CO2 Generation Research Articles

Seismic interpretation of the Mero Field igneous rocks and its implications for pre- and post-salt CO2 generation – Santos Basin, offshore Brazil

Understanding igneous rock emplacement is crucial for deciphering any sedimentary basin's evolution. Its occurrence can be a determining factor for elements of the petroleum system, such as hydrocarbon generation, migration, trap formation, and reservoir quality. The high-impedance nature of igneous rocks in relation to their surrounding host rocks renders amplitude anomaly-based attributes sufficient for the identification of igneous bodies within siliciclastic sequences. However, this is not necessarily valid in pre-salt settings because of the high-impedance carbonates that make the impedance contrast subtle. Furthermore, if the emplacement characterization of the various magmatic pulses that occur in a given area over geological time were better evaluated, it would be possible to assess the gases (such as CO2) they produce with higher reliability. In this paper, the principal geometric and petroelastic characteristics of the igneous rocks of the Mero Field are described in detail in order to estimate the thermogenic production of CO2. Both manual and semi-automatic seismic interpretation were carried out to quantitatively and properly reduce the uncertainties inherent to the seismic mapping of these rocks. Thus, a 3D probabilistic igneous facies classification was performed based on a Bayesian inference using the P- and S-impedance well log data available and seismic elastic inversion volumes. These volumes of occurrence probability were useful for semi-automatically extracting maps and geobodies, which, along with conventional manual seismic interpretation, provided hypothetical volumetric scenarios for Mero igneous rocks and also for CO2 production. Five main intrusive features were recognized based on mainly in seismic geometries found in the Mero Field, two of them being Lower Cretaceous rift-related magmatism synchronous with the pre-salt reservoir deposition and the other three being related to the Santonian/Campanian magmatism. The analyzed data suggests that deep intrusions were responsible for the installation of a multiple hydrothermal vent system in the Santos Basin. During pre-salt sedimentation in the Lower Cretaceous, the emplacement of tholeiitic sills, primarily in low-energy facies at structural depressions, may have played a significant role in the thermal alteration of the sedimentary framework and would have released a significant amount of CO2 into the atmosphere. It's possible that the reactivation and reuse of these older structures (i.e., sill-related hydrothermal vent complexes generated by tholeiitic intrusions) during alkaline Santonian/Campanian magmatism might have contributed further to the production of additional carbon dioxide, which would be trapped in pre-salt reservoirs in this instance.

Design of a Bioreactor for Aerobic Biodegradation of Biowaste Based on Insight into Its Composition and Estimated Process Parameters

Biowaste, which often accounts for more than 50% of municipal waste, is an environmental problem if disposed of improperly in landfills but has great potential to achieve the recycling targets set out in Directive (EU) 2018/851. Despite the knowledge in theory and practice about the processing of biowaste and the benefits of recycling, there is a lack of methodological approaches in describing the process of aerobic biodegradation in a concise and suitable way for decision makers, environmental engineers, and project designers. This paper presents how basic data on the properties of biowaste can be used, using theoretical models, to determine basic indicators of the dynamics and material balance of the process. The maximum rate of CO2 generation on the 4th day was Rm = 45.3 g/d, with the potential of available, readily biodegradable components of the biowaste sample of P = 526 g CO2/kg VS. A substrate conversion of 51.7% was achieved in the bioreactor by the 17th day of treatment. The results of this analysis, together with future analyses of sensitivity and boundary conditions of the process, are useful for rapidly sizing a biological treatment system for municipal solid waste in a given area.

Efficient adsorption separation of methane from C2–C3 hydrocarbons in a Co(II)-nodes metal–organic framework

Methane (CH4) as a substitute for other mineral fuels plays a crucial role in reducing energy consumption and preventing environmental pollution. The present study employs a solvothermal method to fabricate a porous framework Co-metal–organic framework (Co-MOF) containing two distinct secondary building units (SBUs): an anionic [Co2(μ2-OH)(COO)4(H2O)] and a neutral [CoN2(COO)2]. Notably, within the anionic SBUs, the coordinated water molecules induce the generation of divergent unsaturated Co(II) centers in the unidirectional porous channels, thereby creating open metal sites. The adsorption performance of Co-MOF towards pure component gases was systematically investigated. The results demonstrated that Co-MOF exhibits superior adsorption capacity for C2–C3 hydrocarbons compared to CH4, which offering the potential for efficient adsorption and separation of CH4 from C2–C3 hydrocarbons. The gas selectivity separation ratios of Co-MOF for C2H6/CH4 and C3H8/CH4 were calculated using the ideal adsorbed solution theory method at 273/298 K and 0.1 MPa. The results revealed that Co-MOF achieved remarkable equilibrium separation selectivity for CH4 and C2–C3 hydrocarbon gases among non-modified MOFs, signifying the potential of the synthesized Co-MOF for efficient recovery and purification of CH4 from C2–C3 hydrocarbons. Breakthrough experiments further demonstrate the ability of Co-MOF to purify methane from C2–C3 hydrocarbons in practical gas separation scenarios. Additionally, molecular simulation calculations further substantiate the propensity of anionic SBUs to interact with C2–C3 hydrocarbon compounds. This study provides a novel paradigm for the development of porous MOF materials in the application of gas mixture separation.

Reduced graphene oxide decorated two-dimensional FeSiCr nanosheets for improving flame-retardancy, electromagnetic wave absorption, and thermal conduction of ethylene vinyl acetate composites

Ball milling introduced graphene oxide onto FeSiCr, followed by radiation reduction to convert it to reduced graphene oxide (rGO). The materials, FeSiCr-rGO and FeSiCr-GO, were blended with Ethylene-Vinyl Acetate (EVA) to create composites. Compared to pure EVA, EVA/FeSiCr-rGO composites showed significant reductions in peak heat release rate (71.3 %), total heat release (33.0 %), and total smoke production (18.3 %). CO and CO2 generation rates decreased, enhancing overall fire resistance. FeSiCr-rGO significantly improved thermal conductivity with minimal impact on mechanical properties compared to FeSiCr-GO. In electromagnetic absorption, FeSiCr-rGO notably enhanced low-frequency and X-band absorption for EVA composites. At 2 mm thickness, EVA/FeSiCr-rGO achieved a maximum reflection loss of -24.8 dB in the X-band, surpassing FeSiCr and FeSiCr-GO. At 3 mm thickness, it effectively absorbed electromagnetic waves in the 6–8 GHz range.

Electric vehicles application - environmental justification

The transport sector is the second largest source of greenhouse gas pollution in terms of total carbon dioxide emissions in the European Union. Reducing emissions in transport is more expensive than in other sectors because transport is still heavily reliant on fossil fuels. For years, electric vehicles have played a prominent role in the transport sector in terms of solving the f harmful gas emissions problem. They have the potential to reduce CO2 emissions by offering an alternative to conventional vehicles based on internal combustion engines. Although they have zero CO2 emissions in the tailpipe, electric vehicles require the consumption of electricity to produce them as well as to power the battery, which contributes to the creation of CO2 emissions. The paper compares the use of a delivery vehicle with an internal combustion engine and an electric vehicle in the field of road transportation of the postal sector from the aspect of environmental sustainability. The electric vehicle use showed a lower generation of CO2 by 114.2 g/km, taking into account the average emission of carbon dioxide for electric vehicles according to the data of the European Union.

Porous C3N4 nanosheet supported Au single atoms as an efficient catalyst for enhanced photoreduction of CO2 to CO

Artificial photosynthesis utilizing solar energy to convert carbon dioxide (CO2) and water (H2O) into fuels and high-value chemicals offers a promising technology for mitigating energy consumption and environmental pollution. However, the development of efficient photocatalysts with high product selectivity remains a big challenge due to the sluggish dynamic transfer of photogenerated charge carriers. Herein, porous C3N4 nanosheet supported Au single atoms photocatalyst (Au1@CN) with AuN4 coordination is fabricated via a facile “impregnation + freeze-drying” process. The as-synthesized Au1@CN exhibits efficient and stable CO2 photoreduction activity with a CO evolution rate of 0.58 μmol h−1 (amount of catalyst: 10 mg), CO selectivity of 94 %, and a turnover frequency (TOF) of 10.0 h−1 using H2O as the reductant, which exceed most previous works on C3N4-based single-atom photocatalysts for CO2 reduction. Experimental studies and density functional theory (DFT) calculations reveal that the unique Au—N4 coordination promotes the dynamic transfer of photogenerated charge carriers, facilitates the adsorption/activation of CO2 molecules and generation of *COOH intermediate, thereby significantly enhancing the CO2 photoreduction activity with high CO selectivity. This study demonstrates an effective strategy for the design of M—N4 coordinated single-atom catalyst toward efficient and selective photoreduction of CO2 to CO.

Relationship between low-temperature oxidation activity and second-stage ignition delay: Experimental insights on n-pentanol / hydrogenated catalytic biodiesel blends

N-pentanol exhibits promising potential as a sustainable and eco-friendly biomass energy source. However, certain challenges such as ignition difficulty and unstable combustion exist. This study investigates the influence of low-temperature auto-ignition of n-pentanol/HCB (Hydrogenated Catalytic Biodiesel) blends on ignition and combustion characteristics and evaluates the correlation between low-temperature oxidation and second-stage ignition delay. Results show a linear positive correlation between the HCB content in n-pentanol and its low-temperature oxidation reactivity. The stronger the low-temperature oxidation activity of the blends, the shorter the second-stage ignition delay of blends. When the HCB content in blends is below 40 %, the low-temperature oxidation rate initially increases and then decreases. However, the low-temperature oxidation rate increases again when the HCB content exceeds 40 %. Moreover, the relationship between the initial CO2 generation rate and the HCB blending ratio follows an Exp exponential function under different critical compression ratios. Beyond 43.7 % HCB, an acceleration in the high-temperature combustion rate owing to an increase in the low-temperature oxidation rate again. In addition, the minimum ignition limit of n-pentanol/HCB blends was identified with 40 % HCB blends closely resembling diesel conditions and 50 % HCB blends showing a lower ignition limit, characterized by a critical temperature and pressure of 517.3 K and 8.66 bar, respectively. Furthermore, two distinct conditions for the minimum ignition boundary region of n-pentanol/HCB blends were defined, offering practical insights. In summary, a blend with a 50 % HCB ratio provides a promising solution for the low-temperature ignition and stable combustion of n-pentanol, addressing the challenges of simultaneous use in internal combustion engines.

Field Comparison of Carbon Dioxide Source with Biogents Sentinel-2 and Pro Traps for Adult Aedes Mosquito Surveillance.

The BG Sentinel-2 (BGS-2) and BG-Pro traps (BGS-2 configuration) were compared for their effectiveness to collect Aedes vectors and related nuisance mosquitoes in north central Florida during 2022. Traps were baited with either dry ice pellets, pressurized carbon dioxide (CO2) gas, or the novel BG yeast-derived CO2 generator. Additionally, each trap was fitted with the BG Sweetscent lure. Sixteen species were collected including Aedes albopictus and Ae. aegypti, which accounted for about 20% of the collections. The BGS-2 collected more mosquitoes compared to the BG-Pro, but the relative percent abundance of each species to total collection from each trap type was similar. Overall mosquito abundance was significantly greater in both trap types baited with dry ice compared with the other CO2 sources. Significantly more Ae. albopictus were collected from BGS-2 traps baited with dry ice than all other CO2 and trap configurations. Lastly, we did not observe any significant differences in Ae. aegypti abundance between trap type or CO2 source.

Exploring carbon dioxide generation in combustion of long-flame coal in Huating mining area by using ReaxFF MD

Coal combustion contributes to 44% of global fuel CO2 emissions. Until now, there has less effective means to study the generation mechanism of carbon dioxide. To approach the generation mechanism of CO2 in coal combustion process at atomic level, the structure information of long-flame coal from Huating mining area, Gansu, China was characterized by ultimate analysis, 13C NMR and XPS. According to these information, one new average structure model was established, its parameters are consistent with the experimental results. Then reactive force field (ReaxFF) molecular dynamics (MD) simulations in 2000–3500 K were performed. Four types of intermediates (Rn–O, Rn–CHO, Rn–CO2, and C2O2) that correspond to four generation routes of CO2 were obtained from the ReaxFF MD simulations. The intermediates can generate CO2 through attacks from oxygen-containing radicals or cleavage of the C–C bond. Rn–O and Rn–CHO can generate CO as intermediates. The oxidation route of acetylene, which first oxidised into C2O2 and then further oxidised into CO2, was analysed using density functional theory (DFT) calculations at the M062X/6–311** level. The DFT results demonstrate the precision of ReaxFF MD calculations. The results can improve the understanding of CO2 generation during coal combustion.

In situ copper faceting enables efficient CO2/CO electrolysis

The copper (Cu)-catalyzed electrochemical CO2 reduction provides a route for the synthesis of multicarbon (C2+) products. However, the thermodynamically favorable Cu surface (i.e. Cu(111)) energetically favors single-carbon production, leading to low energy efficiency and low production rates for C2+ products. Here we introduce in situ copper faceting from electrochemical reduction to enable preferential exposure of Cu(100) facets. During the precatalyst evolution, a phosphate ligand slows the reduction of Cu and assists the generation and co-adsorption of CO and hydroxide ions, steering the surface reconstruction to Cu (100). The resulting Cu catalyst enables current densities of > 500 mA cm−2 and Faradaic efficiencies of >83% towards C2+ products from both CO2 reduction and CO reduction. When run at 500 mA cm−2 for 150 hours, the catalyst maintains a 37% full-cell energy efficiency and a 95% single-pass carbon efficiency throughout.

General synthesis and atomic arrangement identification of ordered Bi-Pd intermetallics with tunable electrocatalytic CO2 reduction selectivity.

Intermetallic compounds (IMCs) with fixed chemical composition and ordered crystallographic arrangement are highly desirable platforms for elucidating the precise correlation between structures and performances in catalysis. However, diffusing a metal atom into a lattice of another metal to form a controllably regular metal occupancy remains a huge challenge. Herein, we develop a general and tractable solvothermal method to synthesize the Bi-Pd IMCs family, including Bi2Pd, BiPd, Bi3Pd5, Bi2Pd5, Bi3Pd8 and BiPd3. By employing electrocatalytic CO2 reduction as a model reaction, we deeply elucidated the interplay between Bi-Pd IMCs and key intermediates. Specific surface atomic arrangements endow Bi-Pd IMCs different relative surface binding affinities and adsorption configuration for *OCHO, *COOH and *H intermediate, thus exhibiting substantially selective generation of formate (Bi2Pd), CO (BiPd3) and H2 (Bi2Pd5). This work provides a comprehensive understanding of the specific structure-performance correlation of IMCs, which serves as a valuable paradigm for precisely modulating catalyst material structures.

Quarter-Wave Plate Metasurfaces for Generating Multi-Channel Vortex Beams.

Metasurfaces of quarter-wave plate (QWP) meta-atoms have exhibited high flexibility and versatile functionalities in the manipulation of light fields. However, the generation of multi-channel vortex beams with the QWP meta-atom metasurfaces presents a significant challenge. In this study, we propose dielectric metasurfaces composed of QWP meta-atoms to manipulate multi-channel vortex beams. QWP meta-atoms, systematically arranged in concentric circular rings, are designed to introduce the modulations via the propagation phase and geometric phase, leading to the generation of co- and cross-polarized vortex beams in distinct channels. Theoretical investigations and simulations are employed to analyze the modulation process, confirming the capability of QWP meta-atom metasurfaces for generating the multi-channel vortex beams. This study presents prospective advancements for the compact, integrated, and multifunctional nanophotonic platforms, which have potential applications in classical physics and quantum domains.

Carbon Footprint Evaluation in Tunnels Excavated in Rock Using Tunnel Boring Machine (TBM)

The generation of CO2 is an important element in assessing the environmental impact generated in a tunnel construction project, making this knowledge very useful for evaluating different alternatives. In this study, an analysis of the carbon footprint has been carried out, including the main elements during the construction phase of a tunnel employing a tunnel boring machine (TBM). The research proposes several options for an easy and quick calculation of CO2 generation in a design phase. Its determination can be crucial for decision-making before and during the execution of any tunnel in the near future. The estimation models have been validated based on real case studies, defining the carbon footprint of each construction element. The proposed procedure can apply to any tunnel. However, it should be noted that it is an approximate analysis, and the limitations described in each section should be considered. The main CO2 generator found in the construction process is the lining element; the percentage varies between 50% in tunnels with smaller diameters (4–5 m) and 75% for tunnels with larger diameters (9–10 m), followed by the auxiliary elements, 16%, and the operation of the tunnel boring machine itself, 11.2%, while the other parts remain in a range between 1.3 and 5.7%. This knowledge makes it possible to define the aspects on which efforts should be focussed to reduce the carbon footprint of the tunnel construction process.

Investigation of dislocation and twinning behavior in HMX under high-velocity impact employing molecular dynamics simulations.

Under the ReaxFF/lg force field, the multiscale shock technique (MSST) was employed to investigate the decomposition behavior of perfect, dislocated, and twinned octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) at a velocity of 11 km/s. This study aimed to analyze the changes in system temperature, bond formation and breaking, variations in the number of small molecules, and the number of clusters. The results indicated that the sensitivity of dislocated HMX was the lowest, while the sensitivity of twinned and perfect HMX was comparable. Comparing the formation and breaking of bonds in HMX during the shock process, it was found that the change in the number of bonds in dislocated HMX was similar to that in perfect HMX, whereas twinning accelerated the breaking of bonds. By analyzing the changes in small molecular fragments (CO, CO2, H, H2, H2O, N2, N2H, NH2, NO, NO2, and O) during the shock process of HMX, it was found that dislocation had a relatively minor effect on the small molecular fragments, while twinning promoted the generation of CO, H, NO, and O and accelerated the decomposition of NO. A comparison of the number, weight, and atomic ratio of clusters under perfect, dislocated, and twinned conditions revealed that under the influence of shock, the number of clusters initially increased sharply and then decreased slowly. Meanwhile, compared to the perfect and dislocated explosives, the number of clusters under the twinned structure was significantly fewer, indicating that the twinned structure could reduce cluster formation. The proportion of oxygen to carbon in the twinned HMX was lower than that in the perfect and dislocated explosives, possibly due to the higher content of small molecular fragment O in twinned HMX. Different structures of HMX crystals were constructed, including twinned defect structure (with a supercell containing 6458 atoms), dislocation defect structure (with a supercell containing 2352 atoms), and perfect structure (also with a supercell containing 2352 atoms). The modeling of defect crystal structures was carried out using the Atomsk software. For the twinned defect structure, we first constructed a mirror symmetric structure of the original configuration and then merged these two structures together. For the dislocation defect structure, we shifted a segment of the originally ordered perfect crystal structure by a certain distance using Atomsk. Before conducting the simulations, we performed geometric optimization of the models using the conjugate gradient (CG) algorithm and carried out 10 ps of NVT and NPT simulations to equilibrate the energy, temperature, and other parameters within the system. Finally, a 50-ps MSST impact simulation was performed using Large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS).

PEM Electrolysis in a Stirred‐Tank Bioreactor Enables Autotrophic Growth of Clostridium ragsdalei with CO2 and Electrons

AbstractAcetogenic bacteria produce CO2‐based chemicals in aqueous media by hydrogenotrophic conversion of CO2, but CO is the preferred carbon and electron source. Consequently, coupling CO2 electrolysis with bacterial fermentation within an integrated bio‐electrocatalytical system (BES) is promising, if CO2 reduction catalysts are available for the generation of CO in the complex biotic electrolyte. A standard stirred‐tank bioreactor was coupled to a zero‐gap PEM electrolysis cell for CO2 conversion, allowing voltage control and separation of the anode in one single cell. The cathodic CO2 reduction and the competing hydrogen evolution enabled in‐situ feeding of C. ragsdalei with CO and H2. Proof‐of‐concept was demonstrated in first batch processes with continuous CO2 gassing, as autotrophic growth and acetate formation was observed in the stirred BES in a voltage range of −2.4 to −3.0 V. The setup is suitable also for other bioelectrocatalytic reactions. Increased currents and lower overvoltages are however required. Atomically‐dispersed M−N−C catalysts show promise, if degradation throughout autoclaving can be omitted. The development of selective and autoclavable catalysts resistant to contamination and electrode design for the complex electrolyte will enable efficient bioelectrocatalytic power‐to‐X systems based on the introduced BES.

PdCu alloy anchored defective titania for photocatalytic conversion of carbon dioxide into methane with 100% selectivity

The photoreduction of CO2 into CH4 with simultaneous high activity and selectivity is a promising strategy to increase energy supply and alleviate global warming. However, the absence of the active sites that is responsible for the adsorption and activation of CO2 and the generation of CO and H2 via side reactions often lead to poor efficiency and low selectivity of the catalyst. Herein, Cu, Pd, and PdCu metal clusters cocatalyst-anchored defective TiO2 nanotubes (Cu/TiO2-SBO, Pd/TiO2-SBO, and Pd1Cu1/TiO2-SBO) were designed via a simple solution impregnation reduction and applied for photocatalytic conversion of CO2 to CH4. The Pd1Cu1/TiO2-SBO photocatalyst exhibits excellent catalytic performance among the other catalysts for photoreduction of CO2 into CH4. More interestingly, the product selectivity of CH4 reaches up to 100% with a rate of 25 µmol g−1 h−1. In-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and density functional theory (DFT) simulations indicate that the main reasons for the high selectivity of CH4 are attributed to the PdCu alloy and oxygen vacancies, which jointly enhance the photoinduced carrier separation and lower energy barriers of key intermediates. Moreover, due to the tunable d-band center of the Cu site in the PdCu alloy, the generated intermediates can be well prevented from poisoning and promoted to participate in further reactions. Hopefully, the current study will provide insight into the development of new, highly selective photocatalysts for the visible light-catalytic reduction of CO2 into CH4.

Bioleaching of a lateritic ore (Piauí, Brazil) in percolators

Heap leaching of laterites for extraction of nickel and cobalt is an attractive alternative to capital and energy intensive high pressure acid leaching, the dominant hydrometallurgical processing technology for limonitic laterites. Conventional approach for heap leaching of laterites is leaching with sulfuric acid. Consumption of sulfuric acid during heap leaching is substantial and industrial-scale operations require construction of a sulfuric acid production plant on site. In this study, heap bioleaching of laterites was simulated in laboratory scale column percolators and bioleaching of nickel and cobalt from lateritic material was successfully demonstrated for the first time. The process is based on biooxidation of the bacterially modified “wet sulfur” inside column percolators by sulfur-oxidizing acidophilic bacteria Acidithiobacillus thiooxidans. The “wet sulfur“ was generated in a bioreactor with the bacterial culture, harvested, and mixed with lateritic ore before forming agglomerates to be filled in the percolator columns. Liquid was circulated with a flow rate of 8 mL/min. Maximum metal extraction was 66% nickel, 95% cobalt, 10% iron, 55% magnesium and 89% manganese from the Piauí lateritic ore after one month bioleaching. For comparison, chemical leaching with 1 M sulfuric acid with or without addition of 10 g/L of ferrous sulfate heptahydrate as reductant resulted in extraction of approximately 80% nickel, 86% cobalt, 33% iron, 50% magnesium and 81% manganese. With bioleaching a higher cobalt but lower nickel and iron extraction was achieved, i.e. a better selectivity of nickel over iron extraction, as well as a relatively higher pH of the pregnant leach solution requiring less limestone and, consequently, lower CO2 emission and generation of iron cake waste in case of laterite bioleaching. Overall, the results are promising and show potential of laterite heap bioleaching to be further developed to application on industrial scale.

The fate of carbon dioxide generated by decomposition of the organic matter in the Boom Clay upon heating at 80 °C: The buffering role of carbonates and implications for the geological disposal of heat-emitting waste

Short-term and long-term hydrothermal experiments were performed with the bulk Boom Clay (Rupelian, Belgium) involving all its constituents (organic matter, minerals and water) in order to follow CO2 generation primarily formed by organic matter decomposition at 80 °C, the temperature to be reached in the near-field of a repository hosting heat-emitting radioactive waste. The carbon speciation and isotopic data in the sampled gas, liquid and solid phase served as a base for mass balance calculations and evaluation of the fate of the carbon dioxide in the studied system. The maximum CO2 yields are lower (1.9 mmol CO2/kg clay after 21 days) in the short-term hydrothermal tests as compared to the long-term tests (maximum 13.3 mmol CO2/kg clay after 7 years) thus underestimating the total capacity of the clay to generate CO2. This is supported by still continuous generation of the carboxylic acids, important precursors of the released CO2 gas, after 21 days. The stable isotope data (δ13C and δ18O) confirm that CO2 gas released from the Boom Clay is of organic origin. The early released CO2 gas is isotopically lighter (−22.2 to −23.3‰) than the reference δ13C of the CO2 (g) and isotopically heavier than the parent kerogen (−25.5 ‰) in the undisturbed Boom Clay. The early CO2 gas is likely out of isotope equilibrium with either dissolved inorganic carbon or solid carbonates. However, measured and extrapolated δ13C values of CO2 gas indicate the tendency towards isotope equilibrium between CO2 gas and both dissolved and solid inorganic carbon on the longer runs (up to 7 years). The precipitation of the carbonates and recycling of the organic matter derived CO2 in the carbonates is further supported by elemental chemistry and mass balance calculations. Altogether, our results suggest that the CO2 (g) released by Boom Clay organic matter is buffered by the carbonates (both dissolved and solid) present in Boom Clay. Thus, no net accumulation of CO2 (g) from organic matter is expected.

Thermodynamic analysis of small-scale polygeneration systems producing natural gas, electricity, heat, and carbon dioxide from biomass

Agricultural greenhouses are still heavily dependent on fossil fuel-based products despite the abundant residual biomass at their disposal. This paper presents two novel decentralized systems that can convert biomass simultaneously into synthetic natural gas (SNG), electricity, useful heat, and a CO2-rich stream. To do so, the electricity and H2/O2 production features of reversible solid oxide cells (RSOCs) are exploited. A steam dual fluidized bed (DFB) gasifier is used in the first proposed system, while the second one adopts a simpler oxygen/steam-blown downdraft gasification approach. Thermodynamic simulations using Aspen Plus software reveal that the total polygeneration process efficiency could reach 86.6%, with a CO2 generation capacity exceeding 275g per kilogram of biomass input. If not used inside the greenhouse atmosphere to enhance crop growth, this high-purity CO2 stream could be sequestered/liquefied to render the process carbon negative. The flexibility of the polygeneration systems is investigated through parametric analysis, where maximum SNG efficiencies that are on par with large-scale plants are obtained. The possibility of storing surplus electricity from intermittent sources as chemical energy in SNG is also highlighted.

Polyphosphide anion-mediated simultaneous P, Au co-alloying with Pd for anti-poisoning formic acid oxidation.

An innovative polyphosphide route is developed to synthesize a series of P-doped PdAu ternary alloys. The alloying of P and Au optimizes the electronic structure and reduces the back-donation of d electrons to CO. Meanwhile, the generation of CO is largely inhibited by the highly selective direct pathway arising from the synergistic electron/ligand effect of Au and P, leading to a remarkable anti-poisoning capability for formic acid oxidation.