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At least 577 records · Page 32

Geochemical assessment of mineral sequestration of carbon dioxide in the midcontinent rift

Abstract This study examines the potential of Midcontinent Rift rocks to facilitate long‐term CO 2 sequestration by providing the necessary Ca and Mg for carbonate mineralization. Surface samples were collected from the Oronto and Bayfield‐Jacobsville Groups around Lake Superior and used for petrography and X‐ray diffraction to determine their mineral composition. Also, X‐ray fluorescence was also used to assess their bulk chemical composition. The samples were then exposed to CO 2 and deionized water in Teflon‐lined vessels at 90°C, and the resulting leachate fluids were analyzed for the cation released during the testing. SEM microscopy was used to examine the samples for potential mineralization of carbonate minerals. The Oronto Group sediments consist primarily of feldspathic to feldspathic lithic arenites with a chlorite‐dominated matrix, and the primary porosity is blocked by calcite and hematite cement. The Bayfield–Jacobsville sequences are porous quartz arenites to feldspathic quartz arenites that do not contain significant accumulation of Ca‐, Mg‐, and Fe‐bearing minerals. The leachate fluids obtained from Oronto Group samples exhibit a maximum Ca release rate (5.2 × 10 −4 mole/cm 2 .day), indicating rapid calcite cement dissolution and increased porosity and permeability. SEM/EDS microanalysis revealed areas where pore‐filling calcite was preferentially dissolved. Longer‐term rock‐water reactions resulted in induced carbonate mineralization, as evidenced by calcite crystals observed in a sample reacted for 102 days. © 2024 Society of Chemical Industry and John Wiley & Sons, Ltd.

Energy & Fuels↗

Technologies and policies to decarbonize global industry: Review and assessment of mitigation drivers through 2070

Fully decarbonizing global industry is essential to achieving climate stabilization, and reaching net zero greenhouse gas emissions by 2050–2070 is necessary to limit global warming to 2 °C. This paper assembles and evaluates technical and policy interventions, both on the supply side and on the demand side. It identifies measures that, employed together, can achieve net zero industrial emissions in the required timeframe. Key supply-side technologies include energy efficiency (especially at the system level), carbon capture, electrification, and zero-carbon hydrogen as a heat source and chemical feedstock. There are also promising technologies specific to each of the three top-emitting industries: cement, iron & steel, and chemicals & plastics. These include cement admixtures and alternative chemistries, several technological routes for zero-carbon steelmaking, and novel chemical catalysts and separation technologies. Crucial demand-side approaches include material-efficient design, reductions in material waste, substituting low-carbon for high-carbon materials, and circular economy interventions (such as improving product longevity, reusability, ease of refurbishment, and recyclability). Strategic, well-designed policy can accelerate innovation and provide incentives for technology deployment. High-value policies include carbon pricing with border adjustments or other price signals; robust government support for research, development, and deployment; and energy efficiency or emissions standards. These core policies should be supported by labeling and government procurement of low-carbon products, data collection and disclosure requirements, and recycling incentives. In implementing these policies, care must be taken to ensure a just transition for displaced workers and affected communities. Similarly, decarbonization must complement the human and economic development of low- and middle-income countries.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Carbon nanofibers (CNFs) dispersed in ultra-high performance concrete (UHPC): Mechanical property, workability and permeability investigation

This paper presents experimental data on the effect of carbon nano-fiber (CNF) dispersion on mechanical behavior, workability, and permeability of ultra-high-performance concrete containing CNF (UHPC-CNF). The addition of CNFs in concrete has been shown to provide improved performance. However, an inhomogeneous distribution of CNFs in the cement matrix can result in no impact or decreased mechanical performance. Due to the van der Waal's forces and hydrophobic surface properties of the CNFs, good dispersion in mix fluids and cement paste is challenging. Experimental studies of UHPC-CNF with different dispersion methods are provided. Further mixing with optimized UHPC paste allowed for the investigation of the optimal dosage of CNFs, impact on porosity, compressive strength, flexural strength, hydration rate, and slump. Scanning electron microscopy (SEM) analysis visually revealed the effect of dispersion. Our results indicate that shear mixing and subsequent ultrasonic dispersion with chemical surfactants can provide a well-dispersion liquid admixture of CNFs resulting in high mechanical performance of UHPC-CNFs composites. The water permeability and chloride resistance of optimized UHPC-CNFs composites were further evaluated with the wicking test and ponding test to reveal improved performance for these properties as well.

36 MATERIALS SCIENCE↗

Carbonation, strength development, and characterization of calcined limestone as a potential construction material

The emergence of the modern Portland cement has led to the downfall of lime as a construction material. Consequentially, its use has been limited to repair and restoration of historical buildings. Yet, its lower calcination temperature (~950 °C) and the ability to gain strength through carbonation implies its potential as a sustainable alternative to cement. In this study, calcined limestone was studied concerning its carbonation and strength development. Superplasticizer, raw limestone, and different carbonation regimes were explored as techniques to improve the composite strength development, a shortfall that hinders its re-adoption. The results indicated that the raw limestone as a partial replacement of the calcined limestone significantly improved the carbonation degree and mechanical properties. The average compressive strength reached 20 MPa under 20% CO{sub 2} due to the formation of an interconnected network of calcite as the dominant carbonation product. Supercritical CO{sub 2}, in contrast, formed disjoint particles or agglomerates of carbonates.

36 MATERIALS SCIENCE↗

The reaction between metakaolin and limestone and its effect in porosity refinement and mechanical properties

In limestone calcined clay cements (LC{sup 3}), more hemicarboaluminate and monocarboaluminate is observed, as compared to other blended cements, from the reaction of metakaolin with limestone. In this study, it is shown that the formation of these carboaluminate phases, predominantly occurs during a “third” hydration peak, after the main alite and aluminate peaks. The influence of the metakaolin content, level of sulfate addition and the water to binder ratio on the position and magnitude of this peak were investigated. This precipitation of hemi and monocarboaluminate has a significant effect on porosity refinement and strength development. It was also observed that alumina from metakaolin can contribute to the precipitation of ettringite if sufficient sulfate is available.

36 MATERIALS SCIENCE↗

Efficacy of SCMs to mitigate ASR in systems with higher alkali contents assessed by pore solution method

This study demonstrates the efficacy of supplementary cementitious materials (SCMs) to mitigate alkali-silica reaction (ASR) even when used in conjunction with cement of higher alkali contents (up to 1% Na{sub 2}O{sub eq}). The expansion of concrete prisms was studied immersed in simulated pore solution in order to address the limitations of conventional ASR testing methods, accelerated mortar bar test (AMBT) and concrete prism test (CPT). Expansion results demonstrate that 25% fly ash and 50% slag are both sufficient to mitigate ASR even with cements with alkali content up to 1% Na{sub 2}O{sub eq} and that the pore solution method is a viable alternative ASR testing method. Massive amounts of ASR products (~20 μm thickness) were observed in concretes without SCMs consistent with high degree of expansion and extensive cracking. Small amounts of ASR products (≤5 μm thickness) were also observed in concrete with SCMs despite absence of significant expansion.

36 MATERIALS SCIENCE↗

Synthesis, characterization, and thermodynamic study of selected K-based zeolites

Potassium-rich zeolites often occur in cementitious systems, as K{sup +} is widespread in various cementitious materials, such as Portland, blended and alkali-activated cements. The knowledge of their stability and of thermodynamic models for solid solutions with Na{sup +} and Ca{sup 2+} are critical to understand long-term development and durability in such cements. Completing previous studies on Na- and Ca-based zeolites, the current work aims to determine the thermodynamic data of 14 types of K-based zeolites, which could possibly form in cementitious systems. The zeolites were synthesized hydrothermally, exchanged with K{sup +}, and characterized thoroughly with respect to framework structures, elemental compositions, water contents, and bond variations. Their thermodynamic properties were derived from the experimental solubility data, which allowed establishing predominance diagrams in the K{sub 2}O-SiO{sub 2}-Al{sub 2}O{sub 3}-H{sub 2}O system. The K-based zeolites typically showed the lowest solubility between 0 and 100 °C, with the notable exception of Ca-gismondine and two Na-based zeolites: natrolite and Na-mordenite.

36 MATERIALS SCIENCE↗

Atomistic thermodynamics and kinetics of dicalcium silicate dissolution

Low-temperature cement manufacturing has garnered academic and industrial attention for its low environmental footprints. However, the sluggish hydration kinetics of the resultant cement affects their early-age strength development. This motivates fundamental studies to unravel the mechanistic picture of the dissolution process and discover science-informed pathways to accelerate hydration. Standard atomistic simulations seldomly exceed a microsecond making them impractical to study slow dissolution processes. We are using rare event sampling techniques, we provide the mechanistic picture of Ca 2+ ion dissolution from a kink site on the dicalcium silicate surface. The Ca 2+ ion dissolution is comprised of two sequential stages: breaking restraints from the kink sites to form a ledge adatom and detaching from the ledge/terrace adatom sites into the solution. The first and second stages feature free energy barriers of ~63 kJ/mol and ~ 29 kJ/mol respectively, making the first stage the rate-limiting step of the entire Ca 2+ dissolution kinetics. Using the reactive flux method, the rate and equilibrium constants for each reaction step are calculated, which yield the Ca 2+ ion activity of ~1.03 × 10 -5 . The diffusion calculations indicate that the surface effects lower the self-diffusion coefficient of Ca 2+ ions at the solid-water interface.

36 MATERIALS SCIENCE↗

A mesoscale 3D model of irradiated concrete informed via a 2.5 U-Net semantic segmentation

The concrete biological shield in light-water reactors is exposed to neutron and gamma irradiation, which deteriorates the concrete’s mechanical properties in the long term. To assess the irradiation-induced damage, predictive mechanical models are developed and used in parallel with the characterization of irradiated concrete samples. Realistic 3D simulation domains can drastically improve a model’s prediction. In this work, we utilized x-ray computed tomography (XCT) data of a concrete specimen to reconstruct its 3D microstructure. The XCT data shows low contrast between the concrete’s aggregates and cement paste, resulting in poor image segmentation when using traditional unsupervised techniques. To address this issue, we developed and trained a 2.5D U-Net model on only 24 pre-labeled XCT layers to segment 651 layers of the XCT data. The overall F1-score of the model is approximately 96%. Then, we created a 3D finite element (FE) mesh based on the stack of segmented images. The FE model contains radiation-induced expansion, damage, and creep. The constitutive equations are adapted to each phase (aggregates and cement paste). Here, we simulated the effects of neutron irradiation in the concrete specimen as well as the specimen’s mechanical response to uniaxial compression. Finally, model validation was performed using experimental data on similar concrete specimens in the literature.

2.5D U-Net↗

Influence of alkali-silica reaction on the shear capacity of reinforced concrete beams with minimum transverse reinforcement

A growing number of critical concrete infrastructure are affected by alkali-silica reaction (ASR) damage such as the Seabrook Nuclear Power Plant in New Hampshire, Parker arch-gravity dam in Arizona, and several highway bridges in California and Texas. ASR causes expansion and cracking and degrades the concrete mechanical properties. Despite a wealth of material level studies there is still limited large-scale experimental data regarding the effects of ASR on reinforced concrete (RC) members. Due to the brittle nature of the shear failure in RC structures, this study focuses on the shear response of full-scale ASR damaged RC beams with minimum shear reinforcement. Six RC beams were built with different levels of ASR susceptibility and conditioned in different environments during which continuous expansion monitoring was performed. The beams all contained reactive fine aggregate (sand) and two of them had additional alkali, 1.25% by weight of cement, to accelerate ASR. The highest expansion rate of the beams happened during the first 150 days and the expansions stayed constant after 240 days and 330 days for beams conditioned in outdoor and laboratory conditions, respectively, until the last measurement at 575 days. The highest expansion, 0.4%, was seen in the beams with additional alkali and conditioned outside with regular water spray. Out of the six beams, three were selected at different levels of ASR damage and two shear tests were performed on the minimally reinforced spans close to the ends of each beam. Results indicated that beams gain shear strength from ongoing cement hydration in the presence of moisture for ASR expansions less than 0.2%. Compared to one of the beams with 0.2% ASR expansion, one of the other samples with 0.4% expansion lost 6% of its shear strength, 25% of its shear stiffness, and showed about two times larger shear cracks and shear deformations at peak load. Finally, the shear reinforcement yielded at 20% less load in the beam with 0.4% expansion compared to the beam with 0.2% expansion.

42 ENGINEERING↗

Context and mitigation of lost circulation during geothermal drilling in diverse geologic settings

Lost circulation is one of the most common and expensive problems facing geothermal energy development, representing up to 30% of drilling costs. We examined drilling records from four geothermal fields—McGinness Hills in central Nevada, Don A. Campbell and Steamboat Hills in western Nevada, and Puna Geothermal Venture on the Big Island of Hawai'i— to identify geologies most prone to lost circulation, as well as common mitigation strategies. Depths of lost circulation events varied, but their frequency often increased in the production interval. Lost circulation commonly occurred near fault intersections, and heavily faulted fields like McGinness Hills and Don A. Campbell showed secondary mineralization within approximately 100 m (328 ft) or less of where circulation was lost. Lost circulation mitigation strategies included using locally available materials (e.g., cotton seed hulls) as well as more expensive proprietary lost circulation materials, cement plugs above the reservoir, and drilling blind with aerated, polymer-based mud in the production zone. Addressing lost circulation using a well thought out decision-making approach and materials above the reservoir will save time and cost, and provide needed well integrity. Mitigation often requires a series of steps, typically applied from perceived least expensive to most, and are dependent on the severity and location in the well where circulation was lost and availability of materials. Placing cement plugs can cure lost circulation events, however these plugs are often expensive, time-consuming, and may not be successful.

15 GEOTHERMAL ENERGY↗

Impacts on mechanical strength of chemical reactions induced by hydrous supercritical CO2 in Boise Sandstone

Geomechanics experiments were used to assess mechanical alteration of Boise Sandstone promoted by reactions with supercritical carbon dioxide (scCO 2 ) and water vapor. During geologic carbon storage, scCO 2 is injected into subsurface reservoirs, forming buoyant plumes. At brine-plume interfaces, scCO 2 can dissolve into native brines, and water from brines can partition into scCO 2 , forming hydrous scCO 2 . This study investigates the effect of hydrous scCO 2 on the strength of Boise Sandstone. Samples are first exposed to recirculating hydrous scCO 2 for 24 h at 70 °C and 13.8 MPa scCO 2 pressure. Samples are reacted with scCO 2 with added water contents up to 500 mL. After scCO 2 exposure, samples are deformed at room temperature under confining pressures of 3.4, 6.9, and 10.3 MPa. The results demonstrate that hydrous scCO 2 induces chemical reactions in Boise Sandstone, with ions migrating from the solid into the hydrous scCO 2 phase. At the longer time-scales, these reactions could lead to mechanical weakening in the samples; however, on the scale of our experiments, the strength changes are within sample variability. Because the solubility of water in scCO 2 is extremely low (0.008 mol H 2 O per 1 mol CO 2 ), the mineral dissolution of Boise Sandstone was under 0.002 wt.%. Additionally, mineral grains and pore throats in Boise Sandstone are cemented with quartz, which is not susceptible to dissolution at these conditions. Our results indicate that humidity in scCO 2 plumes is unlikely to sustain chemical reactions and induce long term strength changes in quartz cemented sandstones due to resistant mineralogies and low water solubility.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Estimation of abatement potentials and costs of air pollution emissions in China

Understanding the air pollution emission abatement potential and associated control cost is a prerequisite to design cost ef?cient control policies. In this study, a linear programming algorithm model, International Control Cost Estimate Tool, was updated with cost data for applications of 56 types of end-of-pipe technologies and ?ve types of renewable energy in 10 major sectors namely power generation, industry combustion, cement pro-duction, iron and steel production, other industry processes, domestic combustion, transportation, solvent use, livestock rearing, and fertilizer use. The updated model was implemented to estimate the abatement potential and marginal cost of multiple pollutants in China. The total maximum abatement potentials of sulfur dioxide (SO2), nitrogen oxides (NOx), primary particulate matter (PM2.5), non-volatile organic compounds (NMVOCs), and ammonia (NH3) in China were estimated to be 19.2, 20.8, 9.1, 17.2 and 8.6 Mt, respectively, which accounted for 89.7%, 89.9%, 94.6%, 74.0%, and 80.2% of their total emissions in 2014, respectively. The associated control cost of such reductions was estimated as 92.5, 469.7, 75.7, 449.0, and 361.8 billion CNY in SO2, NOx, primary PM2.5, NMVOCs and NH3, respectively. Shandong, Jiangsu, Henan, Zhejiang, and Guangdong provinces exhibited large abatement potentials for all pollutants. Provincial disparity analysis shows that high GDP regions tend to have higher reduction potential and total abatement costs. End-of-pipe technologies tended be a cost-ef?cient way to control pollution in industries processes (i.e., cement plants, iron and steel plants, lime production, building ceramic production, glass and brick production), whereas such technologies were less cost- effective in fossil fuel-related sectors (i.e., power plants, industry combustion, domestic combustion, and transportation) compared with renewable energy. The abatement potentials and marginal abatement cost curves developed in this study can further be used as a crucial component in an integrated model to design optimized cost-ef?cient control policies.

Zhang, Fenfen↗

Reassessing early-age strength development of high-volume fly ash concretes for precast buildings

Increasing beneficial use of fresh or landfilled fly ash as a replacement for Portland cement can be more challenging for the construction of precast buildings or similar applications requiring rapid strength development. Therefore, the framework presented in this paper aims to reassess high-volume fly ash concretes but in the context of facilitating more sustainable precast buildings. More specifically, the framework was used to characterize strength development of concrete mixes with a target minimum 24-hour compressive strength of 24.1 MPa (3500 psi), selected as an example strength development metric to demonstrate the framework, and comprised of 40% Class C, Class F, and landfilled (harvested) fly ash – as a high-volume replacement of Type III or Type IL cement. High-early strength was driven by optimized dosages of commercial grade gypsum and accelerating admixtures, in addition to optimal aggregate packing and mix proportioning strategies. Early-age mechanical properties including compressive strength, modulus of rupture, and modulus of elasticity were reevaluated within 24 hours of batching with respect to common precast production demands. Simple data analyses were then used to highlight cases where currently accepted design provisions for the aforementioned properties are either overly-conservative or unconservative with respect to test data. Furthermore, the framework and demonstration of example mixes presented herein aim to promote confidence for using larger fractions of fresh or landfilled fly ashes for precast buildings to further enhance environmental benefits without sacrificing pertinent early-age structural performance.

42 ENGINEERING↗

Three-Dimensional Pore Networks in Miocene Stevens Sandstone of California: Implications for CO 2 Geologic Storage

The Miocene Stevens Sandstone in the San Joaquin Basin of California is increasingly recognized as a promising candidate for CO 2 geological storage due to the enormous storage capacity, proven sealing, and existing infrastructure. In this study, computed microtomography imaging and pore network modeling were employed to investigate the influence of pore geometry and wettability on the CO 2 injectivity and residual trapping. Image analysis revealed that a significant fraction of the cement and matrix consists of microporous regions. The microporosity can substantially increase the overall pore space, yet its contribution to permeability remains modest, particularly in samples with low permeability. The intrinsic heterogeneity of turbidite reservoirs further complicates the reservoir properties among different layers. Two-phase flow simulations under varying wettability conditions (water-wet, weak water-wet, and neutral-wet) demonstrated that the CO 2 injection is predominantly controlled by macropores. CO 2 invades microporous regions only after these larger pores are filled. The presence of microporosity leads to a decrease in both initial and residual CO 2 saturations, with the magnitude of the reduction being influenced by wettability. Neutral-wet scenarios exhibit higher CO 2 mobility and thus lower residual trapping than water-wet scenarios. The results imply that heterogeneity in pore geometry and cement distribution across different layers can result in stratified CO 2 flow pathways, complicating efforts to predict injection performance. Overall, the Stevens Sandstone shows considerable promise for CO 2 geologic storage, but effective implementation will require detailed characterization of the pore structure as well as the integration of reactive fluid flow to account for potential mineral dissolution and fines migration.

fluids↗

Computational Chemistry-Based Evaluation of Metal Salts and Metal Oxides for Application in Mercury-Capture Technologies

Anthropogenic mercury emission to the atmosphere adversely affects the environment, wildlife, and human health. Accordingly, the design and implementation of improved mercury-capture technologies have received increased attention. We present a computational chemistry-based screening study to guide the development of mercury-capture materials. We use density functional theory (DFT) to probe the efficacy of metal salts and metal oxides (NaCl, NaBr, KCl, KBr, CaCl 2 , CaBr 2 , NaNO 3 , and MgO) toward mercury capture and their ability to be regenerated for continued use. We focus on three primary sources of mercury emission as elemental gaseous mercury (Hg(0)) or oxidized gaseous mercury species (Hg(II); HgCl 2 or HgBr 2 ): (i) Hg(0) emission from artisanal Au production; (ii) Hg(II)/Hg(0) emission from inlet/outlet streams for flue-gas desulfurization (FGD) operation; and (iii) Hg(0) and Hg(II) emission from cement production. Our results suggest that CaCl 2 and CaBr 2 are good candidates for capturing Hg(0) in artisanal Au production. For FGD operation, KBr, MgO, CaCl 2 , and CaBr 2 are good candidates for capturing HgCl 2 and HgBr 2 , while CaBr 2 is the only studied material that can capture Hg(0) from the outlet FGD stream. For cement production, CaBr 2 is the only material of those studied that can capture Hg(0), HgCl 2 , and HgBr 2 . Furthermore, our DFT results can accelerate the development of cheap and regenerable mercury-capture materials, as well as better prevent the release of mercury to the environment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of Lithium Doping on MgO Hydroxylation and Carbonation

Recovery of magnesium from brines can potentially be used to source MgO (periclase) as a CO 2 sorbent or for Mg-based cements. However, it is not clear how common impurities in brines, such as lithium, affect the resulting MgO reactivity. Here, to test the effect of lithium incorporation on MgO reactivity for hydration and carbonation, we combined computational simulations with experiments. Experimentally altered (Mg,Li)O with a low dopant concentration (0.012 ± 0.002% w/w Li) was characterized using synchrotron-based X-ray scattering and high-resolution electron microscopy to measure reaction layer formation on (Mg,Li)O. Single-crystal X-ray diffraction analysis of (Mg,Li)O demonstrates that the incorporation of lithium leads to the formation of oxygen vacancies. The presence of vacancies is likely causing faster hydroxylation rates as predicted by ab initio molecular dynamics simulations. However, the faster hydroxylation rates likely lead to faster passivation of the surface because we observe thinner reaction layers on (Mg,Li)O samples both over short time periods (30 days) and over long time periods (28 years). After 28 years, the reaction layer on the (Mg,Li)O sample was less than one-third of the thickness of that of the pure MgO sample. In addition, over 30 days, reaction layers on (Mg,Li)O samples primarily formed at steps rather than on terraces, in contrast to our previous observations on MgO. Based on our results, naturally occurring impurities in MgO modify its reactivity even at very low concentrations and need to be considered for accurate reaction rate prediction for application of MgO as a CO 2 sorbent or in cements.

MgO↗

Geo-Responsive Chemomechanics in Aluminum Oxyhydroxide via Alkali-Driven Dehydroxylation for Supercritical Geothermal Systems

Widespread use of enhanced geothermal systems can revolutionize global renewable electrical power access, yet its advancement is hindered by the inherent instability of Portland cement-based chemistries for geothermal well construction under high-temperature corrosive conditions. Here, in this work, we demonstrate the tunable mechanical performance of aluminum oxyhydroxides as cementitious materials through an alkali-controlled dehydroxylation reaction pathway for long-term applications under supercritical geothermal environments. Notably, the synthesized aluminum oxyhydroxides demonstrate remarkable stability, maintaining superior mechanical performance under supercritical conditions for over 30 days. Synchrotron X-ray diffraction, spectroscopy measurements and geochemical thermodynamic modeling uncover that the gibbsite dehydroxylation pathway functions as a key dial for tuning the chemomechanics, rendering the aluminum oxyhydroxide a strong cementitious material. By uncovering the mechanistic role of alkali-driven dehydroxylation, this work proposes a cementitious chemistry distinct from conventional Portland cement and geopolymer-dominated alkali-activated systems, laying the groundwork for developing next-generation cementitious materials for supercritical geothermal energy exploitation.

15 GEOTHERMAL ENERGY↗