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A U.S. scientific community review of carbon cycle science gaps and opportunities to better support earth system science and carbon management

Greenhouse gas (GHG) emissions continue to grow, while natural carbon reservoirs are becoming increasingly vulnerable to anthropogenic pressures, climate extremes, and disturbance. These changes are impacting humans, ecosystems, and natural resources worldwide. Tracking and mitigating GHG emissions require a pivot to operational monitoring of regional carbon flux and stock changes. The current GHG observing system is addressing needs at two distinct scales: 1) Local scale (< 1 km), related to anthropogenic point source emissions, and 2) global scales (> 1000 km), related to land and ocean carbon sinks. More focus on intermediate (10–1000 km) scales is needed to more effectively monitor progress in reducing carbon emissions, enhancing removals, and maintaining sinks. Representatives from carbon cycle biomass and flux communities across United States government agencies and academic institutions met in September 2024 to discuss the rationale and scientific context for more effectively implementing an operational system for GHG monitoring in support of urban and national carbon management needs. To guide development of this system, we propose a multi-tiered global spaceborne observing framework for carbon flux and stock, prioritizing: 1) frequent GHG partial columns for carbon emissions and removals; 2) continuous time series and data fusion of biomass from Lidar and Synthetic Aperture Radar (SAR) for carbon stocks, and 3) expanded coverage of tropical, high latitude, and oceanic regions to monitor carbon cycle tipping points and feedbacks. This system should be complemented by expanded surface and airborne networks for oceanic and terrestrial/aquatic ecosystems for calibration, ground truthing, and study of under-sampled regions.

54 ENVIRONMENTAL SCIENCES↗

Spatially explicit terrestrial carbon densities for calibrating the carbon cycle in human-Earth system Models

Soil and vegetation carbon stocks play a critical role in human-Earth system models. These stocks (denominated as densities in MgC/ha) affect variables such as land use change emissions and also influence land use change pathways under climate forcing scenarios where terrestrial carbon is assigned a carbon price. Here we present reharmonized soil and vegetation carbon densities both at the 5-arcmin resolution grid cell level and also aggregated to 235 water sheds for 4 land use types (Cropland, Grazed land, Urban land and unmanaged vegetation) and 15 unmanaged land cover types. Moreover, we use the distribution of carbon within and across pixels to define statistical "states" of carbon, once again differentiated by land type. These statistical states are used to define a range of possible carbon values that can be used for defining initial conditions of soil and vegetation carbon in human-Earth system models. We implement these data in a state-of-the-art multi sector dynamics model, namely the Global Change Analysis Model (GCAM), and show that these new data improve several land use responses, especially when terrestrial carbon is assigned a carbon price.

54 ENVIRONMENTAL SCIENCES↗

Nannochloropsis oceanica IMET1 and its bacterial symbionts for carbon capture, utilization, and storage: biomass and calcium carbonate production under high pH and high alkalinity

ABSTRACT To combat the increasing levels of carbon dioxide (CO 2 ) released from the combustion of fossil fuels, microalgae have emerged as a promising strategy for biological carbon capture, utilization, and storage. This study used a marine microalgal strain, Nannochloropsis oceanica IMET1, which thrives in high CO 2 concentrations. A high-pH, high-alkalinity culture was designed for CO 2 capture through algal biomass production as well as permanent sequestration through calcium carbonate (CaCO 3 ) precipitation. This was accomplished by timed pH elevation and the addition of sodium bicarbonate to cultures of N. oceanica grown at lab scale (1 L) and pilot scale (500 L) with 10% and 5% CO 2 , respectively. Our data showed that 0.02 M NaHCO 3 promoted algal growth and that sparging cultures with ambient air after 12 days raised pH and created favorable CaCO 3 formation conditions. At the 1 L scale, we reached 1.52 g L −1 biomass after 12 days and an extra 9.3% CO 2 was captured in the form of CaCO 3 precipitates. At the 500 L pilot scale, an extra 60% CO 2 was captured (Day 40) with a maximum CO 2 capture rate of 63.2 g m −2 day −1 (Day 35). Bacterial communities associated with the microalgae were dominated by two novel Patescibacteria. Functional analysis revealed that genes for several plant growth-promotion traits (PGPTs) were enriched within this group. The microalgal-bacterial coculture system offers advantages for enhanced carbon mitigation through biomass production and simultaneous precipitation of recalcitrant CaCO 3 for long-term CO 2 storage. IMPORTANCE Capturing carbon dioxide (CO 2 ) released from fossil fuel combustion is of the utmost importance as the impacts of climate change continue to worsen. Microalgae can remove CO 2 through their natural photosynthetic pathways and are additionally able to convert CO 2 into a stable, recalcitrant form as calcium carbonate (CaCO 3 ). We demonstrate that microalgae-based carbon capture systems can be greatly improved with high pH and high alkalinity by providing optimal conditions for carbonate precipitation. Our results with the microalga, Nannochloropsis oceanica strain IMET1, show an extra 9.3% CO 2 captured as CaCO 3 at the 1 L scale and an extra 60% CO 2 captured at the 500 L (pilot) scale. Our optimized system provides a novel approach to capture CO 2 through two mechanisms: (i) as organic carbon within microalgal biomass and (ii) as inorganic carbon stored permanently in the form of CaCO 3.

20 FOSSIL-FUELED POWER PLANTS↗

Nonenergy Biomass Carbon Removal and Storage (BiCRS): Assessing Durability of Nongaseous Carbon Products Across Terrestrial Storage Fates

Biomass Carbon Removal and Storage, or BiCRS, pathways use plants or algae that remove carbon dioxide from the atmosphere through photosynthesis and store it underground or in long-lived products. While some BiCRS approaches generate an energy product, all BiCRS approaches generate a carbon product. A new subset of BiCRS approaches focus on the storage of these raw or converted carbon products for generation of carbon credits. However, the durability of these approaches is highly variable as carbon products vary widely in their “form” and the conditions of their “fate.” We organize our thinking about carbon products and their durability around these two primary axes. The durability of carbon product “forms” is mediated by chemical recalcitrance and ranges substantially across agricultural residues, municipal solid waste, woody biomass, and nongaseous products of thermochemical conversion (e.g., biochars and bio-oils). Meanwhile, terrestrial storage “fates” vary in the mechanism employed to stall decay, including surface storage, dry storage, shallow anoxic storage, and deep or geologic anoxic storage (or injection). Each mechanism has different implications for suitability with different feedstock forms as well as long-term risks. We present a framework for assessing durability of solid or liquid raw and conversion carbon products under terrestrial storage fates, highlighting knowns, unknowns, and research priorities moving forward.

09 BIOMASS FUELS↗

Quantification of the carbon bonding state in amorphous carbon materials: A comparison between EELS and NEXAFS measurements

In this report the quantitative determination of the carbon hybridization is critical for establishing processing-structure-properties relationships for carbon-based materials, including amorphous carbon coatings. While several techniques have been employed to characterize the amount of sp 2 and sp 3 carbon in these materials, direct comparisons between analytical results are limited. Here, we compare near edge X-ray absorption fine structure (NEXAFS) spectra of a silicon- and oxygen-containing hydrogenated amorphous carbon (a-C:H:Si:O) coating acquired in synchrotron-based scanning transmission X-ray microscopy (STXM) mode with electron energy loss spectra (EELS) obtained from the same a-C:H:Si:O lamella. While the fractions of sp 2 carbon computed from STXM and EELS spectra are in close agreement, the comparison of NEXAFS spectra acquired in STXM mode with NEXAFS spectra collected in partial electron yield mode on a flat a-C:H:Si:O surface indicated that the destructive preparation of thin lamellae for STXM analyses induces variations in the structure of a-C:H:Si:O, namely the breakage of carbon-silicon and carbon-hydrogen bonds, a change in ordering of sp 2 -bonded carbon, and an increase in the sp 2 carbon fraction. These findings can help scientists in the careful interpretation of spectroscopic results obtained from the analysis of samples made of metastable materials after the destructive preparation of specimens for analytical purposes.

36 MATERIALS SCIENCE↗

InterCarb: A Community Effort to Improve Interlaboratory Standardization of the Carbonate Clumped Isotope Thermometer Using Carbonate Standards

Abstract Increased use and improved methodology of carbonate clumped isotope thermometry has greatly enhanced our ability to interrogate a suite of Earth‐system processes. However, interlaboratory discrepancies in quantifying carbonate clumped isotope (Δ 47 ) measurements persist, and their specific sources remain unclear. To address interlaboratory differences, we first provide consensus values from the clumped isotope community for four carbonate standards relative to heated and equilibrated gases with 1,819 individual analyses from 10 laboratories. Then we analyzed the four carbonate standards along with three additional standards, spanning a broad range of δ 47 and Δ 47 values, for a total of 5,329 analyses on 25 individual mass spectrometers from 22 different laboratories. Treating three of the materials as known standards and the other four as unknowns, we find that the use of carbonate reference materials is a robust method for standardization that yields interlaboratory discrepancies entirely consistent with intralaboratory analytical uncertainties. Carbonate reference materials, along with measurement and data processing practices described herein, provide the carbonate clumped isotope community with a robust approach to achieve interlaboratory agreement as we continue to use and improve this powerful geochemical tool. We propose that carbonate clumped isotope data normalized to the carbonate reference materials described in this publication should be reported as Δ 47 (I‐CDES) values for Intercarb‐Carbon Dioxide Equilibrium Scale.

58 GEOSCIENCES↗

Systematic observations of enhanced oil recovery and associated changes at carbonate-brine and carbonate-petroleum interfaces

Enhanced oil recovery (EOR) from carbonates is obtained by injection of controlled ionic strength brines containing “active ions” (e.g., SO 4 2- , Mg 2+ , Ca 2+ ). It is generally believed that this occurs through the interaction of the active ions at the carbonate-brine interface (e.g., within a thin brine layer separating the petroleum and the carbonate phases). Here, in-situ observations show how one active ion, SO 4 2- , alters behavior at the carbonate-petroleum interface. Displacement of petroleum from initially oil-wet carbonate rocks using brines with variable SO 4 concentrations systematically changes oil recovery, in situ contact angles, and connectivity of the oil phase, confirming that the active ion alters interactions at the oil/brine/carbonate interface, as expected. Measurements of model calcite-fluid interfaces show that there is no measurable sorption of SO 4 to carbonate-brine interfaces but reveals that the carbonate-petroleum interface is altered by previous exposure to SO 4 -containing brines. These results suggest that EOR in carbonates is controlled indirectly by active ions. We propose that this may be due to a reduced oleophilicity of the carbonate caused by chemical complexation between the active ion and petroleum’s acidic and basic functional groups. This mechanism explains how both anions and cations act as active ions for EOR in carbonates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Adding labile carbon to peatland soils triggers deep carbon breakdown

Peatlands store vast amounts of carbon, with deep peat carbon remaining stable due to limited thermodynamic energy and transport. However, climate change-induced increases in labile carbon inputs could destabilize these stores. Here, we combined DNA stable isotope probing with stable isotope-assisted metabolomics employing a multi-platform approach to investigate microbial dynamics driving deep peat carbon degradation upon labile carbon (e.g., glucose) amendment. Our findings highlight the vulnerability of deep peat carbon, as glucose addition triggers the breakdown of older organic matter. By uniquely integrating these techniques, we identified active glucose metabolizers to specific microbial populations and mapped carbon flow through microbial networks, elucidating their role in priming recalcitrant carbon mineralization. This multi-omics approach offers crucial insights into how changing resources reshape the peatland microbiome, enhancing our understanding of deep carbon processing, and refining model parameterization to predict microbial responses and carbon cycle feedbacks under global change pressures.

59 BASIC BIOLOGICAL SCIENCES↗

Enhanced Carbon Flux Response to Atmospheric Aridity and Water Storage Deficit During the 2015–2016 El Niño Compromised Carbon Balance Recovery in Tropical South America

During the 2015–2016 El Niño, the Amazon basin released almost one gigaton of carbon (GtC) into the atmosphere due to extreme temperatures and drought. The link between the drought impact and recovery of the total carbon pools and its biogeochemical drivers is still unknown. With satellite-constrained net carbon exchange and its component fluxes including gross primary production and fire emissions, we show that the total carbon loss caused by the 2015–2016 El Niño had not recovered by the end of 2018. Forest ecosystems over the Northeastern (NE) Amazon suffered a cumulative total carbon loss of ~0.6 GtC through December 2018, driven primarily by a suppression of photosynthesis whereas southeastern savannah carbon loss was driven in part by fire. We attribute the slow recovery to the unexpected large carbon loss caused by the severe atmospheric aridity coupled with a water storage deficit during drought. We show the attenuation of carbon uptake is three times higher than expected from the pre-drought sensitivity to atmospheric aridity and ground water supply. Our study fills an important knowledge gap in our understanding of the unexpectedly enhanced response of carbon fluxes to atmospheric aridity and water storage deficit and its impact on regional post-drought recovery as a function of the vegetation types and climate perturbations. Our results suggest that the disproportionate impact of water supply and demand could compromise resiliency of the Amazonian carbon balance to future increases in extreme events.

54 ENVIRONMENTAL SCIENCES↗

Lightweight carbon-carbon thermal protection system for STARPROBE

This paper describes the preliminary design, development, and initial testing of prototype carbon-carbon components of the thermal protection system of the NASA STARPROBE spacecraft. The thermal protection system is designed to limit the spacecraft scientific instrument package to a maximum temperature of 55 C during the time of closest approach to the earth's sun when the peak radiative heating rate reaches 393 w/sq cm. The thermal protection system is comprised of a carbon-carbon thin shell primary shield and two carbon-carbon sandwich construction secondary shields which block reradiation from the primary shield to the spacecraft. These shields are joined and stiffened by carbon-carbon structural members and attached to the spacecraft with eight thin-walled carbon-carbon struts. Prototype parts of the principal components have been fabricated and will be tested in a solar radiative flux environment simulating peak mission values in late 1984.

Dirling, R. B., Jr.↗

Ca-Rich Carbonate Melts: A Regular-Solution Model, with Applications to Carbonatite Magma + Vapor Equilibria and Carbonate Lavas on Venus

A thermochemical model of the activities of species in carbonate-rich melts would be useful in quantifying chemical equilibria between carbonatite magmas and vapors and in extrapolating liquidus equilibria to unexplored PTX. A regular-solution model of Ca-rich carbonate melts is developed here, using the fact that they are ionic liquids, and can be treated (to a first approximation) as interpenetrating regular solutions of cations and of anions. Thermochemical data on systems of alkali metal cations with carbonate and other anions are drawn from the literature; data on systems with alkaline earth (and other) cations and carbonate (and other) anions are derived here from liquidus phase equilibria. The model is validated in that all available data (at 1 kbar) are consistent with single values for the melting temperature and heat of fusion for calcite, and all liquidi are consistent with the liquids acting as regular solutions. At 1 kbar, the metastable congruent melting temperature of calcite (CaCO3) is inferred to be 1596 K, with (Delta)bar-H(sub fus)(calcite) = 31.5 +/- 1 kJ/mol. Regular solution interaction parameters (W) for Ca(2+) and alkali metal cations are in the range -3 to -12 kJ/sq mol; W for Ca(2+)-Ba(2+) is approximately -11 kJ/sq mol; W for Ca(2+)-Mg(2+) is approximately -40 kJ/sq mol, and W for Ca(2+)-La(3+) is approximately +85 kJ/sq mol. Solutions of carbonate and most anions (including OH(-), F(-), and SO4(2-)) are nearly ideal, with W between 0(ideal) and -2.5 kJ/sq mol. The interaction of carbonate and phosphate ions is strongly nonideal, which is consistent with the suggestion of carbonate-phosphate liquid immiscibility. Interaction of carbonate and sulfide ions is also nonideal and suggestive of carbonate-sulfide liquid immiscibility. Solution of H2O, for all but the most H2O-rich compositions, can be modeled as a disproportionation to hydronium (H3O(+)) and hydroxyl (OH(-)) ions with W for Ca(2+)-H3O(+) (approximately) equals 33 kJ/sq mol. The regular-solution model of carbonate melts can be applied to problems of carbonatite magma + vapor equilibria and of extrapolating liquidus equilibria to unstudied systems. Calculations on one carbonatite (the Husereau dike, Oka complex, Quebec, Canada) show that the anion solution of its magma contained an OH mole fraction of (approximately) 0.07, although the vapor in equilibrium with the magma had P(H2O) = 8.5 x P(CO2). F in carbonatite systems is calculated to be strongly partitioned into the magma (as F(-)) relative to coexisting vapor. In the Husereau carbonatite magma, the anion solution contained an F(-) mole fraction of (approximately) 6 x 10(exp -5).

Treiman, Allan H.↗

Exploring Coupled Land-Atmosphere Carbon Dynamics and Seasonal Carbon Forecast Skill

Terrestrial biosphere is an integral part of the climate system and plays a vital role in controlling the dynamics of the Earth’s carbon cycle. In this talk, I will present recent efforts to explore coupled land-atmosphere carbon dynamics and seasonal carbon cycle predictability. First, by imposing an idealized spring drought in coupled land‐atmosphere ensemble simulations, we investigated the impact of a regional drought on land and atmospheric carbon. Through the drought-induced impact on remote meteorology, the capability of the land’s carbon uptake is altered in both the drought area and the adjacent areas. The induced anomalies of the atmospheric CO2 extend to an area up to three times of that of the imposed drought, which suggests that atmospheric transport needs to be considered in the interpretation of the drought impact on carbon anomalies. Increase in column‐averaged monthly CO2 is at the edge of the uncertainty from single soundings of current greenhouse gas observing satellites. Secondly, the seasonal carbon forecast skill was explored using NASA’s subseasonal-to-seasonal (S2S) ensemble forecast and terrestrial biosphere model. The result demonstrates an ability to accurately predict spring-summer carbon uptake in the Northern Hemisphere mid and high latitude land at multi-month leads. The prediction skill appears to be achieved by accurate forecasts of snow removal timing, which provides a latent predictability to the forecast system, and by proper initialization of carbon and nitrogen states. Additionally, I will briefly discuss other ongoing research to improve hydrometeorological prediction by integrating biogeochemical processes, to evaluate forecast skill of wildfire carbon, and to apply subseasonal forecasts to water resources management.

Eunjee Lee↗

Intrinsic self-stressing and low carbon Engineered Cementitious Composites (ECC) for improved sustainability

Highlights: • A self-stressing criterion for ECC was established and experimentally verified. • An intrinsic self-stressing ECC was developed by utilizing LC3 and CSA cement. • Initial maximum expansion and later expansion loss were successfully tailored. • Expansion mechanism was identified by XRD patterns. • Self-stressing ECC has 64% of the carbon footprint of conventional concrete. Engineered Cementitious Composites (ECC) is an emerging cementitious composite material with ultra-high ductility. However, its higher cement dosage limits its material greenness and leads to concerns with drying shrinkage. In this research, an ECC utilizing limestone calcined clay cement (LC3) and calcium sulphoaluminate cement (CSA) is investigated, focusing on minimizing the material's embodied carbon while enhancing its durability with intrinsic self-stressing functionality. A self-stressing criterion is theoretically established and experimentally verified. X-ray diffraction patterns reveal an ettringite quantity that modulates the initial expansion and later expansion-reversal of LC3-CSA-ECC to support a persistent self-stressing mechanism. LC3-CSA-ECC has a lower (64%) carbon footprint and similar embodied energy compared to conventional concrete. When combined with the durability advantage (tiny crack, high ductility of 5.5%, and self-stressing function), this low carbon self-stressing ECC holds promise as a sustainable repair material that lowers the embodied and operational carbon in civil infrastructure.

36 MATERIALS SCIENCE↗

Formation of Carbon–Carbon Interlinkage Bonds under High Pressure

The formation of carbon–carbon interlinkage bonds (CCIBs) via the chemical binding of interlayer carbon atoms of many sp 2 -bonded carbon precursors is an essential step for synthesizing various diamond and diamond-like materials. Although the existence of CCIBs may be reasonably assumed under high-pressure conditions, direct experimental evidence has been scarce. Micro-Raman spectroscopy is here employed to track in situ the evolution of C–C bonds in a pressure range from ambient to 54 GPa. A pressure-induced two-stage (polynomial and linear) shift of the G peak and new generation of the CCIB peak at about 1550 cm –1 are observed in multiple types of layer-structured carbon precursors, including glassy carbon, natural graphite, and carbon nanotubes. In conclusion, the experimental discovery of CCIBs holds significance in comprehending phase transitions of sp 2 -bonded carbon materials and has implications for the advancement of novel carbon structures.

Anode materials↗

Revisiting “Additional Carbon”: Tracking Atmosphere–Ecosystem Carbon Exchange to Establish Mitigation and Negative Emissions From Bio-Based Systems

Climate stabilization plans rely heavily on advanced bioenergy and bioproducts for substitution of fossil-based energy sources and materials, and increasingly, for negative emissions via the direct sequestration of biogenic carbon. Yet, there remain persistent, largely unresolved critiques of bioenergy assessment methodology, particularly in the areas of land use and biogenic carbon accounting. The concept of “additional carbon” calls for evaluating the climate performance of bio-based systems by whether feedstock production creates measurable new local agro-ecosystem uptake of carbon from the atmosphere. This concept is challenging to operationalize for first-generation biofuels, and has largely been advanced as a negative critique. However, carbon additionality is more straightforward to establish—and less critical to overall system mitigation performance—in advanced bioenergy systems. In this Perspective, I review the additional carbon critique, and why it is analytically challenging to address in first-generation biofuel systems based on conventional food crops with large existing markets. Next, I make a case that carbon additionality (1) is more readily achievable with cellulosic feedstocks, (2) is more directly observable for dedicated biomass crops, and (3) is not a strict requirement for achieving net mitigation in carbon-negative bio-based systems. I end by discussing how centering atmosphere–ecosystem carbon exchanges in bio-based system assessment could create new opportunities for enterprise-scale performance monitoring and verification, augmenting and diversifying the current reliance on model-based life-cycle assessment approaches.

54 ENVIRONMENTAL SCIENCES↗

How Much Blue Carbon do Hudson Estuary Marshes Sequester? A Full-Depth Carbon Stock Estimation of Iona Marsh, Lower Hudson, NY

Tidal marshes function as a key ecosystem, by serving as nurseries, improving water quality, protecting biodiversity, preventing erosion of coastlines, and preserving archives of paleoclimate and paleoecology. In the last few decades, researchers have come to appreciate coastal marshes’ carbon sequestration function. However, full peat depth is required for estimating the true carbon content of marshes, and very little research has been done to discover the full peat depth along coastlines. We selected Iona Marsh (73°58’44.972”W, 41°18’6.366”N), situated adjacent to Bear Mountain Park and part of the National Estuarine Research Reserve, to document the belowground storage of blue carbon. In order to calculate marsh volume, three full-depth transects were performed from 2020 to 2022, two from east to west in different regions of the marsh, and one from north to south at a minimum of 10 m intervals. We found that marsh depth ranged from 5.1 m to 13.2 m. We calculated marsh volume from the full peat depth and marsh area, obtained through the National Wetlands Inventory database, by applying the average marsh depth over its entire surface area. In order to calculate carbon content, we extracted a 9m sediment core and used loss-on-ignition (LOI) to determine organic matter, then estimate carbon content as half of the organic matter. We used 198 LOI samples to calculate the carbon, which formed at this site over 6000 years ago. We intend to apply this methodology framework to other marshes in the Hudson region. Because many previous carbon stock estimates only account for the top 1 m of peat, the role of these ecosystems in carbon sequestration is significantly underestimated. By determining the full-depth carbon stock of these marshes, we hope to emphasize the value of marshes to the community, beyond what is traditionally recognized, particularly in light of sea level rise and the vulnerability of marshes to erosion.

Tidal marshes↗

Modeling the effects of carbon payments and forest owner cooperatives on carbon storage and revenue in Pacific Northwest forestlands

The forestlands of the Pacific Northwest store a significant amount of carbon, provide wildlife habitat, generate revenue for forestland owners, and provide for sustainable generation of forest products. Promoting forest carbon storage is increasingly recognized as a key management objective to mitigate climate change. We developed an agent-based model to examine the effectiveness of current land management practices in sustaining forest carbon storage and revenue flows, and the utility of market-based carbon payments in improving carbon storage while also improving revenue generation in the Pacific Northwest. We find that while market based incentives can improve both forest carbon storage and revenue, they are limited in their benefit to small forest owners. Our results highlight the crucial need for additional policy interventions to reduce barriers to market access for small private owners and ensure sustainable forest management in this region. We further show that a forest owners’ cooperative, which aggregates small owners to reduce the costs of participating in a carbon market, can help overcome these barriers and result in both greater carbon storage and a more equitable benefit from carbon payments.

54 ENVIRONMENTAL SCIENCES↗

Electrochemical carbon deposition from CO 2 in molten carbonates: substrate-dependent growth

Electrochemical carbon deposition from molten carbonate salts using inert electrodes and no additional catalyst is systematically examined. At sufficiently cathodic potentials, carbon formation occurs within 30 min and transitions from substrate-dependent nucleation to carbon-on-carbon growth. Although deposits formed on either mild-steel or graphite cathodes exhibit comparable thicknesses and salt contents, their macrostructures differ, reflecting differences in early-stage growth rates and surface chemistry. Characterization by ICP-OES, Raman spectroscopy, SEM/EDS, synchrotron powder X-ray diffraction, and C K-edge X-ray absorption near edge structure reveals that the as-deposited carbon is predominantly disordered sp 2 -bonded material. However, post-treatment reveals latent turbostratic ordering in select samples, indicating that short-range order is established during deposition but is obscured by an entrained electrolyte and kinetically formed amorphous phases. No anode-derived contamination is detected, and carbon grown on graphite cathodes shows minimal metallic impurities. These results clarify the role of cathode surface chemistry and provide pathways for controlling electrode-derived impurity incorporation and carbon structure in catalyst-free molten carbonate systems.

36 MATERIALS SCIENCE↗