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.

The impact of damming on riverine fluxes to the ocean: A case study from Eastern Iceland.

Anthropogenic water management has extensively altered the world's river systems through impoundments and channel diversions to meet the human's need for water, energy and transportation. To illuminate the effect of such activities on the environment, this study describes the impact of the installation of the Kárahnjúkar Dam in Eastern Iceland on the transport of riverine dissolved- and particulate material to the ocean by the Jökulsá á Dal and the Lagarfljót rivers. This dam, completed in 2007, collects water into the 2.2 km3 Hálslón reservoir and diverts water from the glacial Jökulsá á Dal river into the partially glaciated Lagarfljót lagoon via a headrace tunnel. The impact of the damming was evaluated by sampling water from both the Jökulsá á Dal and the Lagarfljót rivers over a 15 year period spanning from 1998 to 2013. The annual flux of most dissolved elements increased substantially due to the damming. The fluxes of dissolved Zn, Al, Co, Ti and Fe increased most by damming; these fluxes increased by 46-391%. These differences can be attributed to changed saturation states of common secondary minerals in the Jökulsá á Dal due to reduced discharge, increased residence time and dissolution of suspended material, and, to a lesser degree, reduced photosynthesis due to less transparency in the Lagarfljót lagoon. The removal of particulate material and thus decreasing adsorption potential in the Jökulsá á Dal is the likely reason for the Fe flux increase. In contrast, approximately 85% of the original riverine transported mass of particulate material is trapped by the dam; that which passes tends to be relatively fine grained, increasing the average specific surface area of that which continues to flow towards the ocean. Consequently, the particulate geometric surface area flux is decreased by only 50% due to the damming. The blooming of silica diatoms during the spring consumes dissolved silica from the coastal waters until it becomes depleted; making the riverine spring dissolved silica flux an important source of this nutrient. Despite extensive riverine flux changes due to the Kárahnjúkar dam construction, the total spring dissolved silica flux increased, and thus so too the potential for a silica diatom spring bloom in the coastal waters. This is likely because the spring flux is dominated by snow melting downstream of the dam.

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.

The dissolution rates of SiO2 nanoparticles as a function of particle size.

There is a critical need to better define the relationship among particle size, surface area, and dissolution rate for nanoscale materials to determine their role in the environment, their toxicity, and their technological utility. Although some previous studies concluded that nanoparticles dissolve faster than their bulk analogs, contradictory evidence suggests that nanoparticles dissolve more slowly. Furthermore, insufficient characterization of the nanoparticulate samples and the solution chemistry in past studies obscures the relationship between particle size, surface area, and dissolution rate. Here we report amorphous SiO(2) dissolution rates in aqueous solutions determined from complementary mixed-flow and closed reactor experiments at 6.9 ≥ pH ≥ 11.2 and 25 °C as a function of particle diameter from 25 to 177 nm. Experiments were performed at far-from-equilibrium conditions to isolate kinetic effects from those of changing the reaction driving force on overall dissolution rates. Measured far-from-equilibrium mass normalized dissolution rates are nearly independent of particle size, but corresponding BET surface area normalized rates decrease substantially with decreasing particle size. Combining these observations with existing established kinetic rate equations allows the prediction of nanoparticle dissolution rates as a function of both particle size and aqueous fluid saturation state.

Surface charge and zeta-potential of metabolically active and dead cyanobacteria.

Zeta potential and acid-base titrations of active, inactivated, and dead Planktothrix sp. and Synechococcus sp. cyanobacteria were performed to determine the degree to which cell surface electric potential and proton/hydroxyl adsorption are controlled by metabolism or cell membrane structure. Surface OH(-) excess from potentiometric data, showed differences in surface charge between active and dead cyanobacteria from pH 3 to 10. Average zero salt effect pH (pH(pzse)) of 5.8+/-0.1 and 6.3+/-0.1 were obtained for active Planktothrix sp. and Synechococcus sp., respectively. Similarly for dead cyanobacteria pH(pzse) values of 5.8+/-0.1 and 4.6+/-0.1 were obtained. Zeta potentials of active Planktothrix sp. and Synechococcus sp. were positive at alkaline conditions, with a maximum of +13.7+/-1.5 mV at a pH of 9.0+/-0.1 for both species. This positive potential diminished in the presence of 1 mM HCO(-)(3). The zeta potential of Planktothrix sp. and Synechococcus sp. cells was negative at alkaline pH following their exposure to NaN(3), a metabolic inhibitor. The zeta potential of dead cyanobacteria was negative for Planktothrix sp., from pH 2.5 to 10.5, at -30 to -20 mV. Dead Synechococcus sp. exposed to a pH 2.5 solution recorded negative potentials to a minimum of -30 mV at pH 8, but positive potentials were found at higher pH reaching a maximum of +10 mV at pH 9.1. Zeta potentials for dead, but non-acidified Synechococcus sp. remained negative at -30 mV from an initial pH of 5.6 to 10.5, reflecting differences in cell wall structure between these species. These results indicate that Planktothrix sp. and Synechococcus sp. may metabolically control their surface charge to electrostatically attract bicarbonate anions at alkaline pH, required for photosynthesis.

Can dawsonite permanently trap CO2?

Thermodynamic calculations indicate that although dawsonite (NaAlCO3(OH)2) is favored to form at the high CO2 pressures associated with carbon dioxide injection into sandstone reservoirs, this mineral will become unstable as CO2 pressure decreases following injection. To assess the degree to which dawsonite will persist following its formation in sandstone reservoirs, its dissolution rates have been measured at 80 +/- 3 degrees C as a function of pH from 3 to 10. Measured dawsonite dissolution rates normalized to their BET surface area are found to be nearly independent of pH over the range of 3.5 < pH < 8.6 at 1.58 x 10(-9) mol/(m2 x s). Use of these dissolution rates in reactive transport calculations indicate that dawsonite rapidly dissolves following the decrease of CO2 pressure out of its stability field, leading mainly to the precipitation of secondary kaolinite. This result indicates that dawsonite will provide a permanent mineral storage host only in systems that maintain high CO2 pressures, whereas dawsonite may be an ephemeral phase in dynamic settings and dissolve once high CO2 pressure dissipates either through dispersion or leakage.