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At least 1,315 records · Page 73

Toward implementation of carbon-conservation networks in nonmodel organisms

Decarboxylation — the release of carbon dioxide (CO 2 ) from a substrate — reduces the carbon yield of bioproduced chemicals. When overlaid onto central carbon metabolism, carbon-conservation networks (CCNs) that reroute flux around CO 2 release can theoretically achieve higher carbon yields for products derived from intermediates that traditionally require CO 2 release, such as acetyl-CoA. Recently, CCNs have started to be implemented in model organisms to produce compounds at higher carbon yields. However, implementation of CCNs in nonmodel hosts may have the greatest impact given their ability to assimilate a larger array of feedstocks, greater environmental tolerance, and unique biosynthetic pathways, ultimately enabling access to a wider range of products. Here, we review recent advances in CCNs with a focus on their application to nonmodel organisms. The differences in central carbon metabolism among different nonmodel hosts reveal opportunities to engineer and apply new CCNs.

59 BASIC BIOLOGICAL SCIENCES↗

Activated carbon supported Ni, Fe, and bimetallic NiFe catalysts for CO x -free H 2 production by microwave methane pyrolysis

The goal of this study was to test the effect of metal-impregnated carbon-based catalysts on the conversion of methane to hydrogen gas and solid carbon using microwave reactor technology. Monometallic and bimetallic catalysts on activated carbon supports (Ni/AC, Fe/AC, Ni-Fe/AC) are compared during methane pyrolysis testing. Catalytic methane pyrolysis was carried out in a microwave reactor at reaction temperatures of 600 °C and 800 °C. For comparison, one of the catalysts (Ni-Fe/AC) was tested in a conventionally heated reactor at 800 °C. The prepared catalysts were characterized by X-ray diffraction (XRD), while post-reaction catalysts were characterized by XRD and SEM. During reaction testing, the monometallic Ni/AC catalyst exhibited the best catalytic activity (CH 4 conversion: 46.0 and H 2 yield: 46.9%) when reacted in the microwave reactor, however, it suffered from rapid deactivation from carbon deposition (carbon yield: 0.39 gC/g catalyst). The bimetallic Ni-Fe/AC catalyst was slightly less active (CH 4 conversion: 36.9 and H 2 yield: 40.5%) but it was more resistant to carbon formation (carbon yield: 0.27 gC/g catalyst) suggesting it may have greater long-term stability. The Ni-Fe/AC catalyst was also the most energy efficient as it required the least microwave power to maintain the 800 °C reaction temperature compared to the other catalysts tested. Methane conversion of the bimetallic Ni-Fe/AC at 800 °C under microwave irradiation was three times the conversion under conventional heating at the same reaction temperature. Finally, this work demonstrates the use of microwave-specific catalysts for catalytic methane pyrolysis in a microwave reactor, and can be used as a foundation for further methane pyrolysis process and catalyst optimization for CO x -free H 2 production.

08 HYDROGEN↗

Implications of carbon content for the processing, stability, and mechanical properties of cast and wrought Ni-based superalloy Nimonic 105

As the temperature and pressure requirements in land-based turbines for power generation increase, the shift towards more advanced alloys, e.g., Ni-based superalloys, requires improved understanding of their long-term stability and mechanical properties. Additionally, the larger size of the components also presents fabrication and cost-reduction problems. In this study, we investigated Nimonic 105 as a potential rotor material at two carbon content levels – the commonly used maximum of the alloy specification and a lower carbon content variant. Reducing the carbon content presented fabrication challenges, resulting in surface crack formation during hot working. Additionally, a lower M 6 C carbide fraction was present after fabrication/solutioning, leading to a significantly larger grain size. After the standard aging treatment, similar γ' populations formed in the two variants, however the M 6 C carbides in the high-carbon variant already started transforming to intergranular M 23 C 6 . Although we did not observe a noticeable effect on the tensile properties of the two variants, the lower carbon content alloy possessed a superior creep property – mainly due to the larger grain size as the microstructural stability was inferior. Further, upon prolonged thermal exposure, the M 6 C carbides in the low-carbon variant further decomposed to intergranular and intragranular σ and μ precipitates, as opposed to mainly M 23 C 6 as in the high-carbon variant.

36 MATERIALS SCIENCE↗

A universal method to fabricating porous carbon for Li-O 2 battery

The main bottleneck in the application of biomass-based carbon material in energy field is the development of an economical, nanoscale controllable and universal fabrication method. Herein, we demonstrate that a biomass-derived carbon consisting of loose carbon nanosphere clusters could serve as an ideal cathode material for high performance Li-O 2 batteries. The carbon nanomaterial can be prepared from both biomass derivatives and crude biomass by a low cost, facile and nanoscale controllable method. The open slit-shaped hierarchical pore structure endows the electrode sufficient active surface sites and mass transport channels that are not easily asphyxiated by the discharge products. The concentration of oxygenic groups and structure defects on the surface of obtained carbon materials is very low, which minimizes the side reactions associated with carbon decomposition. Finally, the unique pore structure and surface properties of the carbon electrode give rise to a superhigh specific capacity of 20,300 mA h g -1 and an extremely long cycle life which a cyclic capacity retention of 100% is maintained for 543 cycles with current density of 0.2 mA cm -2 at controlled discharge-charge depths of 500 mA h g -1 .

25 ENERGY STORAGE↗

Advancing Porous Carbons: Understanding the Importance of Surface Chemistry for the Energy–Environment Nexus

This review intends, in a critical way, the comprehensive view of the importance of porous carbons surface chemistry for their applications in an energy− environment nexus. Surface chemistry is presented as a combination of functional heteroatom-containing groups, dopants, and structural defects. First, we briefly address carbon surface chemical environment and the methods of its modification and characterization, indicating their practical limitations. Then, the effects of surface chemistry on separation, catalysis, energy storage, sensing and microwave absorption are introduced. Besides a critical analysis of published findings on these topics, we also include our views on the advancement in the processes which rely on porous carbons surface chemistry, and identify strategic areas and directions that should deserve further attention. We focus on new findings and important original contributions to the field. Since the community of carbon researchers grows following the strategic application of these materials, the role of functional groups, dopants and structural defects in various cutting-edge applications is emphasized, showing the progress in the field and the evolution of findings. A clear determination of the effects of carbon surface is often a challenge since carbons porosity and the locations of specific bonds/sites/ defects in the carbon texture provide nanoconfinement effects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis and Characterization of Carbon Microbeads

We report a microfluidic-based droplet generation platform for synthesizing micron-sized porous carbon microspheres. The setup employs carbon materials such as graphite, carbon nanotubes, graphene, fullerenes, and carbon black as starting materials. Custom composition, structure, and function are achieved through combinations of carbon materials, cross-linkers, and additives along with variations in process parameters. Carbon materials can be assembled into spheres with a mean diameter of units to hundreds of μm with relatively tight size distribution (<25% RSD). Pore structure and size (tens to hundreds of angstrom) can be modulated by incorporating porogen/coporogen dilutants during synthesis. The microbeads have excellent mechanical stability with an elastic modulus of hundreds of MPa. They can sustain high dynamic fluid flow pressures of up to 9000 psi. This work lays the foundation for synthesizing novel tailorable and customizable carbon microbeads. It opens avenues for applying these novel materials for composite and additive manufacturing, energy, life science, and biomedical applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Permafrost Carbon: Progress on Understanding Stocks and Fluxes Across Northern Terrestrial Ecosystems

Significant progress in permafrost carbon science made over the past decades include the identification of vast permafrost carbon stocks, the development of new pan-Arctic permafrost maps, an increase in terrestrial measurement sites for CO 2 and methane fluxes, and important factors affecting carbon cycling, including vegetation changes, periods of soil freezing and thawing, wildfire, and other disturbance events. Process-based modeling studies now include key elements of permafrost carbon cycling and advances in statistical modeling and inverse modeling enhance understanding of permafrost region C budgets. By combining existing data syntheses and model outputs, the permafrost region is likely a wetland methane source and small terrestrial ecosystem CO 2 sink with lower net CO 2 uptake toward higher latitudes, excluding wildfire emissions. For 2002–2014, the strongest CO2 sink was located in western Canada (median: -52 g C m -2 y -1 ) and smallest sinks in Alaska, Canadian tundra, and Siberian tundra (medians: -5 to -9 g C m -2 y -1 ). Eurasian regions had the largest median wetland methane fluxes (16–18 g CH4 m -2 y -1 ). Quantifying the regional scale carbon balance remains challenging because of high spatial and temporal variability and relatively low density of observations. More accurate permafrost region carbon fluxes require: (a) the development of better maps characterizing wetlands and dynamics of vegetation and disturbances, including abrupt permafrost thaw; (b) the establishment of new year-round CO 2 and methane flux sites in underrepresented areas; and (c) improved models that better represent important permafrost carbon cycle dynamics, including non-growing season emissions and disturbance effects.

54 ENVIRONMENTAL SCIENCES↗

Shrub Expansion Can Counteract Carbon Losses From Warming Tundra

Arctic warming is causing substantial compositional, structural, and functional changes in tundra vegetation including shrub and tree-line expansion and densification. However, predicting the carbon trajectories of the changing Arctic is challenging due to interacting feedbacks between vegetation composition and structure, and surface characteristics. We conduct a sensitivity analysis of the current-date to 2100 projected surface energy fluxes, soil carbon pools, and CO 2 fluxes to different shrub expansion rates under future emission scenarios (intermediate—RCP4.5, and high—RCP8.5) using the Arctic-focused configuration of E3SM Land Model (ELM). We focus on Trail Valley Creek (TVC), an upland tundra site in the western Canadian Arctic, which is experiencing shrub densification and expansion. We find that shrub expansion did not significantly alter the modeled surface energy and water budgets. However, the carbon balance was sensitive to shrub expansion, which drove higher rates of carbon sequestration as a consequence of higher shrubification rates. Thus, at low shrub expansion rates, the site would become a carbon source, especially under RCP8.5, due to higher temperatures, which deepen the active layer and enhance soil respiration. At higher shrub expansion rates, TVC would become a net CO 2 sink under both Representative Concentration Pathway scenarios due to higher shrub productivity outweighing temperature-driven respiration increase. Our simulations highlight the effect of shrub expansion on Arctic ecosystem carbon fluxes and stocks. We predict that at TVC, shrubification rate would interact with climate change intensity to determine whether the site would become a carbon sink or source under projected future climate.

Yazbeck, Theresia [The Ohio State Univ., Columbus,↗

Reversal of carbonate-silicate cation exchange in cold slabs in Earth’s lower mantle

The stable forms of carbon in Earth’s deep interior control storage and fluxes of carbon through the planet over geologic time, impacting the surface climate as well as carrying records of geologic processes in the form of diamond inclusions. However, current estimates of the distribution of carbon in Earth’s mantle are uncertain, due in part to limited understanding of the fate of carbonates through subduction, the main mechanism that transports carbon from Earth’s surface to its interior. Oxidized carbon carried by subduction has been found to reside in MgCO 3 throughout much of the mantle. Experiments in this study demonstrate that at deep mantle conditions MgCO 3 reacts with silicates to form CaCO 3 . In combination with previous work indicating that CaCO 3 is more stable than MgCO 3 under reducing conditions of Earth’s lowermost mantle, these observations allow us to predict that the signature of surface carbon reaching Earth’s lowermost mantle may include CaCO 3 .

58 GEOSCIENCES↗

Fungal community composition predicts forest carbon storage at a continental scale

Forest soils harbor hyper-diverse microbial communities which fundamentally regulate carbon and nutrient cycling across the globe. Directly testing hypotheses on how microbiome diversity is linked to forest carbon storage has been difficult, due to a lack of paired data on microbiome diversity and in situ observations of forest carbon accumulation and storage. Here, we investigated the relationship between soil microbiomes and forest carbon across 238 forest inventory plots spanning 15 European countries. We show that the composition and diversity of fungal, but not bacterial, species is tightly coupled to both forest biotic conditions and a seven-fold variation in tree growth rates and biomass carbon stocks when controlling for the effects of dominant tree type, climate, and other environmental factors. This linkage is particularly strong for symbiotic endophytic and ectomycorrhizal fungi known to directly facilitate tree growth. Since tree growth rates in this system are closely and positively correlated with belowground soil carbon stocks, we conclude that fungal composition is a strong predictor of overall forest carbon storage across the European continent.

54 ENVIRONMENTAL SCIENCES↗

The structure of liquid carbon elucidated by in situ X-ray diffraction

Carbon has a central role in biology and organic chemistry, and its solid allotropes provide the basis of much of our modern technology. However, the liquid form of carbon remains nearly uncharted, and the structure of liquid carbon and most of its physical properties are essentially unknown. But liquid carbon is relevant for modelling planetary interiors and the atmospheres of white dwarfs, as an intermediate state for the synthesis of advanced carbon materials, inertial confinement fusion implosions, hypervelocity impact events on carbon materials and our general understanding of structured fluids at extreme conditions. Here we present a precise structure measurement of liquid carbon at pressures of around 1 million atmospheres obtained by in situ X-ray diffraction at an X-ray free-electron laser. Our results show a complex fluid with transient bonding and approximately four nearest neighbours on average, in agreement with quantum molecular dynamics simulations. The obtained data substantiate the understanding of the liquid state of one of the most abundant elements in the universe and can test models of the melting line. The demonstrated experimental abilities open the path to performing similar studies of the structure of liquids composed of light elements at extreme conditions.

74 ATOMIC AND MOLECULAR PHYSICS↗

The interplay of labile organic carbon, enzyme activities and microbial communities of two forest soils across seasons

Soil labile organic carbon (LOC) responds rapidly to environmental changes and plays an important role in carbon cycle. In this study, the seasonal fluctuations in LOC, the activities of carbon-cycle related enzymes, and the bacterial and fungal communities were analyzed for soils collected from two forests, namely Betula albosinensis (Ba) and Picea asperata Mast. (Pa), in the Qinling Mountains of China. Results revealed that the seasonal average contents of microbial biomass carbon (MBC), easily oxidized organic carbon (EOC), and dissolved organic carbon (DOC) of Pa forest soil were 13.5%, 30.0% and 15.7% less than those in Ba soil. The seasonal average enzyme activities of β-1,4-glucosidase (βG), and β-1,4-xylosidase (βX) of Ba forest soils were 30.0% and 32.3% higher than those of Pa soil while the enzyme activity of cellobiohydrolase (CBH) was 19.7% lower. Furthermore, the relative abundance of Acidobacteria was significantly higher in summer than in winter, whereas the relative abundance of Bacteroidetes was higher in winter. Regarding the fungal communities, the relative abundance of Basidiomycota was lowest in winter, whereas Ascomycota predominated in the same season. In addition, the soil LOC was significantly positively correlated with the CBH, βG and βX activities. Changes in LOC were significantly correlated with Acidobacteria, Bacteroidetes and Basidiomycota. We conclude that the seasonal fluctuations in forest soil LOC fractions relied on carbon cycle-associated enzymatic activities and microorganisms, which in turn were affected by climatic conditions.

54 ENVIRONMENTAL SCIENCES↗

Local structure and distortions of mixed methane-carbon dioxide hydrates

A vast source of methane is found in gas hydrate deposits, which form naturally dispersed throughout ocean sediments and arctic permafrost. Methane may be obtained from hydrates by exchange with hydrocarbon byproduct carbon dioxide. It is imperative for the development of safe methane extraction and carbon dioxide sequestration to understand how methane and carbon dioxide co-occupy the same hydrate structure. Pair distribution functions (PDFs) provide atomic-scale structural insight into intermolecular interactions in methane and carbon dioxide hydrates. We present experimental neutron PDFs of methane, carbon dioxide and mixed methane-carbon dioxide hydrates at 10 K analyzed with complementing classical molecular dynamics simulations and Reverse Monte Carlo fitting. Mixed hydrate, which forms during the exchange process, is more locally disordered than methane or carbon dioxide hydrates. The behavior of mixed gas species cannot be interpolated from properties of pure compounds, and PDF measurements provide important understanding of how the guest composition impacts overall order in the hydrate structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis of the land carbon fluxes of the Amazon region between 2010 and 2020

The Amazon is the largest continuous tropical forest in the world and plays a key role in the global carbon cycle. Human-induced disturbances and climate change have impacted the Amazon carbon balance. Here we conduct a comprehensive synthesis of existing state-of-the-art estimates of the contemporary land carbon fluxes in the Amazon using a set of bottom-up methods (i.e., dynamic vegetation models and bookkeeping models) and a top-down inversion (atmospheric inversion model) over the Brazilian Amazon and the whole Biogeographical Amazon domain. Over the whole biogeographical Amazon region bottom-up methodologies suggest a small average carbon sink over 2010-2020, in contrast to a small carbon source simulated by top-down inversion (2010-2018). However, these estimates are not significantly different from one another when accounting for their large individual uncertainties, highlighting remaining knowledge gaps, and the urgent need to reduce such uncertainties. Nevertheless, both methodologies agreed that the Brazilian Amazon has been a net carbon source during recent climate extremes and that the south-eastern Amazon was a net land carbon source over the whole study period (2010-2020). Overall, our results point to increasing human-induced disturbances (deforestation and forest degradation by wildfires) and reduction in the old-growth forest sink during drought.

54 ENVIRONMENTAL SCIENCES↗

Soil moisture-atmosphere interactions drive terrestrial carbon-water trade-offs

Soil moisture is coupled with vegetation and atmosphere, influencing global cycling of water, carbon, and energy. However, it remains unclear how soil moisture-atmosphere interactions affect land-atmosphere carbon and water exchanges simultaneously. Using Earth system model experiments, we show widespread carbon-water trade-offs between net ecosystem production and precipitation-minus-evapotranspiration driven by soil moisture dynamics. Soil moisture positively controls net ecosystem production and negatively affects precipitation-minus-evapotranspiration, through direct soil water stress and indirect soil moisture-atmosphere feedbacks. While soil moisture variability magnifies the interannual variability of net ecosystem production, it moderates that of precipitation-minus-evapotranspiration over land. These opposing effects lead to a pronounced carbon-water trade-off, which originates from the interplay between carbon acquisition through photosynthesis and water extraction through evapotranspiration. This trade-off is projected to intensify in a warming and drying future, as soil moisture increasingly regulates carbon and water exchanges, posing a serious challenge to sustaining both terrestrial carbon sink and water supply.

54 ENVIRONMENTAL SCIENCES↗

Complex carbonate phases drive geologic CO2 mineralization

Abstract Geologic carbon sequestration in mafic and ultramafic reservoirs is a scalable strategy for carbon dioxide removal, offering permanent storage via mineralization as stable carbonates. However, there is limited information on the structure and composition of key mineralization endpoints during sequestration. Here, we unravel the atomic structure, composition, and nanoscale morphology of carbonates recovered from a field-scale demonstration of CO 2 mineralization in basalt. Using transmission electron microscopy, we mapped mineralogical variations from the initial to later stages of subsurface carbonate growth and identified a previously unknown cation-ordered ankerite phase that exerts a primary control over carbonation processes. This study has provided a new understanding of subsurface carbonation pathways which will impact the parameterization of predictive geochemical models for future sequestration efforts in basalt formations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Carbon mineralization pathways in interfacial adsorbed water nanofilms

Carbon mineralization in humidified carbon dioxide offers a promising route to mitigate anthropogenic emissions in a world stressed by water security. Despite its technological importance, our understanding of carbonation in water-poor environments lags, as traditional dissolution-precipitation pathways struggle to explain the adsorbed water nanofilm-mediated reactivity. Here, we utilize in operando X-ray diffraction (XRD) and advanced molecular simulations to investigate nanoconfined reactions driving forsterite carbonation, the magnesium-rich olivine. By examining magnesium ion dissolution and transport in atomistic simulations of the forsterite-water-carbon dioxide interface and comparing these with the in operando XRD activation energies, we identify both processes as rate-limiting at saturation. Our simulations reveal a mechanistic view of interfacial carbonation, where dissolution and precipitation are mediated by anomalous quasi two-dimensional diffusion. The transport process involves intermittent diffusive hopping in the desorbed state, separated by crawling events that are spatially short but temporally long. This understanding transcends carbon mineralization, with implications for understanding the transport of contaminants in geosystems, the design of multifunctional materials, water desalination, and molecular recognition systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Raman spectroscopy of thermally perturbed carbon fibers: Discriminating spectral responses of modulus classes and defect types

The mechanical strength properties of carbon fibers are generally thought to be correlated with the presence of underlying atomic-level defects. These defects serve to break the underlying translational symmetry of the graphitic or graphene subunits of the fiber construction, resulting in the emergence of new Raman-active spectral features. However, historical attempts to classify the precise origin of defect contributions to the Raman spectra have been challenging because of indistinct and overlapping features in the carbon fiber Raman spectra. Further, while substantial research exists on high-temperature exposure in inert atmospheres for carbon fiber composites, comparatively less addresses microscale behaviors and Raman spectral alterations to monofilament carbon fibers exposed to high-temperature atmospheric environments. Here, we report Raman spectral responses of nine commercially available high-performance, polyacrylonitrile-based carbon fibers exposed to various atmospheric heat treatments. In this work, we introduce a model-independent characterization method, the integrated absolute difference, to quantify the spectral responses to heat treatment of different fiber modulus classes. We combine this new method with a newly reported strategy to standardize spectral fitting for carbon fibers. With this approach, we show that atomic-scale defects in the underlying fiber microstructure manifest in measurably distinct manners and have distinct responses to thermal perturbation. These combined approaches may lay the foundation for disentangling contributions from specific defects in the Raman spectra of carbon fibers.

36 MATERIALS SCIENCE↗