerical modeling studies performed in sandstones of the saline aquifer of the Rio Bonito Formation, Paraná Basin, are presented. The Rio Bonito Formation consists of paralic sandstones deposited in the intracratonic Paraná Basin, southern Brazil, during the Permian (Artinskian–Kungurian). These rocks have the largest potential for CO₂ storage because of their appropriated reservoir quality, depth and proximity to the most important stationary CO₂ sources in Brazil. Here it is suggested that CO₂ can be permanently stored as carbonates as CO₂ reacts with rocks of the Rio Bonito Formation and forms CaCO₃ at temperatures and pressures similar to those encountered for CO₂ storage in geological formations. Results of this work will be useful for studies of partitioning mechanisms for C trapping in CO₂ storage programs.     

Geochemical modelling of fluid–rock interactions in the context of the Soultz-sous-Forêts geothermal system

The development of the Enhanced Geothermal System (EGS) at Soultz-sous-Forêts (France) has given to scientists an interesting opportunity for the application of geochemical modelling of water–rock interactions, combining theoretical studies with field and experimental data. The main results of four successive and complementary studies are summarized: geochemical modelling of fluid–rock interactions with prediction of dissolution/precipitation of minerals, feed-back effects on the mineralogy and petrography of the rock (major role of silicates in the geological past and of carbonates in the near future of the exploitation), experimental control of the dynamics of silicates under thermal gradient and relation between the evolution of the petrophysics of the rocks and the heat and mass transfers. The thermal cycle of the fluid, between 200 °C and 65 °C in the geothermal loop, may be responsible for dissolution/precipitation of minerals which modify the porosity and permeability of the granite, as it happened in the geological past, in relation with hydrothermal circulations in the Rhine Graben.     

Experimental study on water–rock interactions during CO2 flooding in the Tensleep Formation,Wyoming, USA

The conditions for mineral alteration and formation damage during CO₂ treatment of Tensleep sandstone reservoirs in northern Wyoming, USA, were examined through core-flooding laboratory experiments carried out under simulated reservoir conditions (80°C and 166 bars). Subsurface cores from the Tensleep sandstone, which were cemented by dolomite and anhydrite, and synthetic brines were used. The brines used were (Ca, Mg, Na)SO₄–NaCl solution (9.69 g/l total dissolved solids) for Run 1 and a 0.25 mol/l NaCl solution for Run 2. The solution used in Run 1 was saturated with respect to anhydrite at run conditions, which is characteristic of Tensleep Formation waters.Three major reactions took place during flooding, including (1) dissolution of dolomite, (2) alteration of K-feldspar to form kaolinite, and (3) precipitation (in Run 1) or dissolution (in Run 2) of anhydrite. All sample solutions remained undersaturated with respect to carbonates. The permeability of all the cores (except one used in Run 2) decreased during the experiments despite the dissolution of authigenic cement. Kaolinite crystal growth occurring in pore throats likely reduced the permeability.Application of the experimental results to reservoirs in the Tensleep Formation indicates that an injection solution will obtain saturation with respect to dolomite (and anhydrite) in the immediate vicinity of the injection well. The injection of NaCl-type water, which can be obtained from other formations, causes a greater increase in porosity than the injection of Tensleep Formation waters because of the dissolution of both dolomite and anhydrite cements.     

Thermal–hydraulic measurements and modelling of the brine circuit in a geothermal well

Wellhead temperature and pressure are critical parameters of a geothermal well. Their prediction requires knowledge of the geofluid properties and detailed thermal modelling of the well and formation. High salinity and gas content complicate the task. This article presents a comprehensive thermal–hydraulic wellbore model, which is parameterized and validated with data from the Gross Schoenebeck site, and used for a long-term prognosis. Geofluid properties are calculated based on the specific gas and salt contents by determining the vapour–liquid equilibrium.     

Geochemical characterization of surface water and spring water in SE Kashmir Valley,western Himalaya: Implications to water–rock interaction

Water samples from precipitation, glacier melt, snow melt, glacial lake, streams and karst springs were collected across SE of Kashmir Valley, to understand the hydrogeochemical processes governing the evolution of the water in a natural and non-industrial area of western Himalayas. The time series data on solute chemistry suggest that the hydrochemical processes controlling the chemistry of spring waters is more complex than the surface water. This is attributed to more time available for infiltrating water to interact with the diverse host lithology. Total dissolved solids (TDS), in general, increases with decrease in altitude. However, high TDS of some streams at higher altitudes and low TDS of some springs at lower altitudes indicated contribution of high TDS waters from glacial lakes and low TDS waters from streams, respectively. The results show that some karst springs are recharged by surface water; Achabalnag by the Bringi stream and Andernag and Martandnag by the Liddar stream. Calcite dissolution, dedolomitization and silicate weathering were found to be the main processes controlling the chemistry of the spring waters and calcite dissolution as the dominant process in controlling the chemistry of the surface waters. The spring waters were undersaturated with respect to calcite and dolomite in most of the seasons except in November, which is attributed to the replenishment of the CO₂ by recharging waters during most of the seasons.     

Chemical and strontium isotopic characteristics of shallow groundwater in the Ordos Desert Plateau,North China: Implications for the dissolved Sr source and water–rock interactions

In this study, the chemical and Sr isotopic compositions of shallow groundwater and rainwater in the Ordos Desert Plateau, North China, and river water from the nearby Yellow River, are investigated to determine the dissolved Sr source and water–rock interactions, and quantify the relative Sr contribution from each end-member. Three groundwater systems have been identified, namely, GWS-1, GWS-2 and GWS-3 according to the watershed distribution in the Ordos Desert Plateau. Ca²⁺ and Mg²⁺ are the most dominant cations in GWS-1, while Na⁺ is dominant in GWS-3. In addition, there is more SO₄²⁻ and less Cl⁻ in GWS-1 than in GWS-3. The shallow groundwater in GWS-2 seems to be geochemically between that in GWS-1 and GWS-3. The ⁸⁷Sr/⁸⁶Sr ratios of the shallow groundwater are high in GWS-1 and GWS-2 and are low in GWS-3. By geochemically comparing the nearby Yellow River, local precipitation and deep groundwater, the shallow groundwater is recharged only by local precipitation. The ionic and isotopic ratios indicate that carbonate dissolution is an important process controlling the chemistry of the shallow groundwater. The intensity of the water–rock interactions varies among the three groundwater systems and even within each groundwater system. Three end-members controlling the groundwater chemistry are isotopically identified: (1) precipitation infiltration, (2) carbonate dissolution and (3) silicate weathering. The relative Sr contributions of the three end-members show that precipitation infiltration and carbonate dissolution are the primary sources of the shallow groundwater Sr in GWS-3 whereas only carbonate dissolution is responsible for the shallow groundwater Sr in GWS-1 and GWS-2. Silicate weathering seems insignificant towards the shallow groundwater's chemistry in the Ordos Desert Plateau. This study is helpful for understanding groundwater chemistry and managing water resources.     

Forest biomass carbon dynamics (1980–2009) in western Himalaya in the context of REDD+ policy

Carbon emissions from forests have decreased in the past decade due to conservation efforts, however majority of carbon losses suffered in the past went unnoticed until the role of forests in mitigating climate change was realized. Forestry sector in developing countries is recognized as one of the largest and low cost mitigation options to address climate change. The present study was conducted to assess the multi-temporal biomass carbon mitigation in the temperate forests of western Himalaya using satellite (Landsat MSS, TM, ETM+) and forest inventory data. Forest type density mapping was done through on-screen visual interpretation of satellite data. After conducting preliminary survey in 2009, 45 quadrats (0.1 ha) were laid in six forest types for collecting field inventory data viz., diameter at breast height, tree height, slope and aspect. Biomass carbon (t ha^?1) was estimated for different forest types with different crown densities (open with 10–40% crown density and closed with >40%) using recommended regression equations, ratios and factors. A decreasing trend of carbon (145.13–134.87 mt) was observed over the period of time. Temporal biomass carbon dynamics was analyzed for REDD+ opportunities. The temporal variation of carbon observed was found to be more useful for claiming benefits under negative options (deforestation and forest degradation) of REDD+. The study doesn’t take actual conversions to CO₂ into account. However, the findings are useful in establishing baseline emissions through temporal carbon losses. Further, the study helps in identification of location specific socio-economic drivers of losses that can be used for appropriate mitigation interventions.     

Modelling U-Pb discordance in the Acasta Gneiss: Implications for fluid–rock interaction in Earth's oldest dated crust

The U–Pb isotopic system in zircon is the tool of choice to interrogate high-temperature geological processes, yet this system has potential to investigate lower temperature fluid–rock interaction as well. In some cases, removal of radiogenic Pb is incomplete, potentially allowing regression of discordant U–Pb data on a concordia diagram to determine both the age of crystallization and the timing of fluid-driven isotopic disturbance. However, in rocks preserving more complex histories, simple regression is not effective at resolving multiple Pb loss events. Here, we use a ‘concordant–discordant comparison’ (CDC) test to establish the times of U–Pb disturbance in the Acasta Gneiss Complex (AGC), Canada. AGC c. 4.03 to c. 3.40 Ga orthogneisses experienced a long and complex post-crystallization history, for which U–Pb zircon data reflects not only the heterogeneous nature of the rock, but also the varying degrees and duration of crustal reworking that inevitably involved open system processes. The CDC test calculates the similarity between the concordant age structure and a modelled age structure, the latter inferred from discordant analyses, over a wide range of potential disturbance times. Our analysis reveals concordant zircon components implying new growth and/or recrystallization at 3992 ± 5, 3501 ± 6, 3442 ± 5 and 3126 ± 6 Ma. In addition, we establish episodes of radiogenic-Pb loss driven by fluid–rock interaction at 3150 ± 50 Ma, and probably at 2875 ± 50 Ma and c. 2590 Ma. These Pb-loss episodes correlate with previously recognised events recording growth of zircon rims during metamorphism, granite emplacement, and unroofing. Pb-loss within the AGC shows an antithetic relationship in different samples that are in close geographic proximity. We suggest that zircon alteration and associated new growth effectively rendered those grains that underwent Pb-loss at a particular time less susceptible to alteration during the next episode of fluid interaction.     

U–Pb Zircon Geochronology and Geochemistry of the Neoproterozoic Liujiaping Group Volcanics in the Northwest Margin of the Yangtze Block: Implications For the Breakup of the Rodinia Supercontinent

Investigation of the petrogenesis and the origin of zircons from the volcanic rocks of the Liujiaping Group of the back-Longmenshan tectonic belt in the northwest margin of the Yangtze Block is conducted by analysis of U–Pb geochronology and geochemistry. Results show that selected zircons are characterized by internal oscillatory zonings and high Th/U ratios (0.43–1.18), indicating an igneous origin. Geochronological results of LA–ICP–MS U–Pb dating of the Liujiaping Group zircons yield an age of 809 ± 11 Ma (MSWD = 2.2), implying that the volcanic rocks were formed in the Late Neoproterozoic. Geochemical analysis shows that the rocks are calc-alkaline, supersaturated in Al, and metaluminous to weakly peraluminous. Rare-earth elements are present at high concentrations (96.04–265.48 ppm) and show a rightward incline and a moderately negative Eu anomaly, similar to that of continental rift rhyolite. Trace element geochemistry is characterized by evident negative anomalies of Nb, Ta, P, Th, Ti, inter alia, and strong negative anomalies of K, Rb, Sr, et al. We conclude that the Liujiaping Group volcanic rocks resulted from typical continental crust source petrogenesis and were formed in a continental margin setting, which had no relation to subduction, and thus, were the products of partial melting of the lower crust due to crustal thickening caused by active continental margin subduction and arc–continent collision orogeny in the northwestern Yangtze Block and were triggered by the breakup of the Rodinia supercontinent during the Neoproterozoic.     

U–Pb Zircon Geochronology and Geochemistry of the Neoproterozoic Liujiaping Group Volcanics in the Northwest Margin of the Yangtze Block:Implications For the Breakup of the Rodinia Supercontinent

Investigation of the petrogenesis and the origin of zircons from the volcanic rocks of the Liujiaping Group of the back-Longmenshan tectonic belt in the northwest margin of the Yangtze Block is conducted by analysis of U–Pb geochronology and geochemistry. Results show that selected zircons are characterized by internal oscillatory zonings and high Th/U ratios(0.43–1.18), indicating an igneous origin. Geochronological results of LA–ICP–MS U–Pb dating of the Liujiaping Group zircons yield an age of 809 ± 11 Ma(MSWD = 2.2), implying that the volcanic rocks were formed in the Late Neoproterozoic. Geochemical analysis shows that the rocks are calc-alkaline, supersaturated in Al, and metaluminous to weakly peraluminous. Rare-earth elements are present at high concentrations(96.04–265.48 ppm) and show a rightward incline and a moderately negative Eu anomaly, similar to that of continental rift rhyolite. Trace element geochemistry is characterized by evident negative anomalies of Nb, Ta, P, Th, Ti, inter alia, and strong negative anomalies of K, Rb, Sr, et al. We conclude that the Liujiaping Group volcanic rocks resulted from typical continental crust source petrogenesis and were formed in a continental margin setting, which had no relation to subduction, and thus, were the products of partial melting of the lower crust due to crustal thickening caused by active continental margin subduction and arc–continent collision orogeny in the northwestern Yangtze Block and were triggered by the breakup of the Rodinia supercontinent during the Neoproterozoic.     

Review: Water–rock interactions and related eco-environmental effects in typical land subsidence zones of China

Land subsidence is common in some regions of China. Various eco-environmental problems have arisen due to changes in water–rock interactions in these subsided areas, for which a comprehensive understanding of the hydrogeological setting is needed. This paper presents the general status of land subsidence in three typical subsided areas of China through the compilation of relevant data, and reviews some typical changes in the water–rock interactions in subsided areas along with related eco-environmental issues. It is found that the subsidence development and distribution are controlled by the groundwater-withdrawal intensity externally, and by the thickness and compressibility of unconsolidated sediments internally. The physical changes and related effects of water–rock interactions in subsided areas include: (1) the decreased ground elevation that caused floods, waterlogged farmland, etc.; (2) the differential subsidence that caused ground fissures; and (3) the change of seepage field that caused substantial reduction of the water resource. Chemically, the changes and related effects of water–rock interactions include: (1) the change to the chemical environment or processes due to the hydrogeologic structure alteration, which caused groundwater pollution; and (2) hydrologic mixing (seawater intrusion, artificial recharge; exchange with adjacent aquifers or aquitards), which degraded the groundwater quality. Further research on the subsided areas in China is suggested to reveal the mechanisms regarding biological and gaseous (meteorological) changes from the perspective of interacting systems among water, rocks, biological agents and gases.     

A case-study of complex gas–water–rock–pollutants interactions in shallow groundwater: Šalek Valley (Slovenia)

The complex geochemical interactions in the groundwater of the industrial area of Šalek Valley (Slovenia) between natural and anthropogenic fluids were studied by means of major (Ca, Mg, Na, K, HCO₃ ⁻, Cl⁻ and SO₄ ²⁻) and trace elements’ (As , Cd, Cu, Pb, Zn, Hg, Se and V) abundances, geochemical classification and statistical analysis of data. Cation abundances indicate mixing between a dolomitic end-member and an evaporitic or geothermal end-member. Anion abundances indicate mixing between bicarbonate waters and either sulphate-enriched waters (suggesting hydrothermalism) or chlorine-rich waters. Principal component analysis (PCA) allowed the extraction of seven factors, which describe, respectively: water–rock interaction mainly on dolomitic rocks; redox conditions of water; Cd–Zn enrichment in chlorine-rich waters (probably from industrial wastes); hydrothermal conditions in waters close to major faults; Pb and Cu pollution; V and K enrichments, indicating their common organic source; the role of partial pressure of CO₂ dissolved in water, which is highest in three wells with bubbling gases. Average underground discharge rates of solutes from the Valley range between 0.09 t/a (V) and 1.8 × 104 t/a (HCO₃ ⁻) and indicate how natural fluids can significantly contribute to the levels of elements in the environment, in addition to the amount of elements released by human activities.     

Origin of Late Cenozoic Abaga–Dalinuoer basalts,eastern China: Implications for a mixed pyroxenite–peridotite source related with deep subduction of the Pacific slab

Continental intraplate basalts (15.42–0.16 Ma) from Abaga–Dalinuoer volcanic field (ADVF) in central Inner Mongolia of eastern China, as a part of Cenozoic volcanic province along eastern margin of the Eurasian continent, provide a good opportunity to explore potential links between deep subduction of the Pacific slab and continental intraplate volcanism. In this study, we report an integrated dataset of whole-rock K–Ar ages, major and trace elements and Sr–Nd–Pb isotopes, and olivine major and minor elements for the Abaga–Dalinuoer basalts (ADBs), and propose that mantle source lithology of the ADB magmas may consist of both pyroxenite and peridotite. The ADBs display low SiO₂ (42.3–50.2 wt.%), high MgO (7.3–11.4 wt.%) and moderate K₂O + Na₂O (3.8–6.4 wt.%), and can be subdivided into basanites, alkali basalts and tholeiitic basalts that are all characterized by ocean island basalt (OIB)-like rare earth elements (REE) and enrichment in both large ion lithosphile elements (LILE) and high field strength elements (HFSE). Olivine phenocrysts have higher Ni and Fe/Mn and lower Mn, Ca and Ca/Fe relative to those from peridotite melts, but exhibit clearly lower Ni contents (< 2500 ppm) compared with expected Ni range (> 3000 ppm) for olivines crystallized from olivine-free pyroxenite melts. Estimated compositions of the ADB primary magmas, together with olivine compositions, suggest an iron-rich mantle source related with silica-deficient pyroxenite that is most likely derived from deeply subducted Pacific oceanic crust. Additionally, peridotite and recent subducted sediments are also required to account for high Ni and MgO in primary magmas together with their trace elements and Sr–Nd–Pb isotope systematics. We suggest that a mixed pyroxenite–peridotite source lithology can better match observed whole-rock and olivine signatures in the ADB, compared with either peridotite only or olivine-free pyroxenite only source lithology. In our model, pyroxenite melts would either react with or mechanically mix with peridotite, and the proportion of pyroxenite melts may range from 30% to 45% for mechanical mixing scenario. A continuous spectrum from tholeiitic to alkali melts revealed by melt-peridotite reaction experiment can explain formation of primary magmas of basanites, alkali basalts and tholeiitic basalts by increasing melting degree of a similar mantle source. Relatively higher ²⁰⁶Pb/²⁰⁴Pb of the ADB may suggest more significant role of recent (< 0.5 Ga) subducted Pacific oceanic materials, in contrast to other Cenozoic basalts in eastern China (e.g., Changbai basalts) that exhibit varying contributions from ancient (> 1.5 Ga) subducted continental sediments. We emphasize that coupled geochemical and geodynamic links (i.e., subduction polarity) between deeply subducted Pacific slab and continental intraplate volcanism in eastern China may exist, which directly support the involvement of deeply subducted Pacific materials in petrogenesis of the ADB. From the perspective of plate motion kinetics, decompression partial melting of upwelling fragmented Pacific slab (silica-deficient pyroxenite + recent subducted sediments) may be triggered by rollback of deeply subducted Pacific slab during Late Cenozoic times. Continental intraplate volcanism in the ADVF generally started with termination of opening of the Japan Sea, suggesting that deep subduction of the Pacific slab may have been an important geodynamic mechanism responsible for tectono-magmatic evolution of northeastern Asia. We suggest that the ADBs have the potential to shed light on genetic links between continental intraplate volcanism and deep subduction of the Pacific slab in geochemical and geodynamic processes.