Alteration of Fractured Foamed Cement Exposed to CO2-Saturated Water: Implications for Well Integrity.

Geologic CO2 storage (GCS) is a method to mitigate the adverse impact of global climate change. Potential leakage of CO2 from fractured cement at the wellbore poses a risk to the feasibility of GCS. Foamed cement is widely applied in deepwater wells where fragile geologic formations cannot support the weight of conventional cement. Thus, it is critical to know whether fractures in foamed cement self-seal in a similar manner as conventional cement systems. This study is the first to investigate the changes in physical and chemical attributes of foamed cement under dynamic flow conditions using CO2-saturated water. Self-sealing of fractures in the cement was observed at a solution flow rate of 0.1 mL/min and a pressure of 6.9 MPa. The formation of CaCO3 precipitates in pore spaces and fractures led to a decrease in permeability by 1 order of magnitude. The extents of self-sealing in foamed cement samples, specifically the 20 and 30% air volume formulations, were similar to that of conventional cements. We attribute this to the greater alteration depth in the foamed cement, which compensated for the reduced availability of Portlandite and higher initial porosity. The results can be used to evaluate the risk of leakage associated with foamed cement.

Sulfate-Controlled Heterogeneous CaCO3 Nucleation and Its Non-linear Interfacial Energy Evolution.

Unveiling the effects of an environmental abundant anion "sulfate" on the formation of calcium carbonate (CaCO3) is essential to understand the formation mechanisms of biominerals like corals and brachiopod shells, as well as the scale formation in desalination systems. However, it was experimentally challenging to elucidate the sulfate-CaCO3 interactions at the explicit first step of CaCO3 formation: nucleation. In addition, there is limited quantitative information on the precise control of nucleation kinetics. Here, heterogeneous CaCO3 nucleation is monitored in real time as a function of sulfate concentrations (0-10 mM Na2SO4) using synchrotron-based grazing incidence X-ray scattering techniques. The results showed that sulfate can be incorporated in the nuclei, resulting in a nearly 90% decrease in the CaCO3 nucleation rate, causing a 120% increase in the CaCO3 nucleus size, and inhibiting the vaterite-to-calcite phase transformation. Moreover, this work quantitatively relates sulfate concentrations to the effective interfacial energies of CaCO3 and finds a non-linear trend, suggesting that CaCO3 heterogeneous nucleation is more sensitive at a low sulfate concentration. This study can be readily extended to study other additives and obtain quantitative relationships between additive concentrations and CaCO3 interfacial energies, a key step toward achieving natural and engineered controls on CaCO3 nucleation.

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.

Effects of Na+ and K+ Exchange in Interlayers on Biotite Dissolution under High-Temperature and High-CO2-Pressure Conditions.

Cations in formation brine can affect CO2-induced dissolution of minerals during geologic CO2 sequestration (GCS), affecting the GCS performance. This study investigated the dissolution of biotite with 0-4 M Na+ and 0-10 mM K+ under high temperature and high CO2 pressure (i.e., 95 °C and 100 bar CO2). At <0.5 M Na+ concentration, Na+ replaced K+ in the biotite interlayer and enhanced the biotite dissolution. In >0.5 M Na+, however, the enhancing effect of Na+ was mitigated by an inhibition caused by competing sorption between Na+ and protons. With 0.5 M Na+ concentration, coexisting K+ significantly inhibited the biotite dissolution with high sensitivity at even lower K+ concentrations, such as 0.1-0.5 mM. In this study, we also reported the dissolution of Na-treated biotite, mimicking biotite naturally equilibrated with Na+-abundant brine. Na-treated biotite dissolved faster than natural K-containing biotite, and during the dissolution, it transformed to vermiculite. Aqueous Na+ inhibited the dissolution of Na-treated biotite by suppressing the release of interlayer Na+, and aqueous K+ inhibited the dissolution of Na-treated biotite by replacing the interlayer Na+. These findings contribute to better understanding of biotite dissolution in the presence of potassium-containing clay-swelling inhibitors and different salinities at GCS sites.

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.

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 group's 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.

Anorthite Dissolution under Conditions Relevant to Subsurface CO2 Injection: Effects of Na+, Ca2+, and Al3.

Supercritical CO2 is injected into subsurface environments during geologic CO2 sequestration and CO2-enhanced oil recovery. In these processes, the CO2-induced dissolution of formation rocks, which contain plagioclase, can affect the safety and efficiency of the subsurface operation. In subsurface brines, Na+ and Ca2+ are naturally abundant, and Al3+ concentration increases due to acidification by injected CO2. However, our current understanding of cation effects on plagioclase dissolution does not provide sufficiently accurate prediction of plagioclase dissolution at such high salinities. This study investigated the effects of up to 4 M Na+, 1 M Ca2+, and 200 µM Al3+ on anorthite (as a representative mineral of Ca-containing plagioclase) dissolution under conditions closely relevant to subsurface CO2 injection. For the first time, we elucidated the inhibition effects of Al3+ on anorthite dissolution in far-from-equilibrium systems, and found that the Al3+ effects were enhanced at elevated temperature. Interestingly, Na+ inhibited anorthite dissolution as well, and the effects of Na+ were 50% stronger at 35 °C than at 60 °C. Ca2+ had similar effects to those of Na+, and the Ca2+ effects did not suppress Na+ effects when they coexisted. These findings can contribute to better predicting plagioclase dissolution in geologic formations and will also be helpful in improving designs for subsurface CO2 injection.

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 sulfate's 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.

A mechanistic understanding of plagioclase dissolution based on Al occupancy and T-O bond length: from geologic carbon sequestration to ambient conditions.

A quantitative description of how the bulk properties of aluminosilicates affect their dissolution kinetics is important in helping people understand the regulation of atmospheric CO2 concentration by silicate weathering and predict the fate and transport of geologically sequestered CO2 through brine-rock interactions. In this study, we employed a structure model based on the C1 space group to illustrate how differences in crystallographic properties of aluminosilicates, such as T-O (Tetrahedral site-Oxygen) bond length and Al/Si ordering, can result in quantifiable variations in mineral dissolution rates. The dissolution rates of plagioclases were measured under representative geologic carbon sequestration (GCS) conditions (90 °C, 100 atm of CO2, 1.0 M NaCl, and pH ∼ 3.1), and used to validate the model. We found that the logarithm of the characteristic time of the breakdown of Al-O-Si linkages in plagioclases follows a good linear relation with the mineral's aluminum content (nAl). The Si release rates of plagioclases can be calculated based on an assumption of dissolution congruency or on the regularity of Al/Si distribution in the constituent tetrahedra of the mineral. We further extended the application of our approach to scenarios where dissolution incongruency arises because of different linkage reactivities in the solid matrix, and compared the model predictions with published data. The application of our results enables a significant reduction of experimental work for determining the dissolution rates of structurally related aluminosilicates, given a reaction environment.

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 mineral's 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 feldspar's 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.

Emission of oxygenated polycyclic aromatic hydrocarbons from indoor solid fuel combustion.

Indoor solid fuel combustion is a dominant source of polycyclic aromatic hydrocarbons (PAHs) and oxygenated PAHs (OPAHs) and the latter are believed to be more toxic than the former. However, there is limited quantitative information on the emissions of OPAHs from solid fuel combustion. In this study, emission factors of OPAHs (EF(OPAH)) for nine commonly used crop residues and five coals burnt in typical residential stoves widely used in rural China were measured under simulated kitchen conditions. The total EF(OPAH) ranged from 2.8 ± 0.2 to 8.1 ± 2.2 mg/kg for tested crop residues and from 0.043 to 71 mg/kg for various coals and 9-fluorenone was the most abundant specie. The EF(OPAH) for indoor crop residue burning were 1-2 orders of magnitude higher than those from open burning, and they were affected by fuel properties and combustion conditions, like moisture and combustion efficiency. For both crop residues and coals, significantly positive correlations were found between EFs for the individual OPAHs and the parent PAHs. An oxygenation rate, R(o), was defined as the ratio of the EFs between the oxygenated and parent PAH species to describe the formation potential of OPAHs. For the studied OPAH/PAH pairs, mean R(o) values were 0.16-0.89 for crop residues and 0.03-0.25 for coals. R(o) for crop residues burned in the cooking stove were much higher than those for open burning and much lower than those in ambient air, indicating the influence of secondary formation of OPAH and loss of PAHs. In comparison with parent PAHs, OPAHs showed a higher tendency to be associated with particulate matter (PM), especially fine PM, and the dominate size ranges were 0.7-2.1 µm for crop residues and high caking coals and <0.7 µm for the tested low caking briquettes.

Emissions of PAHs from indoor crop residue burning in a typical rural stove: emission factors, size distributions, and gas-particle partitioning.

Indoor combustion of crop residues for cooking or heating is one of the most important emission sources of polycyclic aromatic hydrocarbons (PAHs) in developing countries. However, data on PAH emission factors (EFs) for burning crop residues indoor, particularly those measured in the field, were scarce, leading to large uncertainties in the emission inventories. In this study, EFs of PAHs for nine commonly used crop residues burned in a typical Chinese rural cooking stove were measured in a simulated kitchen. The measured EFs of total PAHs averaged at 63 ± 37 mg/kg, ranging from 27 to 142 mg/kg, which were higher than those measured in chamber experiments, implying that the laboratory experiment-based emission and risk assessment should be carefully reviewed. EFs of gaseous and particulate phase PAHs were 27 ± 13 and 35 ± 23 mg/kg, respectively. Composition profiles and isomer ratios of emitted PAHs were characterized. Stepwise regressions found that modified combustion efficiency and fuel moisture were the most important factors affecting the emissions. There was 80 ± 6% of PAHs associated with PM2.5, and the mass percentage of PAHs in fine particles increased as the molecular weight increased. For freshly emitted PAHs, absorption into organic carbon, rather than adsorption, dominated the gas-particle partitioning.

Emission factors of particulate matter and elemental carbon for crop residues and coals burned in typical household stoves in China.

Both particulate matter (PM) and black carbon (BC) impact climate change and human health. Uncertainties in emission inventories of PM and BC are partially due to large variation of measured emission factors (EFs) and lack of EFs from developing countries. Although there is a debate whether thermal-optically measured elemental carbon (EC) may be referred to as BC, EC is often treated as the same mass of BC. In this study, EFs of PM (EF(PM)) and EC (EF(EC)) for 9 crop residues and 5 coals were measured in actual rural cooking and coal stoves using the carbon mass balance method. The dependence of the EFs on fuel properties and combustion conditions was investigated. It was found that the mean EF(PM) were 8.19 ± 4.27 and 3.17 ± 4.67 g/kg and the mean EF(EC) were 1.38 ± 0.70 and 0.23 ± 0.36 g/kg for crop residues and coals, respectively. PM with size less than 10 µm (PM(10)) from crop residues were dominated by particles of aerodynamic size ranging from 0.7 to 2.1 µm, while the most abundant size ranges of PM(10) from coals were either from 0.7 to 2.1 µm or less than 0.7 µm. Of various fuel properties and combustion conditions tested, fuel moisture and modified combustion efficiency (MCE) were the most critical factors affecting EF(PM) and EF(EC) for crop residues. For coal combustion, EF(PM) were primarily affected by MCE and volatile matter, whereas EF(EC) were significantly influenced by ash content, volatile matter, heat value, and MCE. It was also found that EC emissions were significantly correlated with emissions of PM with size less than 0.4 µm.

Emission factors and particulate matter size distribution of polycyclic aromatic hydrocarbons from residential coal combustions in rural Northern China.

Coal consumption is one important contributor to energy production, and is regarded as one of the most important sources of air pollutants that have considerable impacts on human health and climate change. Emissions of polycyclic aromatic hydrocarbons (PAHs) from coal combustion were studied in a typical stove. Emission factors (EFs) of 16 EPA priority PAHs from tested coals ranged from 6.25 ± 1.16 mg kg-1 (anthracite) to 253 ± 170 mg kg-1 (bituminous), with NAP and PHE dominated in gaseous and particulate phases, respectively. Size distributions of particulate phase PAHs from tested coals showed that they were mostly associated with particulate matter (PM) with size either between 0.7 and 2.1 µm or less than 0.4 µm (PM0.4). In the latter category, not only were more PAHs present in PM0.4, but also contained higher fractions of high molecular weight PAHs. Generally, there were more than 89% of total particulate phase PAHs associated with PM2.5. Gas-particle partitioning of freshly emitted PAHs from residential coal combustions were thought to be mainly controlled by absorption rather than adsorption, which is similar to those from other sources. Besides, the influence of fuel properties and combustion conditions was further investigated by using stepwise regression analysis, which indicated that almost 57 ± 10% of total variations in PAH EFs can be accounted for by moisture and volatile matter content of coal in residential combustion.