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All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Leveraging the bioeconomy for carbon drawdown

Stringent climate change mitigation scenarios rely on large-scale drawdown of carbon dioxide from the atmosphere. Amongst drawdown technologies, bioenergy with carbon capture and sequestration (BECCS) has received considerable attention in the climate mitigation literature. Recently, attention has shifted further from a relatively narrow focus on BECCS to a broader focus on Biomass Carbon Removal and Storage (BiCRS). The concept of BiCRS has the potential to enable a future where the climate mitigation value of biomass resources is more valuable than the energy value, due to the potential to remove and sequester large quantities atmospheric CO2. This article provides a qualitative overview of prominent BiCRS technologies from which a set of the most promising technologies are assessed quantitively through life cycle assessment. There are numerous opportunities to incorporate carbon removal and management within the bioeconomy, but the majority of immediate carbon removal potential exists in four bioproducts: bioenergy, bioplastics, biochar, and wood products. We analyze the life cycle greenhouse gas emissions and disposition of sequestered carbon over 10 000 years for four bioproducts representative of each broader category: an advanced BECCS pathway, biopolyethylene, oriented strand board, and biochar soil amendment. We find that the BECCS pathway has the greatest magnitude and durability of CO2 storage over all time horizons. However, non-BECCS pathways achieve 34–64% of the drawdown magnitude relative to BECCS and retain 55–67% of their initial drawdown over 100 years (central estimate). We identify three engineering strategies for enhancing carbon drawdown: reducing biomass supply chain emissions, maximizing carbon stored in long-lived products, and extending the term of carbon storage. Finally, we highlight the need to characterize both the magnitude and permanence of carbon drawdown as a means for policymakers and technology developers to deploy limited biomass resources to maximize mitigation benefits.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Leveraging the bioeconomy for carbon drawdown

Stringent climate change mitigation scenarios rely on large-scale drawdown of carbon dioxide from the atmosphere. Amongst drawdown technologies, bioenergy with carbon capture and sequestration (BECCS) has received considerable attention in the climate mitigation literature. Recently, attention has shifted further from a relatively narrow focus on BECCS to a broader focus on Biomass Carbon Removal and Storage (BiCRS). The concept of BiCRS has the potential to enable a future where the climate mitigation value of biomass resources is more valuable than the energy value, due to the potential to remove and sequester large quantities atmospheric CO 2 . This article provides a qualitative overview of prominent BiCRS technologies from which a set of the most promising technologies are assessed quantitively through life cycle assessment. There are numerous opportunities to incorporate carbon removal and management within the bioeconomy, but the majority of immediate carbon removal potential exists in four bioproducts: bioenergy, bioplastics, biochar, and wood products. We analyze the life cycle greenhouse gas emissions and disposition of sequestered carbon over 10,000 years for four bioproducts representative of each broader category: an advanced BECCS pathway, biopolyethylene, oriented strand board, and biochar soil amendment. We find that the BECCS pathway has the greatest magnitude and durability of CO 2 storage over all time horizons. However, non-BECCS pathways achieve 34–64% of the drawdown magnitude relative to BECCS and retain 55–67% of their initial drawdown over 100 years (central estimate). We identify three engineering strategies for enhancing carbon drawdown: reducing biomass supply chain emissions, maximizing carbon stored in long lived products, and extending the term of carbon storage. Finally, we highlight the need to characterize both the magnitude and permanence of carbon drawdown as a means for policymakers and technology develo pers to deploy limited biomass resources to maximize mitigation benefits.

09 BIOMASS FUELS↗
DOE OSTI2020

Organo–organic and organo–mineral interfaces in soil at the nanometer scale

The capacity of soil as a carbon (C) sink is mediated by interactions between organic matter and mineral phases. However, previously proposed layered accumulation of organic matter within aggregate organo–mineral microstructures has not yet been confirmed by direct visualization at the necessary nanometer-scale spatial resolution. Here, we identify disordered micrometer-size organic phases rather than previously reported ordered gradients in C functional groups. Using cryo-electron microscopy with electron energy loss spectroscopy (EELS), we show organo–organic interfaces in contrast to exclusively organo–mineral interfaces. Single-digit nanometer-size layers of C forms were detected at the organo–organic interface, showing alkyl C and nitrogen (N) enrichment (by 4 and 7%, respectively). At the organo–mineral interface, 88% (72–92%) and 33% (16–53%) enrichment of N and oxidized C, respectively, indicate different stabilization processes than at organo–organic interfaces. However, N enrichment at both interface types points towards the importance of N-rich residues for greater C sequestration.

58 GEOSCIENCES↗
DOE OSTI2025

The role of Ca-bridged organic matter in an alkaline soil, as revealed by multimodal chemical imaging

Mineral–organic matter (OM) studies have predominantly focused on acidic soils that are abundant in iron (Fe) oxides and aluminum (Al) oxides. We have probed mineral–OM interactions in an alkaline or calcareous soil of the Aridisols class. Unlike the role of Fe and Al, the role of Ca-minerals (particularly calcite), which are ubiquitous in alkaline soils, in OM sequestration is not well understood. Multiple recent model studies with aqueous Ca2+ or synthetic calcite and a suite of OM compounds have shown Ca-OM assemblages to be spatially correlated with calcite at the microscale. To study the chemical state of both Ca and Fe and their competing role in soil organic matter (SOM) stabilization, we performed laboratory characterization using x-ray diffraction, Mössbauer spectroscopy, x-ray photoelectron spectroscopy, scanning electron microscopy, and scanning transmission electron microscopy, alongside synchrotron-based microscale chemical imaging using scanning transmission x-ray microscopy combined with near-edge x-ray absorption fine structure. Ca mineral–organic associations were found to be ubiquitous in this system and are likely critical for understanding SOM stabilization/degradation in alkaline soils. From our findings on mineralogy, speciation, and the nature of Ca-OM bridging, we identified differences in C and Ca chemistry based on the relative location of OM to Ca minerals. The OM near the calcite crystal was enriched in lipid and protein moieties, Ca-OM next to Fe minerals displayed a strong contribution from aromatic compounds, while on the surface of microbes, the carbonate was believed to be of microbial in origin, as also suggested by preliminary works reporting on the formation of amorphous calcite or nano-calcite. In Ca-OM admixed with carbonate, it was difficult to distinguish Ca-associated OM from amorphous calcite or nano-calcite.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Practical Guide to Measuring Wetland Carbon Pools and Fluxes

Abstract Wetlands cover a small portion of the world, but have disproportionate influence on global carbon (C) sequestration, carbon dioxide and methane emissions, and aquatic C fluxes. However, the underlying biogeochemical processes that affect wetland C pools and fluxes are complex and dynamic, making measurements of wetland C challenging. Over decades of research, many observational, experimental, and analytical approaches have been developed to understand and quantify pools and fluxes of wetland C. Sampling approaches range in their representation of wetland C from short to long timeframes and local to landscape spatial scales. This review summarizes common and cutting-edge methodological approaches for quantifying wetland C pools and fluxes. We first define each of the major C pools and fluxes and provide rationale for their importance to wetland C dynamics. For each approach, we clarify what component of wetland C is measured and its spatial and temporal representativeness and constraints. We describe practical considerations for each approach, such as where and when an approach is typically used, who can conduct the measurements (expertise, training requirements), and how approaches are conducted, including considerations on equipment complexity and costs. Finally, we review key covariates and ancillary measurements that enhance the interpretation of findings and facilitate model development. The protocols that we describe to measure soil, water, vegetation, and gases are also relevant for related disciplines such as ecology. Improved quality and consistency of data collection and reporting across studies will help reduce global uncertainties and develop management strategies to use wetlands as nature-based climate solutions.

Bansal, Sheel (ORCID:0000000312331707)↗
DOE OSTI2024

Model code and data: biomass allocation adjustments induced by elevated CO2 and warming in a C3 brackish marsh, 2017-2022, Maryland

This dataset and R script accompany the published paper Bruns et al. (2024) in Geophysical Research Letters. The data are from the first six years of a field manipulation of whole-ecosystem warming and elevated CO2 experiment (Salt Marsh Accretion Response to Temperature eXperiment, or SMARTX) in the Smithsonian's Global Change Research Wetland (GCReW), a brackish, microtidal wetland site on a subestuary of the Chesapeake Bay. These data were generated to understand how warming and elevated CO2 interact to structure ecosystem-level responses to global change, particularly in terms of carbon sequestration. The dataset covers 2017-2022 and includes peak annual above ground biomass, annual belowground fine root productivity, and porewater NH4 for each experimental plot. The overall experiment is replicated in two locations on the marsh, a lower elevation zone dominated the C3 sedge S. Americanus and a higher elevation plot dominated by the C4 species. This paper and its data release is only for the C3 plot. Variable descriptions for data file is available in variable_descriptions.pdf. The R script Bruns_et_al_2024_GRL_make_figures.Rmd contains model code and other scripts used to generate all paper figures.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Subtask 1.3 – Integrated Carbon Capture and Storage for North Dakota Ethanol Production

The Energy & Environmental Research Center (EERC), in partnership with Red Trail Energy, LLC (RTE), a North Dakota ethanol producer; the North Dakota Industrial Commission (NDIC) Renewable Energy Program (REP); and the U.S. Department of Energy (DOE), conducted a feasibility and implementation study for a commercial carbon capture and storage (CCS) effort. This subtask provided technical support and developed recommended practices of how small-scale industrial CO2 emitters (<1,000,000 tonnes of CO2 emitted annually) may economically deploy CCS. The 64-million-gallon dry mill RTE ethanol facility, emitting an average 180,000 tonnes of CO2 annually, was the subject of the case study. The positive outcome of this research, which shows technical and economic potential for ethanol–CCS in North Dakota, has resulted in RTE acquiring an approved Permit to Drill on December 2, 2019, for a stratigraphic test well in early 2020, a necessary step toward a North Dakota CO2 Storage Facility Permit (SFP) for the RTE CCS effort. Outcomes include 1) validating the Broom Creek Formation as a regional target for CCS, 2) determining the full carbon life cycle of an industrial fuel production facility with CCS, 3) developing a field implementation plan (FIP) for small-scale CCS, and 4) determining the validity and pathway for using CCS to meet low-carbon fuel (LCF) standards. The technical team included the EERC, RTE, Trimeric Corporation, Schlumberger Carbon Services, and Computer Modelling Group (CMG). Findings from activities conducted November 2016 – May 2020 are summarized as follows. Several key steps have been accomplished toward validating the Broom Creek Formation as a CO2 injection and storage target at the RTE CCS site, including verification of the presence and structure of sandstone layers that may comprise the potential CO2 storage reservoir and the several thousand feet of overlying confining zone. Work included site characterization using existing data, interpretation of seismic data within the study area, and geologic modeling simulation of CO2 injection. Interpreted results estimate 3000 feet of confining zone between the Broom Creek Formation (storage target) and the lowermost underground source of drinking water (e.g., the Fox Hills Formation). The thickness of the Broom Creek injection target varies 230–420 ft within the survey area. Results were used to inform the location of a stratigraphic test well and associated characterization test program. No impediments were identified within the targeted CO2 storage complex that would prevent the project from moving forward. A stratigraphic test well is the next step to validate these results and to acquire remaining data necessary to develop a North Dakota CO2 SFP application. The EERC generated full carbon life cycle estimates for CCS integration with the RTE ethanol facility. Results indicated that an average 40% reduction in CO2 emissions is possible through CCS implementation. Approximately half of the carbon in the overall life cycle for a dry mill ethanol plant is generated through the fermentation process and emitted to the atmosphere; this is the CO2 stream targeted for CCS. The remaining carbon is attributed to corn feedstock farming (diesel, fertilizer), energy for fuel processing (natural gas, electricity), and transportation (diesel) of the fuel product. Life cycle carbon estimates are also affected by the anticipated energy consumption of a potential capture facility, which depend on the type of CO2 product generated. For example, a 30%–40% net CO2 emission reduction is estimated if a liquefied CO2 facility were incorporated compared to a 40%–50% net CO2 reduction if a supercritical “injection-grade” CO2 product is generated; i.e., more energy is required to further refine the CO2 stream, affecting the full carbon life cycle estimates. A CCS FIP was developed and initiated at the RTE CCS site, resulting in the development of several guidance documents: a CO2 Capture Process Design Package, a North Dakota CO2 geologic Storage Permits Template, and a Public Outreach Package for CCS in North Dakota. General FIP components include CO2 capture system, pipeline and well designs; monitoring, verification, and accounting (MVA) plans; geologic characterization and testing programs; and permitting and outreach plans. Vendor bids were also acquired for the CO2 liquefaction facility. Near-surface characterization (groundwater and soil gas sampling) and geologic characterization (seismic survey) were initiated to inform development of a UIC Class VI-compliant MVA plan compliant with a North Dakota CO2 SFP. Designs (well and geologic testing) were completed for a stratigraphic test well compliant with a North Dakota CO2 SFP. In addition, the outreach plan was executed, including community open houses, meetings with city/county/state officials, and development of public materials. Although other entities continued to mature incentive programs in 2019–2020, California and the Internal Revenue Service (IRS) currently provide the most advanced economic opportunities for CCS integrated with fuel production. The California Low-Carbon Fuel Standard (LCFS) adopted a CCS Protocol in January 2019, allowing submittal of a design-based pathway (DBP) application for an approved temporary (not certified) carbon intensity value for a fully engineered facility. An ethanol–CCS DBP application to the California LCFS Program (officially approved February 28, 2020) was developed to show that the RTE CCS effort meets LCFS requirements. The approved DBP provides confidence to advance the project and supports potential investments. Other entities continue to mature incentive programs. The IRS issued guidance in February 2020 that addresses the definition of beginning of construction and revenue procedure on partnerships for the Enhancement of Carbon Dioxide Sequestration Credit (a.k.a. Section 45Q) CCS tax credit program; the IRS anticipates issuing further guidance on issues such as secure geologic storage, utilization qualifications, and recapture of claimed credits. Maturing incentive programs coupled with workable permitting regulations provide confidence to advance CCS projects in North Dakota and support financial investment to proceed with designing, constructing, and implementing CCS projects at small-scale fuel production facilities. The largest hurdles for CCS implementation at small-scale industrial systems are often business/economic-related (i.e., not technical). Market uncertainty already exists for agriculture-based alternative fuels such as corn ethanol, for which production has increased by ~33%, and prices have correspondingly lowered since 2015. Passing the Section 45Q tax credit program improves economic feasibility for CCS but may require external investors for a small business to achieve maximum benefits. Public–private partnerships with NDIC and DOE have resulted in foundational technical and regulatory knowledge, growing stakeholder confidence, and a pathway to implementation that enables similar industrial CCS projects in the region to advance. This subtask was funded through the EERC–DOE Joint Program on Research and Development for Fossil Energy-Related Resources Cooperative Agreement No. DE-FE0024233. Nonfederal funding was provided by NDIC and RTE. The authors would also like to thank CMG, ESRI, IHS, Neuralog, and Schlumberger for allowing the use of their software packages in support of this work.

42 ENGINEERING↗
DOE OSTI2025

Soil carbon accrual and biopore formation across a plant diversity gradient

Plant diversity promotes soil organic carbon (SOC) gains through intricate changes in root-soil interactions and their subsequent influence on soil physical and biological processes. We assessed SOC and pore characteristics of soils under a range of switchgrass-based plant systems 12 years after their establishment. The systems represented a gradient of plant diversity with species richness ranging from 1 to 30 species. We focused on soil biopores as indicators of the legacy of root activity and explored biopore relationships with SOC accumulation. Biopores were measured using X-ray computed micro-tomography. Plant functional richness explained 29 % of bioporosity and 36 % of SOC variation, while bioporosity itself explained 36 % of the variation in SOC. The most diverse plant system (30 species) had the highest SOC, while long-term bare soil fallow and monoculture switchgrass had the lowest. Of particular note was a 2-species mixture of switchgrass (Panicum virgatum L.) and ryegrass (Elymus canadensis), which exhibited the highest bioporosity and achieved SOC levels comparable to those of the systems with 6 and 10 plant species, and were inferior only to the system with 30 species. We conclude that plant diversity may enhance SOC through biopore-mediated mechanisms and suggest a potential for identifying specific plant combinations that may be particularly efficient for fostering biopore formation and, subsequently, SOC sequestration.

Kim, Kyungmin [Seoul National Univ. (Korea, Republ↗
DOE OSTI2024

A Test of Functional Balance Theory for Wetland Biomass Allocation in a Global Change Experiment

Abstract Forecasts of root growth and carbon sequestration under global change are compromised by uncertainty in how plants will allocate biomass between above and belowground pools. Here, we develop a simple model to assess whether functional balance theory can explain a complex biomass allocation response observed in a brackish marsh under experimental warming and elevated CO 2 . Our model shows how treatment‐driven changes in nitrogen supply and demand can explain divergent observations of root growth (i.e., maximum responses under intermediate warming and elevated CO 2 ). The model also reveals a surprising interaction between warming and eutrophication, where enhanced N loading to coastal marshes may reduce adverse impacts of warming on root growth. Our findings provide a mechanistic basis for incorporating biomass allocation into forecast models of marsh evolution. They also provide a general example of using ecological theory to decompose complex net responses observed in multi‐factor global change experiments into constituent processes.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2026

Contrasting carbon dynamics in grazed and flood-prone grasslands on mineral and degraded peat soils

Ecosystem-scale methane (CH₄) flux measurements from grazed grasslands remain scarce, despite their importance for understanding grassland contributions to the global carbon budget. In this study, we present full annual budgets of both carbon dioxide (CO₂) and CH₄ derived from eddy covariance measurements at two contrasting grazed grasslands: a floodplain grassland at Marchegg, Austria, and an intensively grazed pasture at Sherman Barn, California. By combining continuous, year-round observations of CO₂ and CH₄, this study provides a rare, comparative assessment of greenhouse gas dynamics across distinct climatic, hydrological, and management regimes. Our results highlight how environmental conditions, grazing intensity, and hydrology jointly regulate CO₂ exchange and CH₄ emissions, underscoring the importance of including methane alongside net ecosystem exchange when evaluating grassland carbon balances. At Marchegg, characterized by seasonal flooding and moderate horse grazing on mineral soils, the ecosystem acted as a weak carbon sink in 2024, with a GWP 100 of 42.2 ± 113.4 g CO₂ eq m⁻². Net CO₂ uptake (–27.3 ± 30.2 g C m⁻² yr⁻¹) was partly offset by CH₄ emissions (1.6 ± 0.04 g C m⁻² yr⁻¹), which were strongly linked to soil moisture and inundation events. In contrast, Sherman Barn, a cattle pasture on degraded peat soils, was a consistent carbon source in 2019, with a GWP 100 of 567.6 ± 120.5 g CO₂ eq m⁻², associated with high ecosystem respiration during summer. The site released 125.3 ± 32.2 g C m⁻² yr⁻¹ of CO₂ and 3 ± 0.06 g C m⁻² yr⁻¹ of CH₄. Across both sites, net ecosystem exchange was primarily linked to photosynthetically active radiation and vegetation greenness, while CH₄ fluxes were related to soil moisture rather than grazing intensity. Flooding at Marchegg reduced CO₂ uptake but enhanced CH₄ emissions, highlighting the critical role of flood timing within the growing season. Moreover, inundation appeared to suppress the spread of invasive plant species, emphasizing the ecological value of dynamic hydrological regimes. Together, these findings reveal the complexity of grassland carbon budgets and the need for site-specific, year-round CO₂ and CH₄ monitoring to inform climate-adaptive management strategies.

Carbon sequestration↗
DOE OSTI2020

Alley cropping affects perennial bioenergy crop root distribution, carbon, and nutrient stocks

This study quantified root biomass distribution; root accrual of C, N, P, and K; and changes in soil organic carbon (SOC) associated with alley-cropped switchgrass (Panicum virgatum L.), prairie cordgrass (Spartina pectinata Bosc ex Link), intermediate wheatgrass [Thinopyrum intermedium (Host) Barkworth and Dewey ‘Rush’], and a native polyculture planted between rows of ‘NM6’ poplar (Populus maximowiczii × P. nigra) and ‘Fish Creek’ willow (Salix purpurea) at two Minnesota sites (Empire and Granada). After 4 yr since establishment, SOC declined at each site but was not influenced by species selection. NM6 poplar–prairie cordgrass systems had among the highest root biomass, C, and nutrient accrual, with up to 16.3 Mg root biomass, 7.0 Mg C, 175 kg N, 31 kg P, and 97 kg K ha -1 . Fine roots were the largest fraction of belowground biomass, although course roots were also a large fraction for poplar and prairie cordgrass. Tree roots extended to 6 m into the crop alley, although 85–89% were within 1 m of tree rows, depending on tree species. Crop fine root biomass was reduced up to 67% at 1 m from tree rows and 20% at 3.5 m and was up to 142% greater in willow than in poplar alleys. Total root C was predominated by poplars at Empire regardless of herbaceous crop type, whereas the proportions of tree and crop root C varied by crop at Granada. These results suggest that prairie cordgrass is well suited to alley cropping and that, due to the competitive ability of poplars, productivity, C sequestration, and nutrient accrual may be greater in willow systems in the long term.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2026

Pre- and post-coppice production and biomass chemistry of eastern cottonwood and hybrid poplars in the southeastern US

Sustainably grown feedstocks for bioenergy and bioproducts are important tools to fight climate change, provide ecosystem services, and sequester carbon. Populus species including hybrid poplars have been utilized around the world, and in the southeastern US native eastern cottonwood (P. deltoides) is often favored due to its resistance to stem cankers. However, P. deltoides has historically been grown in single stem production and its relative performance in short rotation coppice production, prevalent in Europe, is not well documented. Therefore, this study's goals were to evaluate eastern cottonwood (D × D) and hybrid poplar (P. deltoides × P. maximowiczii (D × M) and P. deltoides × P. trichocarpa (D × T) taxa) productivity under a two-year establishment and two-year coppice cycle, analyze biomass chemistry properties, identify drivers of productivity, and select clones suited for marginal vs. optimal sites. We found that D × M and D × D grew best in both establishment and coppice rotation with production increasing after coppice. Taxa and clones exhibited few differences in select biomass chemistry properties despite differences in growth rate and stem size. Across years and sites, production was correlated with the soil's carbon to nitrogen ratio, percentage of sand, and shrink-swell potential of the soil. A D × M clone ‘9709’ tended to perform better than other tested clones on marginal sites and had the highest survival rate after four years. Overall, this research suggests that Populus species can be grown in coppice rotation in the southeastern US with the potential for hybrid poplars to be successful on certain sites in the region although longer term studies are necessary to confirm these results.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Morphological and crystallographic controls in the replacement of calcite and aragonite by cerussite and otavite

Mineral replacement reactions are essential solid-fluid interactions in natural and industrial processes including metasomatism, diagenesis, and metamorphism, and sequestration of metal toxins from polluted water. In this paper, we explore the morphological evolution of aragonite and calcite (polymorphs of CaCO 3 ) during their replacement by cerussite (PbCO 3 , an isomorph of aragonite) and otavite (CdCO 3 , an isomorph of calcite) in acidic aqueous solutions (with initial pH 3 to 4). Observations using scanning electron and synchrotron-based transmission X-ray microscopies reveal the formation of pseudomorphic shells (~5 to 10 µm thick) of cerussite and otavite when Pb 2+ is reacted with either calcite or aragonite and when Cd 2+ is reacted with aragonite. The formation of pore space at the substrate-precipitate interface and within the precipitate is found to be key in promoting chemical exchange between the dissolving phase and the solution. In contrast, minimal reactivity is observed when Cd 2+ is reacted with calcite. These results demonstrate that the lack of substrate-precipitate epitaxy (either because of inconsistent symmetries or due to large lattice constant mismatch) is a critical factor that enables replacement of primary CaCO 3 minerals by Pb- or Cd-bearing secondary minerals while the presence of epitaxial relationships inhibit those reactions. When calcite and aragonite coexist, the replacement of aragonite by cerussite and otavite occurs preferentially over calcite. We postulate that the relative reactivity of calcite and aragonite to Pb 2+ and Cd 2+ can be determined by interplay between morphological and crystallographic properties of CaCO 3 materials as well as solution chemistry. Our results demonstrate that coupled dissolution-precipitation processes of carbonate minerals play an important role in controlling mobility and bioavailability of lead and cadmium in environments where acidic metal-contaminated water interacts with carbonate-rich rocks and soils.

58 GEOSCIENCES↗
DOE OSTI2022

Interrogating organo-mineral interactions by Py-GC/MS and ToF-SIMS

Soil organic matter (SOM) is crucial to soil fertility and agricultural sustainability in the face of climate change, and organo-mineral interactions are a key mechanism for stabilizing SOM. The stability of mineral-associated organic matter (MAOM) can be approximated by the strength of bonds between biomolecules and mineral surfaces. We hypothesized that factors such as mineral reactivity and solution pH would impact bonding strength. To test these factors, sorption isotherms were performed on minerals differing in particle size, morphology, and reactivity (quartz, goethite, gibbsite, kaolinite, montmorillonite), under two pH conditions (4 and 6), and across a range of tannic acid concentration (0-1400 ppm). The quantity and quality of organo-mineral bonds was assessed by quantifying post-sorption solution compounds using an absorbance plate reader and assessing the thermal energy needed to break bonds using evolved gas analysis (EGA) on a pyrolysis gas chromatograph-mass spectrometer (Py-GC/MS). Organo-mineral surfaces were also interrogated using Time-of-flight secondary ion mass spectrometry (ToF-SIMS). Sorption experiments revealed an asymptotic relationship between sorbed tannic acid and increasing initial concentrations which suggests our concentration range saturated available mineral surfaces. Results indicated that mineral identity, chiefly surface area and native pH, impacted the amount of compound sorbed to mineral surfaces. Evolved gas analyses of organo-mineral samples uncovered increased thermal stability of sorbed compounds compared to our tannic acid standard particularly on the iron oxide, goethite. ToF-SIMS revealed that goethite surface ions were covered by increasing concentrations of adsorbed tannic acid with the replacement of chlorine and sulfate ions by tannic acid related ions. Our results indicate that Py-GC/MS and ToF-SIMS are useful techniques to determine the nature and strength of organo-mineral bonds and are steppingstones to understanding controls on carbon sequestration in terrestrial systems.

58 GEOSCIENCES↗
DOE OSTI2025

Bioindicator “fingerprints” of methane-emitting thermokarst features in Alaskan soils

Permafrost thaw increases the bioavailability of ancient organic matter, facilitating microbial metabolism of volatile organic compounds (VOCs), carbon dioxide, and methane (CH 4 ). The formation of thermokarst (thaw) lakes in icy, organic-rich Yedoma permafrost leads to high CH 4 emissions, and subsurface microbes that have the potential to be biogeochemical drivers of organic carbon turnover in these systems. However, to better characterize and quantify rates of permafrost changes, methods that further clarify the relationship between subsurface biogeochemical processes and microbial dynamics are needed. In this study, we investigated four sites (two well-drained thermokarst mounds, a drained thermokarst lake, and the terrestrial margin of a recently formed thermokarst lake) to determine whether biogenic VOCs (1) can be effectively collected during winter, and (2) whether winter sampling provides more biologically significant VOCs correlated with subsurface microbial metabolic potential. During the cold season (March 2023), we drilled boreholes at the four sites and collected cores to simultaneously characterize microbial populations and captured VOCs. VOC analysis of these sites revealed “fingerprints” that were distinct and unique to each site. Total VOCs from the boreholes included > 400 unique VOC features, including > 40 potentially biogenic VOCs related to microbial metabolism. Subsurface microbial community composition was distinct across sites; for example, methanogenic archaea were far more abundant at the thermokarst site characterized by high annual CH 4 emissions. The results obtained from this method strongly suggest that ∼10% of VOCs are potentially biogenic, and that biogenic VOCs can be mapped to subsurface microbial metabolisms. By better revealing the relationship between subsurface biogeochemical processes and microbial dynamics, this work advances our ability to monitor and predict subsurface carbon turnover in Arctic soils.

anaerobic degradation↗
DOE OSTI2022

Biomass to Biochar: Maximizing the Carbon Value - Executive Summary

Converting biomass to biochar presents exciting opportunities to mitigate climate change, improve forest and soil health, decrease wildfire risk, bolster ecosystem services, and revitalize rural economies. Our expert panel examined how biomass is harvested, converted to biochar and applied and where operational changes and funding could significantly magnify biochar's contributions. To advance knowledge and efficacies, we found that a rigorous combination of coordinated long-term research, market research and development and enhancement of business support infrastructure that leads to collaborative policy development is essential. We also identified how barriers to five specific biochar technology sectors could be overcome and provide guidelines for effective funding.

agriculture↗
DOE OSTI2024

Controls and relationships of soil organic carbon abundance and persistence vary across pedo–climatic regions

One of the largest uncertainties in the terrestrial carbon cycle is the timing and magnitude of soil organic carbon (SOC) response to climate and vegetation change. This uncertainty prevents models from adequately capturing SOC dynamics and challenges the assessment of management and climate change effects on soils. Reducing these uncertainties requires simultaneous investigation of factors controlling the amount (SOC abundance) and duration (SOC persistence) of stored C. We present a global synthesis of SOC and radiocarbon profiles (n Profile = 597) to assess the timescales of SOC storage. We use a combination of statistical and depth–resolved compartment models to explore key factors controlling the relationships between SOC abundance and persistence across pedo–climatic regions and with soil depth. This allows us to better understand (i) how SOC abundance and persistence covary across pedo–climatic regions and (ii) how the depth dependence of SOC dynamics relates to climatic and mineralogical controls on SOC abundance and persistence. We show that SOC abundance and persistence are differently related; the controls on these relationships differ substantially between major pedo–climatic regions and soil depth. For example, large amounts of persistent SOC can reflect climatic constraints on soils (e.g., in tundra/polar regions) or mineral absorption, reflected in slower decomposition and vertical transport rates. In contrast, lower SOC abundance can be found with lower SOC persistence (e.g., in highly weathered tropical soils) or higher SOC persistence (e.g., in drier and less productive regions). We relate variable patterns of SOC abundance and persistence to differences in the processes constraining plant C input, microbial decomposition, vertical C transport and mineral SOC stabilization potential. This process–oriented grouping of SOC abundance and persistence provides a valuable benchmark for global C models, highlighting that pedo–climatic boundary conditions are crucial for predicting the effects of climate change and soil management on future C abundance and persistence.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Minimizing Fraud in the Carbon Offset Market Using Blockchain Technologies

Fraud in the Environmental Benefit Credit (EBC) markets is pervasive. To make matters worse, the cost of creating EBCs is often higher than the market price. Consequently, a method to create, validate, and verify EBCs and their relevance is needed to mitigate fraud. The EBC market has focused on geologic (fossil fuel) CO 2 sequestration projects that are often over budget and behind schedule and has failed to capture the "lowest hanging fruit" EBCs - terrestrial sequestration via the agricultural industry. This project reviews a methodology to attain possibly the least costly EBCs by tracking the reduction of inputs required to grow crops. The use of bio- stimulant products, such as humate, allows a farmer to use less nitrogen without adversely affecting crop yield. Using less nitrogen qualifies for EBCs by reducing nitrous oxide emissions and nitrate runoff from a farmer's field. A blockchain that tracks the bio-stimulant material from source to application provides a link between a tangible (bio-stimulant commodity) and the associated intangible (EBCs) assets. Covert insertion of taggants in the bio-stimulant products creates a unique barcode that allows a product to be digitally tracked from beginning to end. This process (blockchain technology) is so robust, logical, and transparent that it will enhance the value of the associated EBCs by mitigating fraud. It provides a real time method for monetizing the benefits of the material. Substantial amounts of energy are required to produce, transport, and distribute agricultural inputs including fertilizer and water. Intelligent optimization of the use of agricultural inputs can drive meaningful cost savings. Tagging and verification of product application provides a valuable understanding of the dynamics in the water/food energy nexus, a major food security and sustainability issue. As technology in agriculture evolves so to must methods to verify the Enterprise Resource Planning (ERP) potential of innovative solutions. The technology reviewed provides the ability to combine blockchain and taggants ("taggant blockchains") as the engine by which to (1) mitigate fraudulent carbon credits; (2) improve food chain security, and (3) monitor and manage sustainability. The verification of product quality and application is a requirement to validate benefits. Recent upgrades to humic and fulvic quality protocols known as ISO CD 19822 TC134 offers an analytical procedure. This work has been assisted by the Humic Products Trade Association and International Humic Substance Society. In addition, providing proof of application of these products and verification of the correct application of prescriptive humic and bio-stimulant products is required. Individual sources of humate have unique and verifiable characteristics. Additionally, methods for prescription of site- specific agricultural inputs in agricultural fields are available. (See US Patents 734867B2, US 90658633B2.) Finally, a method to assure application rate is required through the use of taggants. Sensors using organic solid to liquid phase change nanoparticles of various types and melting temperatures added to the naturally occurring materials provide a barcode. Over 100 types of nanoparticles exist ensuring numerous possible barcodes to reduce industry fraud. Taggant materials can be collected from soil samples of plant material to validate a blockchain of humic, fulvic and other soil amendment products. Other non-organic materials are also available as taggants; however, the organic tags are biodegradable and safe in the environment allowing for use during differing application timeliness.

54 ENVIRONMENTAL SCIENCES↗