CO2 Fluid Research Articles

Gold, antimony and mercury ore formation and metallogenic link in the Sandu-Danzhai area, Jiangnan Orogen, SW China

The turbidite-hosted Au-Sb-Hg deposits in the Sandu-Danzhai area are distributed along the southwestern marginal fault of the Jiangnan Orogen, yet any genetic link among the Au, Sb and Hg mineralization and their respective ore-forming process remain unclear. Here, we investigate the Paiting Au(-Hg) and Miaolong Au-Sb deposits and present a new metallogenic model based on detailed petrographic observations, and in-situ trace element (EPMA and LA-ICP-MS) and sulfur isotope (fs-LA-MC-ICPMS) analyses on sulfide minerals. Our results show that the ore formation in the Sandu-Danzhai metallogenic belt (SDMB) can be divided into Au (pyrite + arsenopyrite + dolomite), Au-Sb (pyrite + arsenopyrite + stibnite + quartz), Sb (stibnite + native antimony + barite + dolomite + quartz) and Hg (cinnabar + calcite) stages, based on mineral paragenetic and vein crosscutting relationships. Trace element compositions suggest that progressive As enrichment in pyrite is accompanied by increasing Au, Sb and Cu contents, implying that these elements may have been leached from the same source via fluid-rock reactions. Sulfur isotope compositions of the sulfates and sulfides in the Au-Sb-Hg ores reveal that the sulfur was originated from thermal-chemical sulfate reduction (TSR) of marine sulfates in the Cambrian ore-bearing strata. Thus, we propose that deep metamorphic fluids (as evidenced from the high fluid CO2 and CH4 contents) may have promoted ore-material (e.g., Au, Sb, As, Hg) mobilization in the metamorphic basement and/or Cambrian strata. As for the metal transport and precipitation mechanism, fluid-rock interaction may have decreased the ore-fluid As content and caused auriferous pyrite precipitation. Meanwhile, changes in temperature and oxygen-sulfur fugacity may have significantly decreased Sb solubility, leading to extensive stibnite precipitation. Cinnabar associated with calcite was likely deposited via carbonate dissolution in the Cambrian strata in late hydrothermal (waning) stage. Overall, we propose that the Au-Sb-Hg deposits in the SDMB are best classified as orogenic type, and the metallogeny was controlled by boundary faults of the Jiangnan Orogen.

Mechanical strength and porosity changes of bituminous coal induced by supercritical CO2 interactions: Influence of saturation pressure

Sequestration of CO2 in the geological formations has great potential to reduce greenhouse gas emissions, and the induced mechanical stability of coal reservoirs is deeply concerned with the long-term safety of CO2 geological storage. After injection, it is likely that CO2 is stored in the form of supercritical state in coal reservoirs. To date, our current knowledge is still lacking in the underlying interaction mechanisms between coal and supercritical CO2 (ScCO2) fluids under the influence of saturation pressure. In this work, ScCO2 saturation was performed on bituminous coal at the pressures from 7.5 to 25 MPa for saturation time up to 10 days. Mercury intrusion porosimetry (MIP), X-ray diffraction (XRD) and uniaxial compression measurements were conducted to evaluate the mechanical strength and microstructure changes of bituminous coal. The results indicate that coal pore structures are greatly changed by ScCO2 interactions, including the increase of pore volume (84.8–173.2%) and surface area (42.1–85.8%). The larger hysteresis effect is found in saturated specimens, illustrating that ScCO2 interactions enhance the pore roughness of coal. The carbonates in coal are sensitive to ScCO2 fluids, which are extensively dissolved during interactions. ScCO2 saturation pressure has significant impact on the mechanical properties of coal. Rapid reduction of mechanical strength (up to 35.6%) was identified when the pressure was increased from 7.5 to 15 MPa. Subsequently, limited further reduction (<9%) occurred as the saturation pressure is further increased up to 25 MPa. Mineral dissolution and porosity changes account for the mechanical degradation, which weakens the cementation degree and interaction force of coal matrix.

Evaluation of different blackcurrant seed ingredients in meatballs by using conventional quality assessment and untargeted metabolomics

Blackcurrants are sources of phenolic compounds, such as anthocyanins, possessing strong antioxidant, antimicrobial and antifungal activity. Therefore, the addition of different blackcurrant pomace ingredients may affect the overall meat quality. The actual chemical profile and bioactivities of blackcurrant pomace ingredients may strongly depend on its preparation; for instance, in our study the highest values of the in vitro antioxidant capacity were determined for blackcurrant seeds after supercritical CO2 extraction. Starting from these background conditions, in this work, we evaluated the ability of three different concentrations (namely 1, 3, and 5% w/w) of blackcurrant (BC) seeds following EtOH/water extraction (BC-AE), before supercritical fluid CO2 extraction (BC-RS), and after supercritical fluid CO2 extraction (BC-ASC) to affect different quality parameters of pork meatballs. These latter were stored considering three different time-points, namely 1, 3 and 6 days at 4 °C packed under modified atmosphere (i.e., 70% N2 and 30% CO2). Untargeted metabolomics allowed to identify several lipid and protein-related oxidation products involved in redox reactions, such as 13-L-hydroperoxylinoleic acid, (12S,13S)-epoxylinolenic acid, 9,10-epoxyoctadecenoic acid, glutathione, glutathione disulfide, L-carnosine, l-ascorbic acid, and tocotrienols. Besides, multivariate statistics applied on the metabolomics dataset confirmed that the chemical profile of meatballs was an exclusive combination of both BC inclusion levels and type of BC-ingredients considered. Our findings showed that the higher the concentration of BC seed ingredients in meatballs, the lower the cooking loss and the higher the fibre content. Also, all the ingredients significantly affected the colour parameters.

A Comprehensive Assessment of the Refrigerant Charging Amount on the Global Performance of a Transcritical CO2-Based Bus Air Conditioning and Heat Pump System

To mitigate the contemporary environmental challenges and to respect the regulations on the progressive ban of hydrofluorocarbons (HFC), natural fluid CO2 was selected as an ideal refrigerant alternative in the transportation domain. In this study, the optimal CO2 charging amount and the refrigerant distribution in a bus air conditioning/heat pump system were analyzed in detail. The results showed that there was a plateau (so named by the best charging amount) of the CO2 charging amount in which the system performance reached an optimal value and maintained it nearly unchanged during this plateau while the performance declined on both sides of the plateau. In addition, the ambient temperature was found to have little effect on the determination of the refrigerant charging plateau, while the refrigerant distribution was affected by the ambient temperature to some extent. Due to the large thermal load and thermal inertia on a bus, the data and conclusions obtained are different from those of ordinary electric small passenger vehicles. This article aims to discover some quantitative parameters and lay a theoretical foundation in this field which is lacking relevant research. Through the research based on the GT-Suite simulation platform, we simulated the transcritical CO2 cycle applied on a bus, and the performance changes of the bus system (COP 1.2–2.2, refrigerating capacity 9.5–18 kW) under different charging rates (3–8 kg) were obtained.

Experimental Evaluation of Combined Plugging System for CO2-Improved Oil Recovery and Storage

High-performance CO2-improved oil recovery (IOR) and storage technology is one of the most promising measures for global oilfield companies to achieve zero carbon targets. Due to the severe heterogeneity of most petroleum reservoirs and the significant density difference between CO2 and reservoir fluid, the efficiency of CO2-IOR and storage is usually limited. In this paper, a high-temperature and high-pressure 30 cm core displacement experiment was used to study the CO2 conformance control performance of both the single- and the combined plugging system in long sandstone cores. The single systems evaluated included polymer gels, CO2 foams, and CO2-responsive thickening polymer (CO2-RTP) systems. The combined systems were pairwise combinations of the three of them. Results show that the pressure rise and maximum breakthrough pressure of the gel system were the highest among three single-plugging systems. Its plugging efficiency was the highest, reaching 86.13%. At the same time, its gas production reduction rate was also the highest, reaching 95.71%. In the parallel 30 cm core plugging experiments, three combined plugging systems all showed excellent plugging and CO2 conformance improvement performance. Among them, the combined plugging systems containing polymer gels had larger plugging efficiency, and their gas production reduction ratios reached about 90%. Compared with single systems, the combined plugging systems had the advantages of easy injection and in-depth propagation, which can significantly improve CO2 conformance and oil recovery. The research results of this study can provide the experimental understanding and theoretical guidance for the current tricky oilfield problems of CO2 channeling.

Extract of Bletilla formosana callus elevates cellular antioxidative activity via Nrf2/HO-1 signaling pathway and inhibits melanogenesis in zebrafish

BackgroundBletilla species are endangered terrestrial orchids used in natural skin care formulas in Asia for a long history. In order to explore the bioactivity potential of Bletilla species as a cosmetic ingredient in a sustainable resource manner, the callus of Bletilla formosana (Hayata) Schltr. was established and extracted by an eco-friendly supercritical fluid CO2 extraction (SFE-CO2) method. The intracellular reactive oxygen species (ROS) scavenging activity and antioxidation-related gene expression of the callus extract were evaluated in both Hs68 fibroblast cells and HaCaT keratinocytes. The melanogenesis-inhibitory effect was investigated in B16F10 melanoma cells and in an in vivo zebrafish model. ResultsThe calli of B. formosana were propagated for 10–15 generations with a consistent yellow friable appearance and then subjected to SFE-CO2 extraction to obtain a yellow pasty extract. Obvious intracellular ROS scavenging activity of the extract was detected in both Hs68 and HaCaT cells with 64.30 ± 8.27% and 32.50 ± 4.05% reduction at the concentration of 250 μg/mL. Moreover, marked expression levels of heme oxygenase-1 (HO-1) and (NAD(P)H) quinone oxidoreductase-1 (NQO1) genes were detected after 6-h and 24-h treatments. These results indicate the cellular antioxidative activity of B. formosana callus extract was probably activated via the nuclear factor erythroid 2-related factor 2 (Nrf2)/HO-1 signaling pathway. Melanogenesis-inhibitory effect of the extract was observed in α-MSH stimuli-inducing B16F10 cells with 28.46% inhibition of intracellular melanin content at the concentration of 50 μg/ml. The effect was confirmed with in vivo zebrafish embryos that showed a relative pigmentation density of 80.27 ± 7.98% at the concentration of 100 μg/mL without toxicity. ConclusionOur results shed light on a sustainable utilization of Bletilla species as a potential ingredient for skin.

Experimental Modeling of the Interaction between Garnets of Mantle Parageneses and CO2 Fluid at 6.3 GPa and 950–1550 °C

Abstract —Experimental modeling of the interaction of eclogitic and lherzolitic garnets with CO2 fluid was carried out on a multianvil high-pressure apparatus of the “split-sphere” type (BARS) in platinum ampoules with inner graphite capsules, using a buffered high-pressure cell with a hematite container, at a pressure of 6.3 GPa and in the temperature range 950–1550 °C. It has been established that the main interaction processes at 6.3 GPa and 950–1250 °C are partial dissolution, recrystallization, and carbonation of garnet which lead to the formation of magnesian carbonate, kyanite, and coesite, a decrease in Mg contents in the recrystallized garnet, and the formation of carbonate, silicate, and oxide inclusions in it. Under these conditions, crystallization of metastable graphite and growth of diamond on the seed at ≥1250 °C were observed. In the temperature range 1350–1550 °C, the garnet underwent partial dissolution and recrystallization in CO2 fluid; no carbonation took place. These processes were accompanied by a decrease in the portion of the grossular component in the garnet and by the enrichment of the fluid phase with calcium. We have established the indicative characteristics of garnet that interacted with CO2 fluid: zoning, with low contents of CaO and MgO in the rims of crystals relative to the cores, and the presence of carbonate, kyanite, coesite, and CO2 inclusions. The compositions of the produced garnet and carbonates are consistent with the data on these minerals in mantle peridotite and eclogite parageneses and in inclusions in diamonds, which suggests a significant role of metasomatism with the participation of CO2 fluid in the evolution of deep-seated rocks and in the diamond formation. In this experimental research, we have first studied the processes of diamond crystallization and determined the boundary conditions for diamond growth in the system silicate–carbonate–CO2, which simulates natural diamond formation media. In general, the established regularities can be regarded as potential indicators of mantle metasomatism and mineral formation with the participation of CO2 fluid.

Heat transfer analysis of supercritical CO2 in a High-Speed turbine rotor shaft cooling passage

This study investigated the turbulent flow heat transfer in a high-speed turbine rotor shaft cooling passage using CFD. Supercritical CO2 is used as the coolant. The coolant temperature, heat transfer coefficient, convection heat transfer, and frictional heat transfer are investigated. The effect of clearance, mass flow rate, shaft rotational speed, and shaft temperature is also investigated. The result showed that the coolant temperature and heat transfer coefficient are independent of the radial clearance. The significant effect of mass flow rate on the coolant temperature is predicted. The convection heat transfer is substantially higher than the frictional heat transfer. This implies that the convection heat transfer is highly dominant over the frictional heat transfer by which the significant cooling provision could be achieved by the supercritical CO2 fluid through the annulus passage. A little agreement is found when the quantity of heat transfer is predicted using correlation and compared with the result obtained by CFD.

Liver Protection of a Low-Polarity Fraction from Ficus pandurata Hance, Prepared by Supercritical CO2 Fluid Extraction, on CCl4-Induced Acute Liver Injury in Mice via Inhibiting Apoptosis and Ferroptosis Mediated by Strengthened Antioxidation

Ficus pandurata Hance (FPH) is a Chinese herbal medicine widely used for health care. This study was designed to investigate the alleviation efficacy of the low-polarity ingredients of FPH (FPHLP), prepared by supercritical CO2 fluid extraction technology, against CCl4-induced acute liver injury (ALI) in mice and uncover its underlying mechanism. The results showed that FPHLP had a good antioxidative effect determined by the DPPH free radical scavenging activity test and T-AOC assay. The in vivo study showed that FPHLP dose-dependently protected against liver damage via detection of ALT, AST, and LDH levels and changes in liver histopathology. The antioxidative stress properties of FPHLP suppressed ALI by increasing levels of GSH, Nrf2, HO-1, and Trx-1 and reducing levels of ROS and MDA and the expression of Keap1. FPHLP significantly reduced the level of Fe2+ and expression of TfR1, xCT/SLC7A11, and Bcl2, while increasing the expression of GPX4, FTH1, cleaved PARP, Bax, and cleaved caspase 3. The results demonstrated that FPHLP protected mouse liver from injury induced by CCl4 via suppression of apoptosis and ferroptosis. This study suggests that FPHLP can be used for liver damage protection in humans, which strongly supports its traditional use as a herbal medicine.

The Collaborative Optimization of the Discharge Pressure and Heat Recovery Rate in a Transcritical CO2 Heat Pump Used in Extremely Low Temperature Environment

Considering the excellent environmental properties and heating capability under wide running conditions of the natural fluid CO2, the transcritical CO2 heat pump system has widely been used in the application of water heaters, commercial heating and cooling, electric vehicle thermal management, etc. Since the performance was highly affected by the discharge pressure and heat recovery rate in a transcritical CO2 system, the collaborative optimization of these two parameters was analyzed in detail in this study. The results showed that the optimal value of the system heating COP, which was the ration of heating capacity to power consumption, was better under a higher heat recovery rate and relatively lower discharge pressure, which is why these kinds of operating conditions are highly recommended from the perspective of collaborative optimization. Additionally, the heat recovery rate had a positive effect on the system performance when the discharge pressure was lower than its optimal value, while the heat recovery rate would present a passive effect on the system performance when the discharge pressure was higher than its optimal value. The relevant conclusions of this study provide a good theoretical basis for the efficient and stable operation of the transcritical CO2 heat pump technology under the conditions of a wide ambient temperature range.

Influence of Supercritical CO2 Fluid on CH4 and CO2 Diffusion in Vitrinite-Rich Coals and Inertinite-Rich Coals

Coal maceral composition has a great effect on gas adsorption and diffusion. The interaction between maceral composition and supercritical CO2 (SCCO2) fluid will affect gas diffusion behavior in coals. Thus, the diffusivity derived from adsorption kinetics of CH4 and CO2 in vitrinite- and inertinite-rich coals with low-violate bituminous rank collected from the Hancheng mine of the Weibei coalfield pre- and post-SCCO2 fluid exposure (SFE) were tested at the conditions of 45 °C and 0.9 MPa. In combination with pore distribution and functional group content, the possible mechanism of the alterations in gas diffusion characteristics in coals with various maceral compositions was addressed. The results show that for vitrinite-rich coals, SFE increases the macropore apparent diffusion coefficient of CH4, while this treatment decreases the micropore apparent diffusion coefficient of CH4. However, the reverse trend is found for CO2 diffusion–adsorption rate. For inertinite-rich coals post-SFE, CH4 diffusion–adsorption rate increases, while an increase and a decrease in diffusivity CO2 occur for macropore and micropore, respectively. Generally, SFE shows a stronger impact on CO2 adsorption rate than CH4 in coals. The results suggest that the diffusion of CH4 and CO2 in coals with different maceral compositions show selectivity to SCCO2 fluid. The possible reason can be attributed to the changes in pore structure and surface functional group content. SFE causes an increase in macro/mesopore volume of all samples. However, SFE induces a reduction in oxygen-containing species content and micropore volume of inertinite-rich coals, while the opposite trend occurs in vitrinite-rich coals. Thus, the changes in pore volume and surface functional group account for the difference in gas diffusivity of coals with different maceral compositions. With regard to the micropore diffusion–adsorption behavior of CH4 and CO2, the impact of oxygen-containing species is superior to pore volume. The oxygen-containing species favor CO2 diffusion–adsorption but go against CH4 transport. This effect accounts for the reduction in the micropore diffusion–adsorption rate of CH4 and the increase in micropore diffusivity of CO2 in vitrinite-rich coals, respectively. However, the aforementioned effect is the opposite for inertinite-rich coals. Overall, the changes in gas diffusion in coals with different maceral composition during the CO2-ECBM process requires further attention.

Preparation of TiO2/PAN-based activated carbon nanofibers assisted by supercritical CO2 fluid

Polyacrylonitrile (PAN)-based activated carbon nanofibers were used as a photocatalyst carrier and framework due to its large specific area and can adsorb organic pollutants. In this paper, the supercritical carbon dioxide was used to deposit TiO2 on the surface of pre-oxidized PAN nanofibers, and the fibers were activated by heat treatment to prepare activated carbon nanofibers-TiO2 (TiO2/ACNF). The morphology, structure and specific surface area of the modified nanofibers were analyzed, and the degradation test of methyl orange was carried out. The results showed that TiO2 nanoparticles can be uniformly loaded on the surface of pre-oxidized PAN nanofibers after supercritical treatment. The specific surface area of the TiO2/ACNF after activated heat treatment can reach 422.8 m2/g, having higher adsorption and photocatalytic degradation performance.

Pore structure and pore size change for tight sandstone treated with supercritical CO2 fluid

The effects of ScCO2 on pore structure should be investigated in order to properly apply supercritical carbon dioxide (ScCO2) fracturing on tight sandstone. ScCO2 treatment was applied to three sets of tight sandstone samples. The pore structure was characterized using a combination of high-pressure mercury intrusion porosimetry and nuclear magnetic resonance. Furthermore, the pore size distribution’s multi-fractal dimensions were estimated. After SCCO2 treatment, the number of transitional pores decreased significantly, while the number of mesopores and macropores increased. At all scales, the fractal dimension characteristics indicate that pore structure gets more complicated and heterogeneous. Furthermore, due to their larger contact area, large pores have a higher fractal dimension than small pores. The accumulative pore volume of the calcite-rich group increases and a decreasing trend occurs for the calcite-rare group. The content of calcite sharply decreased while clay, feldspar, and plagioclase content have a slight drop after ScCO2 treatment, which affects the alternation of pore structure. Thus, the accumulative porosity volume and pore connectivity do not always increase after ScCO2 exposure because re-precipitation and fine migration can potentially clog pores and channels.

Valorization of the Antioxidant Effect of Mantua PGI Pear By-Product Extracts: Preparation, Analysis and Biological Investigation.

For improving the management of the production chain of PGI Mantua pears (which comprises many varieties, including Abate Fetel), applying the cardinal principles of circular economy and sustainability, the fruits with diseases or defects were recovered for producing dried rounds of pears from the Abate Fetel cultivar, a new product with high nutritional value that extends the remaining life. This process led to the production of secondary and residual by-products, which are mainly composed of the highest and lowest part of the fruits, comprising seeds, pulps, peels and petioles. Hence, this study was focused on the valorization of these secondary by-products of Abate Fetel pears through the production of pear extracts using traditional and "green" extraction methods that involve the use of supercritical CO2 fluid extraction. The produced extracts, together with a reference solvent-derived extract, were analyzed by HPLC-ESI-MS, and in parallel, their direct and cellular antioxidant activity were assessed. Evidence has indicated that all the tested extracts reduced the H2O2-induced reactive oxygen species (ROS), lipid peroxidation and nitric oxide (NO) levels, respectively, in human intestinal Caco-2 cells. Hence, this study clearly suggests that extracts obtained from Mantuan PGI pear by-products may be used as valuable sources of bioactive upcycled phytocomplex for the development of dietary supplements and/or functional foods.

Fluid mineralization of the Dongtongyu gold deposit in the southern margin of North China craton: Evidence from microthermometry and composition of fluid inclusions

In this study, petrographic, microthermometric, and synchrotron radiation X-ray fluorescence (SRXRF) analyses of fluid inclusions were conducted to shed light on the mineralization mechanism of the Dongtongyu deposit and provide some evidence of the relationship among CO2, Au, and other ore elements (e.g., Cu, Fe, Zn, and Pb) in ore-forming fluids. The ore-forming fluid is characterized as the H2O–CO2–NaCl system with medium–high temperatures and low salinities. Four structural mineralization stages are distinguished: Pyrite-quartz (Stage 1), gold-quartz-pyrite (Stage 2), gold-quartz-polymetallic sulfide (Stage 3), and quartz-calcite (Stage 4). Fluid inclusions in Stages 1–3 are dominated by the H2O–CO2 type, and most of them contain liquid H2O and liquid CO2 at room temperature. The melting temperatures (Tm-CO2 = −82.1°C to −57.5°C) of solid CO2 in Stage 1 are relatively low. The values of Tm-CO2 in Stages 2–3 are quite close, with ranges of −60.5°C to −56.5°C and −59.2°C to −58.6°C, respectively. The melting temperatures of clathrate in Stages 1–3 are −2.7°C to +7.8°C, −5.5°C to +7.8°C, and +3.7°C to +7.2°C. The homogenization temperatures of the CO2 phase in the H2O–CO2 inclusions of the three stages are measured as −7.5°C to +31.7°C, −7.5°C to +29.3°C, and 7.1°C to +24.1°C. The total homogenization temperatures in Stages 1–3 are 180°C–394°C, 202°C–305°C, and 224°C–271°C, with salinities of 4.3 wt.%–18.2 wt% NaCl, 4.3 wt.%–20.0 wt% NaCl, and 5.3 wt.%–11.0 wt% NaCl, respectively. The laser Raman spectroscopy results show that the CO2–H2O inclusions in the quartz veins contain abundant CO2 and CH4. The SRXFR results show that most of the elements, especially As, Te, and Cu, are more enriched in liquid CO2 than in liquid H2O. The elements of Au, Fe, Ni, Cu, and Pb have higher concentrations in H2O–CO2-type fluid inclusions in Stage 2 than other fluid inclusions in Stages 1–2, suggesting that gold mineralization is closely related to CO2-rich fluids. During the fluid evolution process, fluid immiscibility is an important mineralization mechanism of gold. The increase in CO2 and CH4 and the decrease in the fluid temperature might promote fluid immiscibility.

Polybenzodiazine Aerogels: All-Nitrogen Analogues of Polybenzoxazines─Synthesis, Characterization, and High-Yield Conversion to Nanoporous Carbons

Tetrahydroquinazoline (THQ) was designed as an all-nitrogen analogue of main-stream benzoxazine monomers. THQ solutions in DMF gelled at 100 °C via HCl-catalyzed ring-opening polymerization to polybenzodiazine (PBDAZ) wet gels, which were dried in an autoclave with supercritical fluid CO2 to aerogels. These as-prepared PBDAZ-100 aerogels undergo ring-fusion aromatization at 240 °C under O2. This oxidized form is referred to as PBDAZ-240. Chemical identification of PBDAZ-100 and PBDAZ-240 relied on consideration of all nine possible polymerization pathways, in combination with elemental analysis, infrared and solid-state 13C NMR spectroscopy, and 15N NMR spectroscopy of aerogels from the selectively 15N-enriched THQ monomer. Fully oxidized PBDAZ-240 aerogels were carbonized at 800 °C under Ar to carbon aerogels with 61% w/w yield and with retention of the nanomorphology of the parent PBDAZ-100 aerogels. Direct pyrolysis of PBDAZ-100 at 800 °C, i.e., without prior oxidation, resulted in only 40% w/w yield and complete loss of the fine nanostructure. The evolution of PBDAZ-240 aerogels along pyrolysis toward carbonization was monitored using progressively higher pyrolysis temperatures from 300 to 800 °C under Ar. Aerogels received at 600 and 800 °C (referred to as PBDAZ-600 and PBDAZ-800, respectively) had relatively high surface areas (432 and 346 m2 g–1, respectively), a significant portion of which (79% in both materials) was assigned to micropores. The new polymer aerogels, together with polybenzoxazine aerogels, comprise a suitable basis set for comparing N-rich versus O-rich porous carbons as adsorbers.

Raman spectroscopic evaluation of precision of oxygen isotope ratio of carbon dioxide

We measured the Raman spectra of CO2 fluid at 30 MPa and room temperature (19.1–21.3°C). The spectra showed peaks attributed to the CO2 combining various isotopes such as 12C16O2, 13C16O2, and 12C16O18O. The relative ratio of 12C16O2 to 12C16O18O peaks represents the oxygen isotope ratio of CO2. To evaluate the precision of the peak ratios, we measured the CO2 Raman spectra at different exposure times. We examined the standard deviation (1 σ) of the peak intensity ratios and area ones for 20 measurements at each exposure time. The standard deviations of the intensity ratios and area ones were 2.7 and 3.1%, respectively, at a maximum exposure time of 494 s, conversion to peak intensity of 12C16O2 yields about 2,000,000 counts. The uncertainties are 2.5–3 times greater than expected from the noise of a CCD camera and photon statistics. The oxygen isotope ratios (δ18O) of natural samples have a range of variation of about 16.6%. Compared to that value, the precision we obtained from this study is very small. Raman spectroscopy can be combined with microscopy to analyze areas as small as approx. 1 µm in diameter. Therefore, oxygen isotope measurement using Raman spectroscopy has potential for application to natural samples as a new method for small CO2 fluids such as fluid inclusions.

Geology, mineralization and calcite‐rich potassic alteration at the Humpa Leu East (HLE) porphyry Cu‐Au prospect, Hu'u district, Sumbawa Island, Indonesia

AbstractThe Humpa Leu East (HLE) prospect is one of the newly discovered porphyry Cu‐Au prospects in the Hu'u district, Sumbawa Island, Indonesia. The HLE prospect was formed by calc‐alkaline magmatic activity in an active continental margin setting. The prospect is typical calc‐alkaline porphyry Cu‐Au mineralization related to multiphase diorite and quartz diorite porphyry intrusions, which are hosted by andesitic crystalline tuff, volcanic breccia, and andesite lava. Hydrothermal alteration recognized at the surface includes potassic, propylitic, advanced argillic, intermediate argillic, and argillic alteration. Two styles of Cu‐Au mineralization were identified in the HLE prospect, that is, quartz‐sulfide veins and sulfide dissemination, formed in the early, intermediate, and late stages. The early stage is associated with M (magnetite ± bornite ± chalcopyrite), A (quartz + magnetite), and AB (quartz + magnetite + chalcopyrite ± pyrite) veins. These veins were mainly formed in the potassic alteration zone. The intermediate stage is characterized by B (quartz + chalcopyrite + pyrite) and C (chalcopyrite ± pyrite) veins and mainly associated with the chlorite‐sericite and sericite alteration zones. The late stage is mainly associated with D (calcite + gypsum + quartz + pyrite ± chalcopyrite ± sphalerite ± galena) veins with sericite‐chlorite alteration halo. Petrography and electron microprobe analyses indicate that calcite mainly replaced Ca‐rich plagioclase. Fluid inclusion petrography and Raman spectroscopy revealed that monophase vapor inclusions, as well as two‐phase (V + L) and multiphase (V + S + L) fluid inclusions contain CO2 gas. The potassic alteration with significant amounts of calcite is indicative of CO2‐rich fluids, which is uncommon in other porphyry Cu‐Au deposits. On the basis of textural and fluid inclusion analyses, calcite formed by a reaction between Ca‐rich plagioclase and CO2‐rich hydrothermal fluids. The CO2 in the hydrothermal fluids of the HLE prospect was likely derived from the magma.

Corrosive Influence of Carbon Dioxide on Crack Initiation in Quartz: Comparison With Liquid Water and Vacuum Environments

AbstractThe stimulation of crack growth in quartz and siliceous materials by injecting carbon dioxide (CO2) represents a key technology in long‐term carbon storage and in the development of natural gas wells. While this technology is widely used, the molecular impact of CO2 interactions on the solid matrix is only incompletely understood. In this work, we employ reactive molecular dynamics simulations to study how the CO2 fluid environment affects the mechanical properties of pre‐cracked single‐crystal quartz. The thermodynamic conditions of interest are those relevant to subsurface reservoirs. We report how structural properties of quartz—bond length distribution and crack tip shape—evolve upon introduction of a fluid. These properties are directly related to macroscopic quantities of the global stress–strain curves, thus reaffirming the inherent coupling across multiple scales for fluid–solid interactions in the subsurface. We find that CO2 reduces the fracture toughness of quartz by 12.1% compared to that of quartz in vacuum, thereby promoting crack growth and enhancing fluid transport in the subsurface.

The impact of geological heterogeneity on coupled CO2 storage and geothermal extraction in inclined reservoirs

CO2 plume geothermal (CPG) production is an emerging CO2 utilization approach coupled with CO2 geological sequestration. Geological heterogeneity plays an important role in CO2 fluid and heat flow in the formation. Although the impact of heterogeneity has been investigated during CO2 injection for many sequestration projects, few studies have been reported for CO2-circulation and associated heat extraction. This study aims to numerically assess the impact of spatially correlated heterogeneity on both CO2 plume development (CPD) and subsequential CPG operations in inclined and thinly layered geothermal reservoirs. The simulated field is simplified from a typical depleted oil/gas reservoir block located in a potential geothermal area in North Oman, which had undergone horizontal water flooding as the second oil recovery phase. Formation slope and heterogeneity properties, including variance, azimuth, and correlation lengths, are sampled using the Latin-Hypercube approach in a high dimensional parameter space defined by their ranges. A suite of numerical models simulating CPD-CPG operations by a horizontal well doublet is set up using the slope and heterogeneity parameter samples. Performance metrics for CPD-CPG, including CPD time, CPG time, net injected CO2, maximum pressure decline, minimum CO2 mass fraction in produced fluids, total recovered heat energy, and heat extraction rate, are calculated from each of the numerical models. A response surface model mapping the input (slope and heterogeneity parameters) and output (performance metrics) is developed using these model results. Using the response surface, global sensitivity analysis is efficiently conducted to quantitatively evaluate the impact of slope and heterogeneity on the performance of CPD-CPG operations. It is found that steep slopes can enhance CO2 injectivity, facilitate high CO2 fraction in produced fluids and heat extraction rate; However, it causes early cold CO2 breakthrough to the production well and reduce total recovered heat energy. High variance and x-correlation length of heterogeneous fields create prominent high-permeable preferential paths in the major flow direction (x-axis). Low-permeable lenses created by large y-correlation lengths are perpendicular to the x-axis, acting as flow barriers to both CO2 and brine towards the production well. As for z-correlation length, 15 m is found to be the critical value relative to 20 m of the reservoir thickness. Large z-continuity scale facilitates fluid flow owing to the thick preferential paths when it is below 15 m, but low-permeable lenses tend to significantly block flow as they approximate to the reservoir thickness.