Yujia Min

Structure-Dependent Interactions between Alkali Feldspars and Organic Compounds: Implications for Reactions in Geologic Carbon Sequestration

Organic compounds in deep saline aquifers may change supercritical CO(2) (scCO(2))-induced geochemical processes by attacking specific components in a minerals crystal structure. Here we investigate effects of acetate and oxalate on alkali feldspar-brine interactions in a simulated geologic carbon sequestration (GCS) environment at 100 atm of CO(2) and 90 °C. We show that both organics enhance the net extent of feldspars dissolution, with oxalate showing a more prominent effect than acetate. Further, we demonstrate that the increased reactivity of Al-O-Si linkages due to the presence of oxalate results in the promotion of both Al and Si release from feldspars. As a consequence, the degree of Al-Si order may affect the effect of oxalate on feldspar dissolution: a promotion of ~500% in terms of cumulative Si concentration was observed after 75 h of dissolution for sanidine (a highly disordered feldspar) owing to oxalate, while the corresponding increase for albite (a highly ordered feldspar) was ~90%. These results provide new insights into the dependence of feldspar dissolution kinetics on the crystallographic properties of the mineral under GCS conditions.

Plagioclase Dissolution during CO2–SO2 Cosequestration: Effects of Sulfate

Geologic CO2 sequestration (GCS) is one of the most promising methods to mitigate the adverse impacts of global climate change. The performance of GCS can be affected by mineral dissolution and precipitation induced by injected CO2. Cosequestration with acidic gas such as SO2 can reduce the high cost of GCS, but it will increase the sulfates concentration in GCS sites, where sulfate can potentially affect plagioclase dissolution/precipitation. This work investigated the effects of 0.05 M sulfate on plagioclase (anorthite) dissolution and subsequent mineral precipitation at 90 °C, 100 atm CO2, and 1 M NaCl, conditions relevant to GCS sites. The adsorption of sulfate on anorthite, a Ca-rich plagioclase, was examined using attenuated total reflectance Fourier-transform infrared spectroscopy and then simulated using density functional theory calculations. We found that the dissolution rate of anorthite was enhanced by a factor of 1.36 by the formation of inner-sphere monodentate complexes between sulfate and the aluminum sites on anorthite surfaces. However, this effect was almost completely suppressed in the presence of 0.01 M oxalate, an organic ligand that can exist in GCS sites. Interestingly, sulfate also inhibited the formation of secondary mineral precipitation through the formation of aluminum-sulfate complexes in the aqueous phase. This work, for the first time, reports the surface complexation between sulfate and plagioclase that can occur in GCS sites. The results provide new insights for obtaining scientific guidelines for the proper amount of SO2 coinjection and finally for evaluating the economic efficiency and environmental safety of GCS operations.

Nanoscale Chemical Processes Affecting Storage Capacities and Seals during Geologic CO2 Sequestration

Geologic CO2 sequestration (GCS) is a promising strategy to mitigate anthropogenic CO2 emission to the atmosphere. Suitable geologic storage sites should have a porous reservoir rock zone where injected CO2 can displace brine and be stored in pores, and an impermeable zone on top of reservoir rocks to hinder upward movement of buoyant CO2. The injection wells (steel casings encased in concrete) pass through these geologic zones and lead CO2 to the desired zones. In subsurface environments, CO2 is reactive as both a supercritical (sc) phase and aqueous (aq) species. Its nanoscale chemical reactions with geomedia and wellbores are closely related to the safety and efficiency of CO2 storage. For example, the injection pressure is determined by the wettability and permeability of geomedia, which can be sensitive to nanoscale mineral-fluid interactions; the sealing safety of the injection sites is affected by the opening and closing of fractures in caprocks and the alteration of wellbore integrity caused by nanoscale chemical reactions; and the time scale for CO2 mineralization is also largely dependent on the chemical reactivities of the reservoir rocks. Therefore, nanoscale chemical processes can influence the hydrogeological and mechanical properties of geomedia, such as their wettability, permeability, mechanical strength, and fracturing. This Account reviews our groups work on nanoscale chemical reactions and their qualitative impacts on seal integrity and storage capacity at GCS sites from four points of view. First, studies on dissolution of feldspar, an important reservoir rock constituent, and subsequent secondary mineral precipitation are discussed, focusing on the effects of feldspar crystallography, cations, and sulfate anions. Second, interfacial reactions between caprock and brine are introduced using model clay minerals, with focuses on the effects of water chemistries (salinity and organic ligands) and water content on mineral dissolution and surface morphology changes. Third, the hydrogeological responses (using wettability alteration as an example) of clay minerals to chemical reactions are discussed, which connects the nanoscale findings to the transport and capillary trapping of CO2 in the reservoirs. Fourth, the interplay between chemical and mechanical alterations of geomedia, using wellbore cement as a model geomedium, is examined, which provides helpful insights into wellbore and caprock integrities and CO2 mineralization. Combining these four aspects, our group has answered questions related to nanoscale chemical reactions in subsurface GCS sites regarding the types of reactions and the property alterations of reservoirs and caprocks. Ultimately, the findings can shed light on the influences of nanoscale chemical reactions on storage capacities and seals during geologic CO2 sequestration.

Wollastonite Carbonation in Water-Bearing Supercritical CO2: Effects of Particle Size

The performance of geologic CO2 sequestration (GCS) can be affected by CO2 mineralization and changes in the permeability of geologic formations resulting from interactions between water-bearing supercritical CO2 (scCO2) and silicates in reservoir rocks. However, without an understanding of the size effects, the findings in previous studies using nanometer- or micrometer-size particles cannot be applied to the bulk rock in field sites. In this study, we report the effects of particle sizes on the carbonation of wollastonite (CaSiO3) at 60 °C and 100 bar in water-bearing scCO2. After normalization by the surface area, the thickness of the reacted wollastonite layer on the surfaces was independent of particle sizes. After 20 h, the reaction was not controlled by the kinetics of surface reactions but by the diffusion of water-bearing scCO2 across the product layer on wollastonite surfaces. Among the products of reaction, amorphous silica, rather than calcite, covered the wollastonite surface and acted as a diffusion barrier to water-bearing scCO2. The product layer was not highly porous, with a specific surface area 10 times smaller than that of the altered amorphous silica formed at the wollastonite surface in aqueous solution. These findings can help us evaluate the impacts of mineral carbonation in water-bearing scCO2.

Photothermally Active Reduced Graphene Oxide/Bacterial Nanocellulose Composites as Biofouling-Resistant Ultrafiltration Membranes

Biofouling poses one of the most serious challenges to membrane technologies by severely decreasing water flux and driving up operational costs. Here, we introduce a novel anti-biofouling ultrafiltration membrane based on reduced graphene oxide (RGO) and bacterial nanocellulose (BNC), which incoporates GO flakes into BNC in situ during its growth. In contrast to previously reported GO-based membranes for water treatment, the RGO/BNC membrane exhibited excellent aqueous stability under environmentally relevant pH conditions, vigorous mechanical agitation/sonication, and even high pressure. Importantly, due to its excellent photothermal property, under light illumination, the membrane exhibited effective bactericidal activity, obviating the need for any treatment of the feedwater or external energy. The novel design and in situ incorporation of the membranes developed in this study present a proof-of-concept for realizing new, highly efficient, and environmental-friendly anti-biofouling membranes for water purification.