H2O CO2 Research Articles

Gold Mineralization at the Syenite-Hosted Anwangshan Gold Deposit, Western Qinling Orogen, Central China

The Anwangshan gold deposit is located in the northwestern part of the Fengtai Basin, Western Qinling Orogen (WQO). The gold ore is hosted within quartz syenite and its contact zone. The U–Pb weighted mean age of the quartz syenite is 231 ± 1.8 Ma. It is characterized by high potassium (K2O = 10.13%, K2O/Na2O > 1) and high magnesium (Mg# = 55.31 to 72.78) content, enriched in large ion lithophile elements (Th, U, and Ba) and light rare earth elements (LREE), with a typical “TNT” (Ti, Nb, and Ta) deficiency. The geochemical features and Hf isotope compositions (εHf(t) = −6.68 to +2.25) suggest that the quartz syenite would form from partial melting of an enriched lithospheric mantle under an extensional setting. Three generations of gold mineralization have been identified, including the quartz–sericite–pyrite (Py1) stage I, the quartz–pyrite (Py2)–polymetallic sulfide–early calcite stage II, and the epidote–late calcite stage III. In situ sulfur isotope analysis of pyrite shows that Py1 (δ34S = −1.1 to +3.8‰) possesses mantle sulfur characteristics. However, Py2 has totally different δ34S (+5.1 to +6.7‰), which lies between the typical orogenic gold deposits in the WQO (δ34S = +8 to +12‰) and mantle sulfur. This suggests a mixed source of metamorphosed sediments and magmatic sulfur during stage II gold mineralization. The fluid inclusions in auriferous quartz have three different types, including the liquid-rich phase type, pure (gas or liquid)-phase type, and daughter-minerals-bearing phase type. Multiple-stage fluid inclusions indicate that the ore fluids are medium-temperature (concentrated at 220 to 270 °C), medium-salinity (7.85 to 13.80% NaCleq) CO2–H2O–NaCl systems. The salinity is quite different from typical orogenic gold deposits in WQO and worldwide, and this is more likely to be a mixture of magmatic and metamorphic fluids as well. In summary, the quartz syenite should have not only a spatio-temporal but also a genetical relationship with the Anwangshan gold deposit. It could provide most of the gold and ore fluids at the first stage, with metamorphic fluids and/or gold joining in during the later stages.

Experimental constraints on serpentinite carbonation in the presence of a H2O–CO2–NaCl fluid

Serpentinite carbonation contributes to the deep carbon (C) cycle. Recently, geophysical and numerical studies have inferred considerable hydrothermal alteration in plate bending faults, opening the possibility of significant C storage in the slab mantle. However, there is a lack of quantitative determination of C uptake in serpentinized mantle rocks. Here, we experimentally constrain serpentinite carbonation in H2O–CO2–NaCl fluids to estimate C uptake in hydrated mantle rocks. We find that serpentinite carbonation results in the formation of talc and magnesite along the serpentinite surface. The presence of porous reaction zones (49.2% porosity) promotes the progress of carbonation reactions through a continuous supply of CO2-bearing fluids to the reaction front. Added NaCl effectively decreases the serpentinite carbonation efficiency, particularly at low salinities (< 5.0 wt%), which is likely attributed to the reduction in fluid pH and the transport rate of reactants, and the increase in magnesite solubility. Based on previous and our experiments, we fit an empirical equation for the reaction rate of serpentinite carbonation. Extrapolation of this equation to depths of plate bending fault systems suggests that serpentinite carbonation may contribute to an influx of up to 7.3–28.5 Mt C/yr in subduction zones. Our results provide new insights into serpentinite carbonation in environments with high fluid salinities and potentially contribute to the understanding of the C cycle in subduction zones.

Dynamic evolution of the transcrustal plumbing system in Large Igneous Provinces: Geochemical and microstructural insights from glomerocrysts and melt inclusions

Abstract The nature of the magma plumbing system of Large Igneous Provinces is still poorly understood. Among these exceptional magmatic events from Earth’s past, the end-Triassic Central Atlantic Magmatic Province (CAMP) and the end-Cretaceous Deccan Traps (Deccan) coincided in time with two of the most catastrophic biotic crises during the Phanerozoic. In order to constrain the architecture of their magma plumbing system, glomerocrysts containing abundant bubble-bearing melt inclusions from basaltic lava flows of both CAMP and Deccan were investigated via in situ geochemical and microstructural analyses. The analysed glomerocrysts, dominated by augitic clinopyroxene crystals, represent fragments of a crystal mush entrained by basaltic magmas before eruption. The analysed melt inclusions, consisting of an intermediate to felsic composition glass and CO2-bearing bubbles, represent relics of interstitial melts and fluids within a porous crystal framework forming the crystal mush. The different volume proportions between bubbles and whole inclusions reveal that melt entrapment occurred after volatile exsolution. The minimum observed bubble/inclusion fraction indicates that the CO2 concentration in CAMP and Deccan melts was at least 0.3 wt.%, consistent with a maximum entrapment pressure of about 0.5 GPa at CO2–H2O fluid-saturated conditions. The MgO-rich composition of host clinopyroxene crystals and whole rocks is in contrast with the SiO2-rich composition of (trachy-) andesitic to rhyolitic glass of melt inclusions, pointing to disequilibrium conditions. Thermodynamic and geochemical modelling shows that fractional crystallization alone cannot explain the evolved composition of glass in melt inclusions starting from their whole rock composition. On one side, the oxygen isotope composition of clinopyroxene crystals in glomerocrysts ranges from + 3.9 (± 0.3) to + 5.8 (± 0.3) ‰ and their sample-averaged oxygen isotope composition spans from + 4.4 (N = 10) to + 5.6 (N = 10) ‰, implying that glomerocrysts crystallized from mafic melts with normal (i.e., mantle-like) to slightly low δ18O values. On the other side, the oxygen isotope composition of glass in melt inclusions ranges from + 5.5 (± 0.4) to + 22.1 (± 0.4) ‰, implying that melt inclusions entrapped intermediate to felsic melts with normal (i.e., mantle-like) to extremely high δ18O values, typical of (meta-) sedimentary rocks. Some melt inclusions are compatible with fractionation from the same mafic melts that crystallized their host mineral phase, but most melt inclusions are compatible with variable degrees of crustal assimilation and partial mixing, potentially followed by minor post-entrapment isotope re-equilibration. In the CAMP, where sedimentary basins are abundant, (meta-) pelites and occasionally granitoids were the most likely assimilants. On the contrary, in the Deccan, where sedimentary basins are rare, granitoids and metapelites were the most likely assimilants. Oxygen isotope compositions of glass in melt inclusions, spanning from mantle-like to crust-dominated signatures, suggest that the CO2 within their coexisting bubbles likely derived partly from the mantle and partly from assimilated crustal materials. The investigated glomerocrysts and their bubble-bearing melt inclusions are relics of a multiphase (i.e., solid + liquid + gas phases) crystal mush revealing a dynamic evolution for the magma plumbing system of both CAMP and Deccan, where crystals, silicate melts and exsolved fluids coexisted and interacted through most of the transcrustal section.

Photothermal Synergistic Effect Induces Bimetallic Cooperation to Modulate Product Selectivity of CO2 Reduction on Different CeO2 Crystal Facets

AbstractProduct selectivity of solar‐driven CO2 reduction and H2O oxidation reactions has been successfully controlled by tuning the spatial distance between Pt/Au bimetallic active sites on different crystal facets of CeO2 catalysts. The replacement depth of Ce atoms by monatomic Pt determines the distance between bimetallic sites, while Au clusters are deposited on the surface. This space configuration creates a favourable microenvironment for the migration of active hydrogen species (*H). The *H is generated via the activation of H2O on monatomic Pt sites and migrate towards Au clusters with a strong capacity for CO2 adsorption. Under concentrated solar irradiation, selectivity of the (100) facet towards CO is 100 %, and the selectivity of the (110) and (111) facets towards CH4 is 33.5 % and 97.6 %, respectively. Notably, the CH4 yield on the (111) facet is as high as 369.4 μmol/g/h, and the solar‐to‐chemical energy efficiency of 0.23 % is 33.8 times higher than that under non‐concentrated solar irradiation. The impacts of high‐density flux photon and thermal effects on carriers and *H migration at the microscale are comprehensively discussed. This study provides a new avenue for tuning the spatial distance between active sites to achieve optimal product selectivity.

Fluid evolution and genesis of the Shipenggou gold deposit in Central Jilin Province, China: Constraints from C–H–O and in–situ sulphur isotopes of pyrite and fluid inclusions

The origin and evolution of the Shipenggou gold deposit in the Shipenggou–Jiapigou–Jinchengdong (SJJ) gold belt in Jilin Province, Northeast China, remain poorly understood. In this study, fluid inclusion and C–H–O–S isotopes from the Shipenggou deposit were investigated to clarify the fluid evolution and mineralisation process. The gold mineralisation is hosted in the biotite plagiogneiss of the Archaean Sandaogou Formation and is dominated by gold–bearing quartz veins. The orebodies are controlled by NNE– and NEE–striking brittle–ductile structures. Four stages of mineralisation have been identified: (I) milky quartz–minor pyrite, (II) quartz–pyrite–minor gold, (III) gold–quartz–polymetallic sulphide, and (IV) quartz–carbonate. Fluid inclusions were identified as four types: aqueous (VL–type), CO2–bearing (CL–type), CO2–rich (LC–type), and carbonic (PC–type). VL–, CL–, LC–, and PC–type FIs were developed within quartz from Stages I–II. Stage III quartz contains both CL– and VL–type FIs. Only VL–type FIs were observed in calcite from Stage IV. The total homogenisation temperatures (Tht) of FIs in Stages I, II, III, and IV are of 281.5–324.8, 215.5–269.1, 151.2–198.3, and 125.4–149.5 °C with salinities of 2.8–13.2, 2.8–9.6, 3.2–8.4, and 3.0–5.9 wt% NaCl eqv. Laser Raman spectroscopy analysis indicated the CL– and PC–type FIs from Stages I and II contain CO2 and minor quantities of CH4. The ore–forming fluids have developed from a medium temperature, low–medium salinity immiscible NaCl–H2O–CO2 ± CH4 system to a low temperature, low salinity homogeneous NaCl–H2O system. The HO isotopic compositions indicate that the initial ore–forming fluids were mantle–derived magmatic water. Subsequently, the ore–forming fluids were gradually joined by meteoric water. δ13C values indicate C in the fluids have originated from organic matter. Organic matter may have originated from the mantle, which mixed crust materials influenced by the subduction of the Palaeo–Pacific slab. In–situ, S isotope data of pyrite indicate that the origin of sulphur at the Shipenggou deposit is the mantle containing a crust component. Based on the above analysis results, the Shipenggou gold deposit is a mesothermal magma-hydrothermal vein–type gold deposit.

Fluid inclusion and pyrite geochemistry of the Jiapigou gold deposit, North China Craton: Implication for origin of orogenic gold deposit?

The Jiapigou auriferous belt in Jilin province has been recognized as substantial gold-producers in the North China Craton (NCC). Gold mineralization in this district mainly occurs in mineralized quartz veins and alteration zones, characterized by silicification, pyritization, and argillitization. The quartz veins contain three generations of mineralized quartz, namely, qtz1 (probably oldest), qtz2 (slightly younger), and qtz3 (probably youngest) were identified using SEM-CL. The fluid inclusions in all three generations of quartz are broadly of three types, viz., bi-phase Ia (H2O-CO2), tri-phase Ib (H2O-CO2-NaCl ± CH4), and II (H2O-NaCl).The micro-thermometric analysis of the type Ia and Ib fluid inclusion in qtz1 & qtz2 have aqueous-carbonic composition and exhibit a similar salinity of 1.1 to 7.8 wt% NaCl equivalent, whereas the homogenization temperature (Th) range varies from ∼237 to ∼350 °C. These ore-related fluid inclusions are of low to moderate salinity, and show mixture of CO2 and CH4. On the other hand, Type II fluid inclusions are dominant in qtz3. They have salinity of 3.2 to 12.7 wt% NaCl equivalent and homogenization temperature varying between 180 °C and 210 °C. These data indicate that the ore-forming fluid evolved from a CO2–H2O–NaCl ± CH4 system during the mineralization period.The X-ray elemental maps of pyrite acquired using electron microprobe analysis (EPMA) show irregular zones of Co and Ni indicating two generations of pyrite. The early-stage pyrite which occupies core portion shows high Co and Ni, whereas the later-stage pyrite occupying rim has lower Co and Ni. The laser ablation-inductively coupled plasma-mass spectrometer (LA-ICPMS) analyses of pyrite has indicated that pyrite-1 is rich in Au + Ag + Se + Cu + Co + Ni, whereas, pyrite-2 has lower concentration of these elements. A positive correlation between Fe and other chalcophile elements reported here (i.e. Au + Ag + Se + Cu + Co + Ni), might be due to fluid-rock interaction resulting into a saturated fluid that subsequently precipitated along the microfractures within earlier-formed pyrite and quartz. The in-situ δ34S values in pyrite from Jiapigou deposits overlap in the range of +4.5 to +9.6 ‰, which is consistent with the ore-forming fluids of the crustal origin input during fluid-rock interaction. The systematic pyrite compositional observations and fluid inclusions study documented here to provide new insight into the process of ore formation for the Au enrichment in the Jiapigou deposit

Formation path and kinetics of caking components from modified lignite in subcritical H2O–CO system

ABSTRACT Modification reaction of lignite in subcritical H2O–CO system can significantly increase its caking index to more than 90. Separating and extracting the caking components from modified lignite, exploring the formation path of caking components, and establishing a kinetic model for the generation of these components are of significant importance for lignite hydrogenation reaction control. The lignite modified reaction was carried out in subcritical D2O–CO systems using the isotope tracer method. The formation path of caking components was defined by solvent extraction–IRMS–GPC combination technology. The results show that the soluble substances of tetrahydrofuran (TS) and benzene (BS) are the main caking components causing the structural transformation of lignite (A). The separation of n-hexane soluble (NS) also has an effect on the caking index of the modified coal. In the hydrogenation caking component formation stage, the lignite pyrolysis fragments combine with active hydrogen generated by water gas shift reaction to form caking substances, that is, A → TS + BS + NS. The formation activation energy of caking components is in the range of 0.39–58.24 kJ/mol. In the polycondensation caking component conversion stage, three soluble substances are converted in the order of TS → BS → NS, and the activation energy for the formation of caking components is 31.710–57.616 kJ/mol.

The precipitation mechanisms of scheelite from CO2-rich hydrothermal fluids: Insight from thermodynamic modeling

Scheelite and wolframite are two main tungsten-bearing ore minerals in tungsten deposits. Compared to wolframite formed mostly by NaCl–H2O fluids, scheelite in many but not all tungsten deposits is associated with CO2–bearing hydrothermal fluids, but its precipitation mechanisms from these fluids are poorly understood. The replacement of wolframite by scheelite is common among tungsten deposits where these two tungstates coexist, but how CO2, as the pH-buffering agent, affects their replacement remains unclear. To answer these questions, we first tested the pH-buffering effect of CO2 by comparing available experimental pH values of H2O–CO2±NaCl solutions at 200–280 °C and the corresponding thermodynamic modeling results. The mean absolute errors between the calculated and experimental pH values are 0.14 log units in H2O–CO2 solutions and 0.13 log units in H2O–CO2–NaCl solutions, indicating that the calculated acitivities of H+ in CO2-bearing solutions are reliable. Then, the solubilities of scheelite, scheelite-ferberite, and scheelite-hübnerite in NaCl–H2O–CO2 systems were modeled in this study. Our modeling results suggest that scheelite solubility in CO2-rich fluids is highly dependent on fluid pressure but is insensitive to fluid temperature. A decrease in fluid pressure from lithostatic to hydrostatic levels at a depth of 3–8 km causes CO2 escape and pH rise and precipitates over 70 % of tungsten contents in fluids on average. Therefore, CO2 escape is an efficient mechanism for precipitating scheelite from CO2–rich hydrothermal fluids. The independence of scheelite solubility on temperature at high pressures and the slightly retrograde solubility at low pressures allows CO2–rich hydrothermal fluids to carry a great amount of tungsten far away from its sources. This may be one of reasons why some scheelite deposits occur at greater distances (>500 m) from the granite or extend along its strike for several kilometers. Similar to the cases in NaCl–H2O systems, two mechanisms for scheelite replacing wolframite in CO2–rich fluids are identified, a single decrease in fluid pressure or simple cooling plus an increase in the ratios of total Ca contents to total Fe (or Mn) contents in fluids.

Genesis and fluid evolution of the Hatu orogenic gold deposit in the West Junggar, Western China

The West Junggar in Xinjiang, western China, represents a significant gold mineralization belt hosting over 200 gold deposits, with the Hatu gold deposit being the largest among them. In this study, ore geology and fluid inclusion assemblages of quartz samples from the Hatu gold deposit were investigated in an effort to clarify the mineralization process and its relationship with the geodynamic settings. The mineralization process is delineated into early (pyrite-albite-quartz veins), middle-a (quartz-ankerite veins), middle-b (quartz-ankerite-sulfide-native gold veins), and late (quartz-calcite veins) stages. The early stage veins suggest a compressional setting while the middle-a and middle-b stage veins suggest a tensional shear setting. The late stage veins are typically filled fissures cutting through earlier veins. Scanning electron microscope-cathodoluminescence (SEM-CL) reveals that early stage quartz (Q1) exhibits concentric CL-oscillatory growth zoning, while middle-a stage quartz (Q2a) displays unidirectional zoning and ranges from CL-bright to CL-dark, middle-b stage quartz (Q2b) is CL-bright and weakly zoned, and late-stage euhedral quartz (Q3) shows sector zoning transitioning from CL-gray to CL-dark. Quartz that formed in these stages developed three types of fluid inclusions: pure CO2 (PC-type), CO2–H2O (C-type), and H2O–NaCl (W-type). The early stage quartz contains C- and W-type fluid inclusions homogenizing at 309–345 °C, while the late stage quartz contains only W-type fluid inclusions with homogenization temperatures of 164–229 °C. Microthermometry of fluid inclusion indicated the evolutionary of the metallogenic fluid from a high-temperature, CO2-rich, and minor CH4 metamorphic fluid to a low-temperature, CO2-poor meteoric fluid. From the early to middle-a stages, fluid boiling caused the unloading of ore-forming elements whereas fluid mixing led to the precipitation of polymetallic sulfides and gold in the middle-b stage. Trapping pressures in the middle-b stage were estimated using C-type inclusions, illustrating that gold mineralization took placed at depth of 8.0 km. We propose classifying the Hatu gold deposit as an orogenic deposit, originating from the collisional orogenesis between the Yili-Kazakhstan and Siberian continents in the Late Carboniferous.

Coupling monoclinic Pb2(CrO4)O with Mn3O4 quantum dots as oxygen vacancies-rich S-scheme photocatalysts for visible-light-driven photocatalytic CO2 reduction with H2O

Simulating natural photosynthesis to convert CO2 and H2O into fuels achieving overall reaction is a promising solution for addressing environmental problems and energy crises. Constructing an S-scheme catalyst of two or more catalytic sites with rapid electron transfer and strong redox capability may be an effective strategy for coupling photocatalytic CO2 reduction and H2O oxidation. Here, an oxygen vacancies-rich S-scheme semiconductor photocatalyst composed of monoclinic lead chromate oxide (Pb2(CrO4)O) coupled with Mn3O4 quantum dots (QDs) (Pb2(CrO4)O@Mn3O4QDs) are synthesized and tested for photoconversion of CO2 with H2O under visible light. Through the integration of Pb2(CrO4)O with Mn3O4QDs, the photocatalytic C1-evolution rate on Pb2(CrO4)O@Mn3O4QDs is radically increased by 6.0 and 8.1 times, which is much faster than that of pristine Pb2(CrO4)O and Mn3O4. The origin of the greatly raised activity is revealed by advanced characterizations, and in situ X-ray photoelectron spectroscopy (XPS) confirms the electron transport pathway in Pb2(CrO4)O@Mn3O4QDs with light illumination, unveiling the efficient spatial separation/transfer of charge carriers in oxygen vacancies-rich Pb2(CrO4)O@Mn3O4QDs S-scheme heterojunction. Consequently, powerful photoelectrons and holes accumulate in the Mn3O4 conduction band and Pb2(CrO4)O valence band, respectively, exhibiting prolonged long lifetimes and facilitating their involvement in CO2 photoreduction and H2O photooxidation through altering the interfacial charge dynamics.

Application of High‐ and Low‐Reactivity Cokes in Hydrogen‐Rich Blast Furnaces

The effects of two cokes with different reactivity on the lump ore's metallurgical properties and coke's solution loss are investigated under the high‐temperature load reduction. The work used an improved test device for softening‐melting and dropping characteristics of iron ores in both CO2 and CO2H2O atmospheres. The deterioration behavior of highly reactive cokes is expounded under hydrogen‐rich conditions. High‐reactivity cokes under hydrogen‐rich conditions are more favorable for enhancing the breathability of charge and the penetration of the coke layer. However, it increased the thickness of the softening zone. High‐reactivity cokes had obvious internal and external reaction gradients. The solution loss reaction mostly occurred on the surface, with selectivity. The longitudinal stacking height, layer number, and order degree in the carbon structure decreases after the reaction. The carbon‐structure difference weakens between the shell and core. The enhancement of coke's reactivity, however, results in the significant loss of coke powders on its surface. Unreduced FeO and refractory Fe2SiO4 are more likely to appear in the droplets, which is not conducive to the reduction of Fe and the generation of slag crust in the furnace. The difficulty in separating lump ores and cokes is aggravated, and more iron‐containing charge remain in the furnace.

M/BiOCl-(M=Pt, Pd, and Au) Boosted Selective Photocatalytic CO2 Reduction to C2 Hydrocarbons via *CHO Intermediate Manipulation.

Selective CO2 photoreduction to C2 hydrocarbons is significant but limited by the inadequate adsorption strength of the reaction intermediates and low efficiency of proton transfer. Herein, an ameliorative *CO adsorption and H2O activation strategy is realized via decorating bismuth oxychloride (BiOCl) nanostructures with different metal (Pt, Pd, and Au) species. Experimental and theoretical calculation results reveal that distinct *CO binding energies and *H acquisition abilities of the metal cocatalysts mediate the CO2 reduction activity and hydrocarbon selectivity. The relatively moderate *CO adsorption and *H supply over Pd/BiOCl endows it with the lowest free energy to generate *CHO, leading to its highest activity of hydrocarbon production. Specifically, the Pt cocatalyst can efficiently participate in H2O dissociation to deliver more *H for facilitating the protonation of the *CHO and *CHOH, thereby favoring CH4 production with 76.51% selectivity. A lower *H supply over Pd/BiOCl and Au/BiOCl results in a large energy barrier for *CHO or *CHOH protonation and thus a more thermodynamically favored OC─CHO coupling pathway, which endows them with vastly increased C2 hydrocarbon selectivity of 81.21% and 92.81%, respectively. The understanding of efficient C2 hydrocarbon production in this study sheds light on how materials can be engineered for photocatalytic CO2 reduction.

Construction of An Artificial Photosynthesis System with A Single CdS QDs-Ferritin Hybrid Molecule.

Establishing artificial photosynthesis systems in a simple but effective manner to mitigate the greenhouse effect and address the energy crisis remains challenging. The combination of photocatalysis technology with bioengineering is an emerging field with great potential to construct such artificial photosynthesis systems, but so far, it has barely been explored in this area. Herein, an artificial photocatalysis platform is constructed with high CO2 conversion and H2O splitting capability by integration of CdS QDs into the intra-subunit interface of H-type ferritin (Marsupenaeus japonicus), a natural ferroxidase through protein interface redesign. The crystal structure of the synthesized CdS QDs with engineered ferritin molecules as bio-templates confirmed the design at an atomic level. Notably, upon absorbing desirable visible light (≈420nm), such a single CdS-ferritin hybrid molecule is able to selectively catalyze the reduction of CO2 into HCOOH (≈90%), meanwhile catalyzing the oxidation of H2O into O2 in an aqueous environment. The O2 production rate reached to 180µmolg-1h-1, and the HCOOH output hit almost 800µmolg-1h-1. This work advances the utilization of the four-helix bundle structure for crafting artificial photosynthesis systems, facilitating the seamless integration of bioengineering and photocatalysis technology.

Advanced visualisation of biomass charcoal combustion dynamics using MWIR hyperspectral and LWIR thermal imaging under varied airflow conditions

Biomass charcoal combustion is a complex process, significantly influenced by various operating parameters. Among these parameters, air supply emerges as a critical factor affecting combustion efficiency, gas emissions, and thermal dynamics. In this study, we explored these complex interdependencies using a novel combination of mid-wavelength infrared (MWIR) hyperspectral imaging and long-wavelength infrared (LWIR) thermal imaging, under different airflow rates. Our findings demonstrated that while increased airflow accelerated the overall combustion rate, it simultaneously decreased combustion efficiency. Specifically, the thermal profiles showed an increased surface temperature at a low flowrate (0.5 L/min) while decreasing in temperature with higher flowrates. The decreased system temperature led to a lower combustion efficiency because of the reduced conversion rate from combustible gases (CH4 and CO) into CO2 and H2O. Additionally, the results also demonstrated that cooling effects of the high flowrates primarily impeded the solid-phase combustion stage. This is further corroborated by the temporal and spatial variation in the emissions of key gas species (H2O vapor, CH4, CO, and CO2) observed through hyperspectral imaging. The emission evolution of these gases displayed the different stages of the gas-phase and solid-phase combustion. The spatial distribution of the trace gases showed a decreased distribution radius due to the enhanced diffusion to the fuel surface when the airflow increases, aligning well with the two-film model established in the literature. Furthermore, we utilised spectral radiance ratios (CO/CO2, CH4/CO2, H2O/CO2) to gain additional insights into the combustion dynamics. These ratios evidenced the decrease in combustion efficiency at high airflow rates. Finally, the increased H2O/CO2 ratio further demonstrated the impeded char combustion and a shift towards pyrolysis at higher airflow rates because of the decreased thermal equilibrium of the system. The findings from this study provide critical insights into the dynamics of biomass charcoal combustion and illuminates the path for optimising energy efficiency and assessing the environmental implications from burning biomass fuels.

Amphiphilic heterojunctions with atomically dispersed copper–alkynyl active units for highly efficient CO2 photoreduction

The efficiency of CO2 photoreduction is limited by slow charge kinetics and the mass transfer of hydrophobic CO2 and H2O over the photocatalyst. Herein, we present a copper–alkynyl bond coordination polymer (CA-CP) with atomically-dispersed copper–alkynyl units (ADCAUs). By incorporating hydrophobic CA-CP with hydrophilic iodine vacancy-rich bismuth oxyhalides (IV-BX), we construct amphiphilic heterojunction photocatalysts (CA-CP/IV-BX) for visible-light-driven CO2 photoreduction. CA-CP/IV-BX achieves excellent stability, 100 % CO selectivity and a CO-evolution rate of 157.6 μmol g−1 h−1 coupled with O2 releasing. Experimental and theoretical calculations elucidate that the ADCAUs favor adsorption and activation of CO2, and have high CO selectivity. Moreover, the amphiphilic janus structure not only ensures the spatial synergy effect of CO2 reduction and H2O oxidation, but also promotes charge separation and proton feeding, boosting CO2 photoreduction activity. This work develops Cu–alkynyl coordination polymer photocatalysts with ADCAUs and provides insights into hydrophobic–hydrophilic biphasic photocatalysts for synergistic CO2 reduction and H2O oxidation.

Unambiguous detection of mesospheric CO2 clouds on Mars using 2.7 μm absorption band from the ACS/TGO solar occultations

Mesospheric CO2 clouds are one of two types of carbon dioxide clouds known on Mars. We present observations of mesospheric CO2 clouds made by Atmospheric Chemistry Suite (ACS) onboard the ESA-Roscosmos ExoMars Trace Gas Orbiter (TGO). We analyzed 1663 solar occultation sessions of Thermal InfraRed (TIRVIM) and Middle InfraRed (MIR) channels of ACS covering more than two Martian years that contain spectra of 2.7 μm carbon dioxide ice absorption band. That allowed us to unambiguously discriminate carbon dioxide ice aerosols from mineral dust and water ice aerosols, not relying on the information of atmospheric thermal conditions. CO2 clouds were detected in eleven solar occultation observations at altitudes from 39 km to 90 km. In five cases, there were two or three layers of CO2 clouds that were vertically separated by 5–15 km gaps. Effective radius of CO2 aerosol particles is in the range of 0.1–2.2 μm. Spectra produced by the smallest particles indicate a need for a better resolved CO2 ice refractive index. Nadir optical depth of CO2 clouds is in the range 5 × 10−4–4 × 10−2 at both 2.7 μm and 0.8 μm. Asymmetrical diurnal distribution of detections observed by ACS is potentially due to local time variations of temperature induced by thermal tides. Two out of five cases of carbon dioxide cloud detections made by the TIRVIM instrument reveal the simultaneous presence of CO2 ice and H2O ice aerosols. Temperature profiles measured by the Near InfraRed (NIR) channel of ACS are used to calculate CO2 saturation ratio S at locations of carbon dioxide clouds. Supersaturation S > 1 is detected in only 6 out of 19 cases of CO2 cloud layers; extremely low values of S < 0.1 are found in 9 out of 19 cases.

Experiments and modeling of solid oxide co-electrolysis: Occurrence of CO2 electrolysis and safe operating conditions

Solid Oxide Electrolysis Cell (SOEC) has attracted considerable attention for its potential scalability and high energy conversion efficiency. It is capable of electrolyzing both H2O and CO2 simultaneously, generating syngas that can be further synthesized into carbon-based fuels, which are good energy carriers for long-term energy storage. However, despite its promise, the understanding of the reaction mechanism crucial for extending cell longevity remains incomplete, and concerns persist regarding carbon deposition during co-electrolysis. A dual approach, combining experiments and Multiphysics simulations was adopted to explore the reaction mechanism and carbon deposition risk across a wide range of operating conditions on industrial-size cells. Both experimental observations and simulation results indicate that CO2 electrolysis and carbon deposition are significantly influenced by the inlet water content and flow rates at the fuel electrode. Increasing the inlet H2O concentration and fuel electrode flow rates lead to CO2 electrolysis occurring at higher current densities. Also, carbon deposition, which was found at the interface of fuel electrode and electrolyte, can be mitigated by controlling the conversion rate relative to the inlet H2O content and by increasing the flow rate at the fuel electrode. Additionally, the current density distribution of H2O electrolysis and CO2 electrolysis across the cell were also investigated. The obtained insights hold significance for the practical operation of SOEC co-electrolysis.

SAFT2 equation of state for the CH4–CO2–H2O–NaCl quaternary system with applications to CO2 storage in depleted gas reservoirs

Understanding the phase equilibria and physical-chemical characteristics of the CH4–CO2–H2O–NaCl quaternary system is important for evaluating costs and risks for the storage of CO2 in depleted natural gas reservoirs as well as fluid inclusion studies. In this study, phase equilibria and thermodynamic properties of this system were investigated through the utilization of a statistical association fluid theory-based (SAFT) equation of state (EOS) at temperatures from 298 to 513 K (25–240 °C), pressures up to 600 bar (60 MPa) and concentration of NaCl up to 6 mol/kgH2O. The model parameters were obtained from the fitting of available experimental data of subsystems (i.e., CH4–H2O, CH4–CO2, and CH4–H2O–NaCl) that were judged to be reliable and incorporation of available parameters for the subsystems (i.e., pure component, CO2–H2O, and CO2–H2O–NaCl). Using the SAFT EOS developed in this study, we predicted the solubility of (CH4 + CO2) gas mixtures in pure H2O and compared it with the available experimental data and the predicted values from four popular numerical simulators. The results indicate that our model can provide reliable predictions for the CH4–CO2–H2O ternary system. Subsequently, we further predicted the phase equilibria and density of the CH4–CO2–H2O–NaCl system with NaCl varying from 0 to 6 mol/kgH2O. We also employed the SAFT EOS to predict the solubility of CO2 and CH4 in the water-alternating-gas process for CO2-enhanced oil recovery, demonstrating good agreement with the simulation results obtained through the Peng-Robinson EOS for predicting the CO2 and CH4 solubility. These predicted thermodynamic properties and phase behaviors in the CH4–CO2–H2O–NaCl system provide quantitative insights into the implications of CO2 storage in depleted oil and gas reservoirs.

Supercritical CO2 and Subcritical H2O Analysis Instrument: Automated Lipid Analysis for In Situ Planetary Life Detection.

The search for extraterrestrial extant or extinct life in our Solar System will require highly capable instrumentation and methods for detecting low concentrations of biosignatures. This paper introduces the Supercritical CO2 and Subcritical H2O Analysis (SCHAN) instrument, a portable and automated system that integrates supercritical fluid extraction (SFE), supercritical fluid chromatography (SFC), and subcritical water extraction coupled with liquid chromatography. The instrument is compact and weighs 6.3 kg, making it suitable for spaceflight missions to planetary bodies. Traditional techniques, such as gas chromatography-mass spectrometry (MS), face challenges with involatile and thermally labile analytes, necessitating derivatization. The SCHAN instrument, however, eliminates the need for derivatization and cosolvents by utilizing neat supercritical CO2 with water as an additive. This SFE-SFC-MS method gives efficient lipid biosignature separations with median detection limits of 10 pg/g (ppt) for fatty acids and 50 pg/g (ppt) for sterols. Several free fatty acids and cholesterol were among the detected peaks in biologically lean samples from the Atacama Desert, demonstrating the instrument's potential for in situ life detection missions. The SCHAN instrument addresses the challenges of conventional systems, offering a compact, portable, and spaceflight-compatible tool for the analysis of organics for future astrobiology-focused missions.

Photothermal Synergistic Effect Induces Bimetallic Cooperation to Modulate Product Selectivity of CO2 Reduction on Different CeO2 Crystal Facets.

Product selectivity of solar-driven CO2 reduction and H2O oxidation reactions has been successfully controlled by tuning the spatial distance between Pt/Au bimetallic active sites on different crystal facets of CeO2 catalysts. The replacement depth of Ce atoms by monatomic Pt determines the distance between bimetallic sites, while Au clusters are deposited on the surface. This space configuration creates a favourable microenvironment for the migration of active hydrogen species (*H). The *H is generated via the activation of H2O on monatomic Pt sites and migrate towards Au clusters with a strong capacity for CO2 adsorption. Under concentrated solar irradiation, selectivity of the (100) facet towards CO is 100 %, and the selectivity of the (110) and (111) facets towards CH4 is 33.5 % and 97.6 %, respectively. Notably, the CH4 yield on the (111) facet is as high as 369.4 μmol/g/h, and the solar-to-chemical energy efficiency of 0.23 % is 33.8 times higher than that under non-concentrated solar irradiation. The impacts of high-density flux photon and thermal effects on carriers and *H migration at the microscale are comprehensively discussed. This study provides a new avenue for tuning the spatial distance between active sites to achieve optimal product selectivity.