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Experimental Validation and Continuous Testing of an On-Purpose High-Yield Pitch Synthesis Process for Producing Carbon Fiber from US Domestic Coal

This project aims to develop technology that converts domestic United States (US) raw coal to high quality, high value, and marketable carbon fiber. More specifically, the project aims to significantly improve the selectivity and yield of carbon fiber produced per ton of coal over conventional coal pitch-based production by using low-severity direct coal conversion technology to maximize the yield of pitch from coal, suitable for production of carbon fiber. To meet the stated objective of developing a technology platform, capable of producing high quality, high-value and marketable carbon fiber from domestic US coal, the proposed scope of work involves testing of a low-severity direct coal liquefaction (LS-DCL) process approach. The isotropic pitch produced from the LS-DCL process will be thermally treated using conventional processes to convert to a liquid crystal or “mesophase” pitch as a precursor for structural carbon fibers. This mesophase pitch will then be melt-spun into fiber, oxygen stabilized, and carbonized using conventional processes. The resulting carbon fiber will be evaluated for mechanical properties and suitability for structural applications such as automotive parts and spars for wind turbine blades. The overall process is expected to significantly lower the cost of fiber compared to state of the art fibers produced from polyacrylonitrile (PAN) precursors.

01 COAL, LIGNITE, AND PEAT↗

Onshore U.S. Carbon Pipeline Deployment: Siting, Safety, and Regulation

Carbon capture, utilization, and storage (CCUS) technology has significant potential to reduce greenhouse gas (GHG) emissions and mitigate the impact of climate change, particularly in hard to decarbonize industrial and commercial sectors. CCUS involves capturing carbon dioxide (CO 2 ) from industrial processes or power generation and utilizing it for other purposes, such as enhanced oil recovery (EOR), or storing the captured CO 2 underground. CCUS technology can reduce the environmental impact of continued fossil fuel use while smoothing the transition to a low-carbon economy. CCUS can create new economic opportunities, such as the development of new industries and job creation, and can enhance energy security by diversifying energy sources. For these reasons, enabling CCUS has become a key objective of the Biden-Harris administration’s clean energy policy and has received bipartisan support. Despite its environmental and economic potential, CCUS faces multiple barriers to widespread deployment. One of the main challenges is the high cost and technical difficulty of implementing and operating large-scale CCUS infrastructure. CCUS remains a relatively expensive way to reduce carbon emissions (e.g., compared to solar photovoltaic technology’s displacement of coal generation). Additionally, financial incentives and supportive policies like those enacted to support solar photovoltaic development, especially at the state level, are inconsistent or nonexistent, which can discourage investment in CCUS projects. There are also technical challenges associated with safe and secure underground CO 2 storage and the development of new carbon utilization technologies. Public opposition to various aspects of CCUS technologies, ranging from concerns that CCUS will extend reliance on fossil fuels to CCUS infrastructure being sited in disadvantaged communities, is a growing challenge. This paper focuses on another significant barrier to broad CCUS deployment: the need for considerable expansion of the dedicated land-based CO 2 pipeline network in the United States to meet CCUS goals and the unique regulatory challenges to its development. To reach carbon emissions targets in the United States by 2050, CCUS technology will need to be supported by tens of thousands of miles of CO 2 pipelines. Estimates range from a minimum of roughly 29,000 pipeline miles (according to a 2020 Great Plains Institute study) to 66,000 pipeline miles (as per a 2021 Princeton University–led study). As of October 2022, however, the U.S. Department of Transportation (U.S. DOT) reports fewer than 5,400 miles of U.S. pipelines carrying CO 2 . This deficit—and what it means for the prospect of moving substantially larger quantities of CO 2 from source to use or storage—threatens to stifle the development of CCUS projects and technologies identified as an important tool to meet emissions targets. The current regulatory landscape facing CO 2 pipeline development can best be described as uncertain. At the federal level, the U.S. DOT Pipeline and Hazardous Materials Safety Administration (PHMSA) oversees safety regulation of pipelines transporting hazardous materials, including CO 2 upon commencement of operation. However, PHMSA’s definition of CO 2 as “a fluid consisting of more than 90 percent CO 2 molecules compressed to a supercritical state” has not been updated since its 1991 addition to the Federal Register. Because CO 2 can be transported in a gaseous, liquid, or supercritical state (indeed, the physical state of CO 2 can fluctuate within a single pipeline due to environmental changes), doubts persist about the extent of PHMSA’s purview—and raise questions about what, if anything, states should do to address this apparent gap. PHMSA has begun a major revision of its existing rules, but the agency does not expect a first draft before 2024. Economic oversight of CO 2 pipelines is even less clear. The Federal Energy Regulatory Commission (FERC) and Surface Transportation Board (STB)—which regulate the rates of interstate oil/natural gas and non-energy pipelines, respectively—have both declined jurisdiction over interstate CO 2 pipelines. This presumably leaves economic regulation to state and/or local governments, but few if any states have the laws or resources in place to oversee just and reasonable rates. Further, the interstate nature of CO 2 pipeline development creates questions around how different states should align their rate-making decisions. Onshore U.S. Carbon Pipeline Deployment: Siting, Safety, and Regulation Currently, regulatory responsibilities regarding CO 2 pipeline siting and permitting fall to state and local governments. The variety of laws and regulations across the country, however, creates a maze of requirements for pipeline developers to navigate. To secure necessary permits, most states require pipeline companies to be “common carriers” that provide transport service to the public at uniform rates. However, the specific definition of that term varies. Some states require clear evidence that a pipeline services the public, while others automatically deem any pipeline company transporting energy products or hazardous materials to be a “common carrier”—with little consideration for accessibility to third parties. Other states have eschewed common-carrier terminology entirely, placing private and publicly accessible pipelines on equal footing. Much like the variation in common-carrier requirements, laws governing eminent domain authority to secure rights-of-way (ROW) to commence construction on a planned pipeline route differ by state. Several states have no laws or rules governing CO 2 pipelines. In addition to creating questions about whether long-standing rules for other pipelines (e.g., natural gas or petroleum products) apply to CO 2 , this policy vacuum leaves local governments as the sole authority over sections of pipe within their boundaries. With dozens of counties along a given route, the probability of inconsistent regulation of the same pipeline is significant. Even in states with CO 2 pipeline laws in place, local regulatory attempts to address rising concerns over pipeline routing and safety have triggered lawsuits by pipeline companies seeking to delimit areas of federal, state, and local government responsibility. Meanwhile, legislators across the country have introduced bills to restrict the application of eminent domain to CO 2 pipeline projects, which could threaten a key means of securing ROW that companies cannot secure through negotiation with landowners. Taken separately, any of these regulatory issues—the narrow federal definition of CO 2 , FERC’s and STB’s decisions that CO 2 pipelines are not within their jurisdiction, and the considerable variation in state and local governments’ laws regulating CO 2 pipeline technologies—are extremely difficult to resolve. Adding the required scale of CO 2 pipeline expansion and the currently identified narrow window of time in which to reach climate target goals, the task becomes even more difficult—and raises a host of urgent questions for regulators. How should CO 2 be defined in federal regulations to ensure consistent safety standards across the country? What is the potential impact radius of a CO 2 pipeline rupture, and how should that inform local emergency response? In the absence of centralized federal oversight, what should state legislatures do to increase alignment for interstate CO 2 pipeline projects? This paper intends to serve as a primer for regulators and stakeholders who seek to better understand the regulatory challenges and opportunities facing this critical infrastructure.

42 ENGINEERING↗

Quantitative, trait-based microbial ecology to accurately model the impacts of nitrogen deposition on soil carbon cycling in the Anthropocene (Final Technical Report)

Atmospheric nitrogen pollution has altered fundamental soil processes, challenging our understanding of the extent to which soils will continue to sequester carbon and slow the pace of future environmental change. While most evidence shows that increases in soil nitrogen have enhanced carbon storage in temperate forests, it remains unclear whether these effects will persist as nitrogen pollution continues to decline. Moreover, there remains uncertainty as to why some forests gain more carbon in response to nitrogen pollution than others. At the heart of this knowledge gap is a failure to link nitrogen–induced shifts in microbial biodiversity with gains or losses in their functional ability to decompose, assimilate, and ultimately stabilize soil carbon. Given that this uncertainty impedes the ability of predictive models to project future soil carbon stocks, there is a critical need to determine how key microbial traits drive soil carbon responses to nitrogen pollution. As such the goals of this project were to: (1) Quantify variation in taxon–specific and community–level microbial traits across gradients in microbial community composition, mycorrhizal symbioses, and nitrogen availability. (2) Integrate empirical data into a novel predictive framework that enhances our ability to project the regional soil carbon consequences of historical nitrogen pollution in temperate forests.

54 ENVIRONMENTAL SCIENCES↗

Embodied Carbon Reduction in New Construction: Reference Guide

The U.S. Department of Energy launched the Advanced Building Construction (ABC) Initiative in 2019 to modernize and streamline building renovation and construction processes that facilitate the integration of high-performance and low-carbon solutions in the U.S. building stock. There are four attributes of ABC that are the focus of the Initiative: affordable, fast, appealing, and low carbon. Substantial improvements have been made to reduce operational carbon emissions of buildings through efficiency and electrification. However, to achieve low-carbon new construction buildings, increased efforts to reduce the embodied carbon of buildings are needed. Embodied carbon emissions in buildings come primarily from the manufacturing of building envelope materials such as concrete, steel, lumber, and glass, among others. Recent studies show that construction and renovation of buildings account for 5% of energy use and 10% of carbon emissions globally.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Low-cost, Highly Efficient and Fast Thermally Pressed Scalable Carbon-based Planar Perovskite Solar Cells

This Final Technical Report summarizes work completed under Award Number DEEE0009833, titled "Low-cost, Highly Efficient and Fast Thermally Pressed Scalable Carbon-based Planar Perovskite Solar Cells." The project addressed the central technical problem that carbon-electrode perovskite solar cells (C-PSCs) can reduce electrode costs and improve environmental durability, but they have historically lagged noble-metalcontact devices due to poor carbon/perovskite contact, high carbon-electrode resistance, imperfect hole extraction, and insufficient operational stability. The Statement of Project Objectives (SOPO), therefore, required systematic engineering of thermally pressed carbon-based planar perovskite solar cells by improving the carbon/perovskite interface quality, improving carbon-electrode conductivity, and further increasing device stability. The work advanced understanding of carbon-based perovskite photovoltaics by connecting device performance to three coupled mechanisms: interfacial recombination at the perovskite/hole-transport-layer/carbon stack; lateral and vertical transport losses in carbon contacts; and instability driven by moisture, heat, illumination, ion migration, and slow/variable manufacturing steps.

14 SOLAR ENERGY↗

Modulation of regional carbon uptake by AMOC and alkalinity changes in the subpolar North Atlantic under a warming climate

The slowdown of the Atlantic Meridional Overturning Circulation (AMOC) and associated consequences on ocean carbon uptake could have large implications for the Earth's climate system and its global carbon cycle. This study analyzes ten Earth System Models from the Coupled Model Intercomparison Project Phase 6 (CMIP6) and reveals that the regional carbon uptake in the subpolar North Atlantic under a high CO 2 emission scenario moderately correlates with the decline in AMOC at 40°N. AMOC transports warm and salty subtropical waters to the subpolar regions. Models with stronger AMOC slowdown generally exhibit weaker surface warming and larger decline of surface salinity and alkalinity. We consider two plausible mechanisms linking the AMOC slowdown to the decline of regional CO 2 uptake: the reduction in surface alkalinity and diminished subduction. The decline of surface salinity and alkalinity reduces the ocean's capacity to buffer acids leading to a reduced CO 2 uptake. This important contribution is unique to the North Atlantic. Diminished convective mixing and subduction of surface water can further decrease the downward transport of anthropogenic carbon, as also shown in previous research. The centennial trends of p CO 2 are decomposed into four components driven by temperature, salinity, alkalinity and dissolved inorganic carbon, revealing that alkalinity and dissolved inorganic carbon are both significant contributors. The alkalinity-driven p CO 2 essentially follows surface salinity, establishing the linkage between AMOC slowdown and alkalinity decline. Our results indicate that alkalinity changes are important for the interplay between AMOC and the regional carbon sequestration ability across the late 20 th and the entirety of the 21 st century in the subpolar North Atlantic.

AMOC↗

Rapidly changing high-latitude seasonality: Implications for the 21st century carbon cycle in Alaska: Modeling Archive

This Modeling Archive is in support of an NGEE Arctic publication "Rapidly changing high-latitude seasonality: Implications for the 21st century carbon cycle in Alaska" DOI: 10.1088/1748-9326/ac4362.The dataset contains "ecosys" model outputs reported in Shirley et al. (2022) that explored how climate warming will shift carbon cycle seasonality in Alaska. The study used analysis of seasonal dynamics to support the prediction that high-latitude ecosystems are carbon sinks and will continue to accumulate carbon throughout the century. The study predicts surprisingly large increases in spring net carbon uptake that result in larger net carbon uptake in spring than in summer by year 2100. Included as *.nc files are modeled daily net ecosystem exchange (NEE), net primary productivity (NPP), heterotrophic respiration (Rh), autotrophic respiration (Ra), gross primary productivity (GPP), and plant nitrogen uptake. The output is provided (1) at 25 km resolution across Alaska; (2) for years 2010 through 2100. Scripts to generate publication figures included as text files (*.m) from MATLAB. A user guide included as *.pdf.The Next-Generation Ecosystem Experiments: Arctic (NGEE Arctic), was a research effort to reduce uncertainty in Earth System Models by developing a predictive understanding of carbon-rich Arctic ecosystems and feedbacks to climate. NGEE Arctic was supported by the Department of Energy's Office of Biological and Environmental Research. The NGEE Arctic project had two field research sites: 1) located within the Arctic polygonal tundra coastal region on the Barrow Environmental Observatory (BEO) and the North Slope near Utqiagvik (Barrow), Alaska and 2) multiple areas on the discontinuous permafrost region of the Seward Peninsula north of Nome, Alaska. Through observations, experiments, and synthesis with existing datasets, NGEE Arctic provided an enhanced knowledge base for multi-scale modeling and contributed to improved process representation at global pan-Arctic scales within the Department of Energy's Earth system Model (the Energy Exascale Earth System Model, or E3SM), and specifically within the E3SM Land Model component (ELM).

54 ENVIRONMENTAL SCIENCES↗

Millimeter-scale variations of stable isotope abundances in carbonates from banded iron-formations in the Hamersley Group of Western Australia

Several diamond drill cores from formations within the Hamersley Group of Western Australia have been studied for evidence of short-range variations in the isotopic compositions of the carbonates. For a set of 32 adjacent microbands analyzed in a specimen from the Marra Mamba Iron Formation, carbon isotope compositions of individual microbands ranged from -2.8 to -19.8 per mil compared to PDB and oxygen isotope compositions ranged from 10.2 to 20.8 per mil compared to SMOW. A pattern of alternating abundances was present, with the average isotopic contrasts between adjacent microbands being 3.0 per mil for carbon and 3.1 per mil for oxygen. Similar results were obtained for a suite of 34 microbands (in four groups) from the Bruno's Band unit of the Mount Sylvia Formation. Difficulties were experienced in preparing samples of single microbands from the Dales Gorge Member of the Brockman Iron Formation, but overall isotopic compositions were in good agreement with values reported by previous authors. Chemical analyses showed that isotopically light carbon and oxygen were correlated with increased concentrations of iron. The preservation of these millimeter-scale variations in isotopic abundances is interpreted as inconsistent with a metamorphic origin for the isotopically light carbon in the BIF carbonates. A biological origin is favored for the correlated variations in 13C and Fe, and it is suggested that the 13C-depleted carbonates may derive either from fermentative metabolism or from anaerobic respiration. A model is presented in which these processes occur near the sediment-water interface and are coupled with an initial oxidative precipitation of the iron.

NASA Program Exobiology↗

Taking Stock of Circumboreal Forest Carbon With Ground Measurements, Airborne and Spaceborne LiDAR

The boreal forest accounts for one-third of global forests, but remains largely inaccessible to ground-based measurements and monitoring. It contains large quantities of carbon in its vegetation and soils, and research suggests that it will be subject to increasingly severe climate-driven disturbance. We employ a suite of ground-, airborne- and space-based measurement techniques to derive the first satellite LiDAR-based estimates of aboveground carbon for the entire circumboreal forest biome. Incorporating these inventory techniques with uncertainty analysis, we estimate total aboveground carbon of 38 +/- 3.1 Pg. This boreal forest carbon is mostly concentrated from 50 to 55degN in eastern Canada and from 55 to 60degN in eastern Eurasia. Both of these regions are expected to warm >3 C by 2100, and monitoring the effects of warming on these stocks is important to understanding its future carbon balance. Our maps establish a baseline for future quantification of circumboreal carbon and the described technique should provide a robust method for future monitoring of the spatial and temporal changes of the aboveground carbon content.

Biomass↗

Natural Ocean Carbon Cycle Sensitivity to Parameterizations of the Recycling in a Climate Model

Sensitivities of the oceanic biological pump within the GISS (Goddard Institute for Space Studies ) climate modeling system are explored here. Results are presented from twin control simulations of the air-sea CO2 gas exchange using two different ocean models coupled to the same atmosphere. The two ocean models (Russell ocean model and Hybrid Coordinate Ocean Model, HYCOM) use different vertical coordinate systems, and therefore different representations of column physics. Both variants of the GISS climate model are coupled to the same ocean biogeochemistry module (the NASA Ocean Biogeochemistry Model, NOBM), which computes prognostic distributions for biotic and abiotic fields that influence the air-sea flux of CO2 and the deep ocean carbon transport and storage. In particular, the model differences due to remineralization rate changes are compared to differences attributed to physical processes modeled differently in the two ocean models such as ventilation, mixing, eddy stirring and vertical advection. GISSEH(GISSER) is found to underestimate mixed layer depth compared to observations by about 55% (10 %) in the Southern Ocean and overestimate it by about 17% (underestimate by 2%) in the northern high latitudes. Everywhere else in the global ocean, the two models underestimate the surface mixing by about 12-34 %, which prevents deep nutrients from reaching the surface and promoting primary production there. Consequently, carbon export is reduced because of reduced production at the surface. Furthermore, carbon export is particularly sensitive to remineralization rate changes in the frontal regions of the subtropical gyres and at the Equator and this sensitivity in the model is much higher than the sensitivity to physical processes such as vertical mixing, vertical advection and mesoscale eddy transport. At depth, GISSER, which has a significant warm bias, remineralizes nutrients and carbon faster thereby producing more nutrients and carbon at depth, which eventually resurfaces with the global thermohaline circulation especially in the Southern Ocean. Because of the reduced primary production and carbon export in GISSEH compared to GISSER, the biological pump efficiency, i.e., the ratio of primary production and carbon export at 75 m, is half in the GISSEH of that in GISSER, The Southern Ocean emerges as a key region where the CO2 flux is as sensitive to biological parameterizations as it is to physical parameterizations. The fidelity of ocean mixing in the Southern Ocean compared to observations is shown to be a good indicator of the magnitude of the biological pump efficiency regardless of physical model choice.

Antarctic Ocean↗

Measuring Mangrove Carbon Loss and Gain in Deltas

Demand for mangrove forest resources has led to a steady decline in mangrove area over the past century. Land conversions in the form of agriculture, aquaculture and urbanization account for much of the deforestation of mangrove wetlands. However, natural processes at the transition zone between land and ocean can also rapidly change mangrove spread. In this study, we applied a robust field-based carbon inventory and new structural and temporal remote sensing techniques to quantify the magnitude and change of mangrove carbon stocks in major deltas across Africa and Asia. From 2000–2016, approximately 1.6% (12 270 ha) of the total mangrove area within these deltas disappeared, primarily through erosion and conversion to agriculture. However, the rapid expansion of mangroves in some regions during this same period resulted in new forests that were taller and more carbon-dense than the deforested areas. Because of the rapid vertical growth rates and horizontal expansion, new mangrove forests were able to offset the total carbon losses of 5 332 843 Mg C by 44%. Each hectare of new mangrove forest accounted for ∼84% to ∼160% of the aboveground carbon for each hectare of mangrove forest lost, regardless of the net change in mangrove area. Our study highlights the significance of the natural dynamics of erosion and sedimentation on carbon loss and sequestration potential for mangroves over time. Areas of naturally regenerating mangroves will have a much larger carbon sequestration potential if the rate of mangrove deforestation of taller forests is curbed.

canopy height↗

Global Carbon Cycle and Climate Feedbacks in the NASA GISS ModelE2.1

We present results from the NASA GISS ModelE2.1‐G‐CC Earth System Model with coupled climate‐carbon cycle simulations that were submitted to the sixth phase of the Coupled Model Intercomparison Project (CMIP6) Coupled Climate‐Carbon Cycle MIP (C4MIP). Atmospheric CO2 concentration and carbon budgets for the land and ocean in the historical simulations were generally consistent with observations. Low simulated atmospheric CO2 concentrations during 1850‐1950 were due to excess uptake from prescribed land cover change, which erroneously replaced arid shrublands with higher biomass crops, and assumed high 2004 LAI values in vegetated lands throughout the historical simulation. At the end of the historical period, slightly higher simulated CO2 than observed resulted from the land being an insufficient net carbon sink, despite the net effect of CO2 fertilization and warming‐induced increases to leaf photosynthetic capacity. The global ocean carbon uptake agreed well with the observations with the largest discrepancies in the low latitudes. Future climate projection at 2091‐2100 agreed with CMIP5 models in the northward shift, of temperate deciduous forest climate and expansion across Eurasia along 60 °N latitude, and dramatic regional biome shifts from drying and warming in continental Europe. Carbon feedback parameters were largely similar to the CMIP5 model ensemble. For our model, the variation of land feedback parameters within the uncertainty arises from the fertilization feedback being less sensitive due to lack of increased vegetation growth, and the comparably more negative ocean carbon‐climate feedback is due to the large slowdown of the Atlantic overturning circulation.

Carbon cycle↗

Mineral Inputs, Paleoecological Change, and Holocene Carbon Accumulation at a Boreal Peatland in the Hudson Bay Lowlands, Canada

The Hudson Bay Lowlands (HBL) is a vast contiguous peatland extending over >370,000 km2 in Canada's boreal-subarctic, and is the traditional land of the Omushkego Cree. It is currently undergoing climatic warming alongside other anthropogenic stressors, and contains a large below-ground carbon pool. Understanding how climate variability and multiple stressors impact peat accumulation in this region is critical to discerning how northern peatlands will respond to future climate and land-use changes. Pollen- and macrofossil-based paleoecological reconstructions, and analyses of aluminum (Al) and titanium (Ti) fluxes in a Holocene-aged peat core (VM375) taken from a bog in the Attawapiskat watershed were conducted to link ecosystem changes with hydroclimate and long-term carbon storage. Peat initiation is dated to 5780 cal yr B.P., coincident with land emergence driven by glacial isostatic adjustment. From 4500 to 4200 cal yr B.P., apparent rate of carbon accumulation increased, and was linked to more rapid rates of peat accretion and increases in minerotrophic indicators in the pollen record. This increase in peat accretion and shift in vegetation composition co-occur with higher rates of mineral influx as shown by Ti and Al concentrations, which may have supplied nutrients. A fen to bog transition takes place ~3300 cal yr B.P., with increases in Sphagnum spores and macrofossils, and a decline in the apparent rate of carbon accumulation relative to the earlier half of the record, where paleoecological proxies indicate treed wetland and fen stages. Since peat inception, the total carbon stock of the 260-cm peat column is 110 kg C m−2. This multi-proxy record shows an association between changing peat types and variability in apparent rates of carbon accumulation, and supports the hypothesis that mineral nutrients either supplied by surface hydrology or by eolian deposition played a role in Holocene peat carbon accumulation in eastern North American boreal peatlands.

Dust↗

Investigation of the effect of etch pits on the material properties of carbon fiber structures

It is well known that etch pits are formed on carbon surfaces during their consumption in reactive gas environments such as during ablation of carbon-based thermal protection system (TPS) materials. These pits start out from atomic defects on the carbon surface, grow in size and then ultimately lead to the complete removal of the solid carbon material [1, 2]. However, the effect of such etch pits on the material properties of carbon ablators such as FiberForm are poorly understood, as the maximum size of pits are on the order of microns in size, which makes them hard to observe experimentally. Hence, we have developed a module within the Porous Microstructure Analysis code PuMA [3] that can generate etch pits on an arbitrary material surface, with a prescribed distribution of pit size and density. Figure 1 shows a FiberForm sample with artificially generated pits of varying radii and pit density. We use this newly developed module to calculate material properties of FiberForm, which is the base material for one of the most commonly used TPS materials - Phenolic Impregnated Carbon Ablator (PICA). The detailed microstructure of FiberForm in PuMA will either be generated synthetically or obtained from X-ray microtomography [4]. Our simulations show that material properties such as the thermal conductivity and tortuosity decrease with increasing degree of pitting. This will be helpful to more accurately predict the degradation of carbon-based TPS during ablation, and furthermore may allow us to identify previously unknown TPS failure modes due to pitting.

PuMA↗

Investigation of the Effect of Etch Pits on the Material Properties of Carbon Fiber Structures

It is well known that etch pits are formed on carbon surfaces during their consumption in reactive gas environments such as during ablation of carbon-based thermal protection system (TPS) materials. These pits start out from atomic defects on the carbon surface, grow in size and then ultimately lead to the complete removal of the solid carbon material. However, the effect of such etch pits on the material properties of carbon ablators such as FiberForm are poorly understood, as the maximum size of pits are on the order of microns in size, which makes them hard to observe experimentally. Hence, we have developed a module within the Porous Microstructure Analysis code PuMA that can generate etch pits on an arbitrary material surface, with a prescribed distribution of pit size and density. We use this newly developed module to calculate material properties of FiberForm, which is the base material for one of the most commonly used TPS materials - Phenolic Impregnated Carbon Ablator (PICA). The detailed microstructure of FiberForm in PuMA will either be generated synthetically or obtained from X-ray microtomography. Our simulations show that material properties such as the thermal conductivity and tortuosity decrease with increasing degree of pitting. This will be helpful to more accurately predict the degradation of carbon-based TPS during ablation, and furthermore may allow us to identify previously unknown TPS failure modes due to pitting.

PuMA↗

Feasibility Study of Real-Time Carbon Emission Responsive Electric Vehicle Charging Control in Buildings: Preprint

With the progressing electrification of the transportation sector, the source of carbon emissions is gradually shifting from fossil fuel to grid electricity because of electric vehicles (EVs). The carbon intensity of the grid can fluctuate significantly within hours due to the time-varying power generation mix. Therefore, shifting EV charging loads to cleaner hours in response to the carbon intensity signals can reduce carbon emissions. Existing EV charging control methods typically consider the electricity price or the available generation by distributed energy resources (e.g., photovoltaics) to inform decision-making. Such methods tend to reduce energy costs but may neglect the environmental impact of EV charging activities. We propose and compare four carbon emission responsive EV charging controllers with various control rules. The proposed controllers are evaluated based on simulation experiments using metrics such as carbon emission reduction potential, state of charge (SOC) at departure, and peak demand. We found that the need of EV owners to have full batteries at departure could lead to an emission increase when the curtailed EV charge was compensated before departure. Further, up to 12.7% of carbon emission reduction can be achieved if the EV owners reduce the target SOC at departure by less than 15%.

carbon emission↗

Iodine Co-Precipitation with Calcium Carbonate in the Presence of Silica Ions - 20360

Historical releases of I-129 to the subsurface at the U.S. Department of Energy Hanford Site have resulted in large dilute plumes that cover an area of over 50 km{sup 2}. The most concentrated I-129 plume is associated with the 200 West Area in the 200-UP-1 operable unit of the Hanford Central Plateau, where peak concentrations have been measured up to 30 times the drinking water standard of 1 pCi/L. The mobility of iodine depends on many factors, including chemical speciation, pH, redox conditions, as well as the presence of organic matter, calcium carbonate minerals and microbial activities. Speciation measurements estimate that the majority of the iodine (∼76%) in Hanford groundwater exists as iodate. Information on processes that affect iodate mobility in the Hanford subsurface support evaluation of environmental management options for the I-129 plumes. Iodate can be incorporated into calcium carbonate, which is a potential mechanism of naturally attenuating radioiodine in groundwater. However, the silica content in porewater may impact the contaminant-calcium carbonate incorporation process. Silica is one of the most abundant elements in nature and can have an impact on chemical weathering of alkaline-earth carbonates in the environment. Hence, this research aims to advances knowledge of the iodine co-precipitation process with calcium carbonate in the presence of silica. This information supports the technical basis evaluation of natural attenuation for I-129. Samples for these studies were prepared using calcium carbonate-forming solutions that included certified grade sodium meta-silicate nonahydrate (Na{sub 2}SiO{sub 3}), calcium chloride dehydrate (CaCl{sub 2}.2H{sub 2}O), sodium carbonate (NaCO{sub 2}), and sodium hydroxide (NaOH) solutions for pH adjustments. Triplicate samples were prepared with silica concentrations in the solution of 0 mM, 0.5 mM and 20 mM, mixed with an iodate standard (1000 ppm of IO{sub 3}{sup -} in H{sub 2}O) and sampled over a one-week period. Preliminary data analyses suggest that less iodine remains in solution in the presence of silica (average remaining aqueous fraction 0.23±0.03 at 20 mM of Si) relative to samples without silica (0.52±0.06); an indication that more iodine has been sorbed or incorporated into precipitates. However, the mechanisms for this behavior are still under investigation and need to be interpreted relative to pore water compositions that are representative of Hanford site-specific conditions. Scanning electron microscope equipped with energy dispersive spectroscopy (SEM-EDS) analyses were performed to observe the solid phase morphology in these experiments and showed rhombohedral calcite crystals covered with amorphous Si floccules. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Influence of Real Gas Effects on Chemical Kinetics in Oxycombustion in Supercritical Carbon Dioxide

Oxycombustion in supercritical carbon dioxide is an integral part of the Allam Cycle, a technology that enables carbon-neutral use of fossil-fuels and carbon-negative use of biofuels. We simulate oxycombustion in a realistic combustor geometry for two sets of fuel conditions: pure methane, and a 40 percent methane/60 percent carbon dioxide blend, both at 343.15 K. The fuel jet mixes with a preheated swirler of 20 percent oxygen and 80 percent carbon dioxide at 1005.35 K, with a 100 percent carbon dioxide coflow at 783.15 K. The entire system operates at a pressure of 300 bar, putting the entire system above the critical temperature and pressure of carbon dioxide. Simulations are performed using PeleC, a compressible block-structured adaptive-mesh refinement (AMR) reacting flow code. Direct comparison of results using thermodynamically self-consistent implementations of the ideal gas equation of state and the Soave-Redlich-Kwong (SRK) equation of state allow quantification of the real gas impacts on combustion kinetics, flow temperatures, and pollutant formation.

carbon dioxide↗