Assessing the potential of solubility trapping in unconfined aquifers for subsurface carbon storage.

Carbon capture and storage projects need to be greatly accelerated to attenuate the rate and degree of global warming. Due to the large volume of carbon that will need to be stored, it is likely that the bulk of this storage will be in the subsurface via geologic storage. To be effective, subsurface carbon storage needs to limit the potential for CO2 leakage from the reservoir to a minimum. Water-dissolved CO2 injection can aid in this goal. Water-dissolved CO2 tends to be denser than CO2-free water, and its injection leads immediate solubility storage in the subsurface. To assess the feasibility and limits of water-dissolved CO2 injection coupled to subsurface solubility storage, a suite of geochemical modeling calculations based on the TOUGHREACT computer code were performed. The modelled system used in the calculations assumed the injection of 100,000 metric tons of water-dissolved CO2 annually for 100 years into a hydrostatically pressured unreactive porous rock, located at 800 to 2000 m below the surface without the presence of a caprock. This system is representative of an unconfined sedimentary aquifer. Most calculated scenarios suggest that the injection of CO2 charged water leads to the secure storage of injected CO2 so long as the water to CO2 ratio is no less than ~ 24 to 1. The identified exception is when the salinity of the original formation water substantially exceeds the salinity of the CO2-charged injection water. The results of this study indicate that unconfined aquifers, a generally overlooked potential carbon storage host, could provide for the subsurface storage of substantial quantities of CO2.

Rapid CO2 mineralisation into calcite at the CarbFix storage site quantified using calcium isotopes.

The engineered removal of atmospheric CO2 is now considered a key component of mitigating climate warming below 1.5 °C. Mineral carbonation is a potential negative emissions technique that, in the case of Iceland's CarbFix experiment, precipitates dissolved CO2 as carbonate minerals in basaltic groundwater settings. Here we use calcium (Ca) isotopes in both pre- and post-CO2 injection waters to quantify the amount of carbonate precipitated, and hence CO2 stored. Ca isotope ratios rapidly increase with the pH and calcite saturation state, indicating calcite precipitation. Calculations suggest that up to 93% of dissolved Ca is removed into calcite during certain phases of injection. In total, our results suggest that 165 ± 8.3 t CO2 were precipitated into calcite, an overall carbon storage efficiency of 72 ± 5%. The success of this approach opens the potential for quantification of similar mineral carbonation efforts where drawdown rates cannot be estimated by other means.

High reactivity of deep biota under anthropogenic CO2 injection into basalt.

Basalts are recognized as one of the major habitats on Earth, harboring diverse and active microbial populations. Inconsistently, this living component is rarely considered in engineering operations carried out in these environments. This includes carbon capture and storage (CCS) technologies that seek to offset anthropogenic CO2 emissions into the atmosphere by burying this greenhouse gas in the subsurface. Here, we show that deep ecosystems respond quickly to field operations associated with CO2 injections based on a microbiological survey of a basaltic CCS site. Acidic CO2-charged groundwater results in a marked decrease (by ~ 2.5-4) in microbial richness despite observable blooms of lithoautotrophic iron-oxidizing Betaproteobacteria and degraders of aromatic compounds, which hence impact the aquifer redox state and the carbon fate. Host-basalt dissolution releases nutrients and energy sources, which sustain the growth of autotrophic and heterotrophic species whose activities may have consequences on mineral storage.

Rapid carbon mineralization for permanent disposal of anthropogenic carbon dioxide emissions.

Carbon capture and storage (CCS) provides a solution toward decarbonization of the global economy. The success of this solution depends on the ability to safely and permanently store CO2 This study demonstrates for the first time the permanent disposal of CO2 as environmentally benign carbonate minerals in basaltic rocks. We find that over 95% of the CO2 injected into the CarbFix site in Iceland was mineralized to carbonate minerals in less than 2 years. This result contrasts with the common view that the immobilization of CO2 as carbonate minerals within geologic reservoirs takes several hundreds to thousands of years. Our results, therefore, demonstrate that the safe long-term storage of anthropogenic CO2 emissions through mineralization can be far faster than previously postulated.

Regulation of arsenic mobility on basaltic glass surfaces by speciation and pH.

The importance of geothermal energy as a source for electricity generation and district heating has increased over recent decades. Arsenic can be a significant constituent of the geothermal fluids pumped to the surface during power generation. Dissolved As exists in different oxidation states, mainly as As(III) and As(V), and the charge of individual species varies with pH. Basaltic glass is one of the most important rock types in many high-temperature geothermal fields. Static batch and dynamic column experiments were combined to generate and validate sorption coefficients for As(III) and As(V) in contact with basaltic glass at pH 3-10. Validation was carried out by two empirical kinetic models and a surface complexation model (SCM). The SCM provided a better fit to the experimental column data than kinetic models at high pH values. However, in certain circumstances, an adequate estimation of As transport in the column could not be attained without incorporation of kinetic reactions. The varying mobility with pH was due to the combined effects of the variable charge of the basaltic glass with the pH point of zero charge at 6.8 and the individual As species as pH shifted, respectively. The mobility of As(III) decreased with increasing pH. The opposite was true for As(V), being nearly immobile at pH 3 to being highly mobile at pH 10. Incorporation of appropriate sorption constants, based on the measured pH and Eh of geothermal fluids, into regional groundwater-flow models should allow prediction of the As(III) and As(V) transport from geothermal systems to adjacent drinking water sources and ecosystems.

The impact of sampling techniques on soil pore water carbon measurements of an Icelandic Histic Andosol.

The carbon in soil pore water from a Histic Andosol from Western Iceland was studied at three different scales; in the field, in undisturbed outdoor mesocosms and in laboratory repacked microcosms. Pore water was extracted using suction cup lysimeters and hollow-fibre tube sampler devices (Rhizon samplers). There were significant differences in all measured variables, dissolved inorganic carbon (DIC), dissolved organic carbon (DOC) and pH values between the scales of the experiment. Gaseous constituents of soil solution and pH were more susceptible to changes in scale and the type of sampling devices used. Dissolved inorganic carbon concentrations did not differ significantly between field and mesocosm solutions but where up to 14 times lower in microcosms compared to mesocosms solutions. Rhizon samplers yielded solutions with up to 4.7 times higher DIC concentrations than porous cup lysimeters. Mesocosm surface horizon DOC concentrations were 20 and 2 times higher than in field and microcosms respectively. There was difference in DOC concentration between sampling methods (up to 8 times higher in suction cups than rhizon samplers) above 50 cm depth. Soil solution pH values did not differ between field and mesocosms and mesocosms and microcosms respectively down to 80 cm depth. Direct comparison between field and microcosms was not possible due to the nature of sampling devices. Soil solutions sampled with Rhizon samplers yielded lower pH values (up to 1.3 pH units) than those sampled with suction cups. Twenty percent of annually bound organic carbon at the soils surface under field conditions was lost by leaching of DOC and through decomposition to DIC in disturbed non-vegetated microcosms. This percentage increased to 38% in undisturbed vegetated mesocosms highlighting the importance of surface vegetation in importing carbon to soils. Increased influx of nutrients will increase growth and photosynthesis but decrease carbon sequestration in near surface horizons. Although field studies considering long-term anthropogenic changes in pedogenesis require considerable experimental duration, more rapid experiments can be conducted with confidence in micro- and mesocosms as in this research.