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At least 883 records · Page 49

Isotopic Constraints on the Genesis of Carbonates in Martian Meteorite ALH 84001

Oxygen isotopic analyses in approximately 20 micrometer spots in a chemically diverse suite of carbonates from ALH 84001 show highly variable delta(exp 18)O values from +5.4 to +25.3%. The isotopic data are correlated with the major element composition of the carbonate. The earliest forming (Ca-rich) carbonates have the lowest delta(exp 18)O values and the late-forming Mg-rich carbonates have the highest delta(exp 18)O values. Two models that can explain the isotopic variation were investigated. The carbonates could have formed in a water-rich environment at relatively low, but highly variable temperatures. In this open-system case the lower limit to the temperature variation is approximately 125 C, with fluctuations of over 250 C possible within the constraints of the model, depending on fluid composition. Alternatively the data can be explained by a closed-system model in which carbonates precipitated from a limited amount of a CO2-rich fluid. This scenario can reproduce the range of isotopic values observed, even at relatively high temperatures (greater than 500 C). Thus, the oxygen isotopic compositions do not provide unequivocal evidence for formation of the carbonates at low temperature. Neither of these scenarios is consistent with a biological origin of the carbonates and their associated features. Olivine from ALH 84001 occurs as clusters within orthopyroxene adjacent to fractures containing disrupted carbonate globules and feldspathic shock glass. The inclusions are irregular in shape and range in size from approximately 40 micrometers to submicrometer. The olivine exhibits a limited range of chemical composition from Fo(sub 65) to Fo(sub 66). We measured delta(exp 18)O values of the olivine to be +5.1 +/- 1.4%, indistinguishable within uncertainty from the host orthopyroxene. The data suggest that the olivine formed at high temperature (greater than 800 C), and is probably unrelated to carbonate formation. Instead the olivine probably formed by metamorphic reactions involving either dehydration of hydrous silicates or reduction of opx + spinel. If the reactions took place after carbonate formation, they could have caused devolatilization of siderite, producing the magnetite in the ALH carbonate globules. This scenario is also inconsistent with a biological origin for the features in ALH 84001.

Leshin, Laurie A.↗

Cryogenic Calcite: A Morphologic and Isotopic Analog to the ALH84001 Carbonates

Martian meteorite ALH84001 carbonates preserve large and variable microscale isotopic compositions, which in some way reflect their formation environment. These measurements show large variations (>20%) in the carbon and oxygen isotopic compositions of the carbonates on a 10-20 micron scale that are correlated with chemical composition. However, the utilization of these data sets for interpreting the formation conditions of the carbonates is complex due to lack of suitable terrestrial analogs and the difficulty of modeling under non-equilibrium conditions. Thus, the mechanisms and processes are largely unknown that create and preserve large microscale isotopic variations in carbonate minerals. Experimental tests of the possible environments and mechanisms that lead to large microscale isotopic variations can help address these concerns. One possible mechanism for creating large carbon isotopic variations in carbonates involves the freezing of water. Carbonates precipitate during extensive CO2 degassing that occurs during the freezing process as the fluid s decreasing volume drives CO2 out. This rapid CO2 degassing results in a kinetic isotopic fractionation where the CO2 gas has a much lighter isotopic composition causing an enrichment of 13C in the remaining dissolved bicarbonate. This study seeks to determine the suitability of cryogenically formed carbonates as analogs to ALH84001 carbonates. Specifically, our objective is to determine how accurately models using equilibrium fractionation factors approximate the isotopic compositions of cryogenically precipitated carbonates. This includes determining the accuracy of applying equilibrium fractionation factors during a kinetic process, and determining how isotopic variations in the fluid are preserved in microscale variations in the precipitated carbonates.

Niles, P. B.↗

Carbonates in fractures of Martian meteorite Allan Hills 84001: petrologic evidence for impact origin

Carbonates in Martian meteorite Allan Hills 84001 occur as grains on pyroxene grain boundaries, in crushed zones, and as disks, veins, and irregularly shaped grains in healed pyroxene fractures. Some carbonate disks have tapered Mg-rich edges and are accompanied by smaller, thinner and relatively homogeneous, magnesite microdisks. Except for the microdisks, all types of carbonate grains show the same unique chemical zoning pattern on MgCO3-FeCO3-CaCO3 plots. This chemical characteristic and the close spatial association of diverse carbonate types show that all carbonates formed by a similar process. The heterogeneous distribution of carbonates in fractures, tapered shapes of some disks, and the localized occurrence of Mg-rich microdisks appear to be incompatible with growth from an externally derived CO2-rich fluid that changed in composition over time. These features suggest instead that the fractures were closed as carbonates grew from an internally derived fluid and that the microdisks formed from a residual Mg-rich fluid that was squeezed along fractures. Carbonate in pyroxene fractures is most abundant near grains of plagioclase glass that are located on pyroxene grain boundaries and commonly contain major or minor amounts of carbonate. We infer that carbonates in fractures formed from grain boundary carbonates associated with plagiociase that were melted by impact and dispersed into the surrounding fractured pyroxene. Carbonates in fractures, which include those studied by McKay et al. (1996), could not have formed at low temperatures and preserved mineralogical evidence for Martian organisms.

Carbonates/analysis↗

Micromechanics Modeling of Functionally Graded Interphase Regions in Carbon Nanotube-Polymer Composites

The effective elastic properties of a unidirectional carbon fiber/epoxy lamina in which the carbon fibers are coated with single-walled carbon nanotubes are modeled herein through the use of a multi-scale method involving the molecular dynamics/equivalent continuum and micromechanics methods. The specific lamina representative volume element studied consists of a carbon fiber surrounded by a region of epoxy containing a radially varying concentration of carbon nanotubes which is then embedded in the pure epoxy matrix. The variable concentration of carbon nanotubes surrounding the carbon fiber results in a functionally graded interphase region as the properties of the interphase region vary according to the carbon nanotube volume fraction. Molecular dynamics and equivalent continuum methods are used to assess the local effective properties of the carbon nanotube/epoxy comprising the interphase region. Micromechanics in the form of the Mori-Tanaka method are then applied to obtain the global effective properties of the graded interphase region wherein the carbon nanotubes are randomly oriented. Finally, the multi-layer composite cylinders micromechanics approach is used to obtain the effective lamina properties from the lamina representative volume element. It was found that even very small quantities of carbon nanotubes (0.36% of lamina by volume) coating the surface of the carbon fibers in the lamina can have a significant effect (8% increase) on the transverse properties of the lamina (E22, k23, G23 and G12) with almost no affect on the lamina properties in the fiber direction (E11 and v12).

Seidel, Gary D.↗

Cryogenic Origin for Mars Analog Carbonates in the Bockfjord Volcanic Complex Svalbard (Norway)

The Sverrefjell and Sigurdfjell eruptive centers in the Bockfjord Volcanic Complex (BVC) on Svalbard (Norway) formed by subglacial eruptions ca. 1 Ma ago. These eruptive centers carry ubiquitous magnesian carbonate deposits including dolomitemagnesite globules similar to those in the Martian meteorite ALH84001. Carbonates in mantle xenoliths are dominated by ALH84001 type carbonate globules that formed during quenching of CO2-rich mantle fluids. Lava hosted carbonates include ALH84001 type carbonate globules occurring throughout lava vesicles and microfractures and massive carbonate deposits associated with vertical volcanic vents. Massive carbonates include < or equal 5 cm thick magnesite deposits protruding downwards into clear blue ice within volcanic vents and carbonate cemented lava breccias associated with volcanic vents. Carbonate cements comprise layered deposits of calcite, dolomite, huntite, magnesite and aragonite associated with ALH84001 type carbonate globules lining lava vesicles. Combined Mossbauer, XRD and VNIR data show that breccia carbonate cements at Sverrefjell are analog to Comanche carbonates at Gusev crater.

Amundsen, H. E. F.↗

Growing Aligned Carbon Nanotubes for Interconnections in ICs

A process for growing multiwalled carbon nanotubes anchored at specified locations and aligned along specified directions has been invented. Typically, one would grow a number of the nanotubes oriented perpendicularly to a silicon integrated-circuit (IC) substrate, starting from (and anchored on) patterned catalytic spots on the substrate. Such arrays of perpendicular carbon nanotubes could be used as electrical interconnections between levels of multilevel ICs. The process (see Figure 1) begins with the formation of a layer, a few hundred nanometers thick, of a compatible electrically insulating material (e.g., SiO(x) or Si(y)N(z) on the silicon substrate. A patterned film of a suitable electrical conductor (Al, Mo, Cr, Ti, Ta, Pt, Ir, or doped Si), having a thickness between 1 nm and 2 m, is deposited on the insulating layer to form the IC conductor pattern. Next, a catalytic material (usually, Ni, Fe, or Co) is deposited to a thickness between 1 and 30 nm on the spots from which it is desired to grow carbon nanotubes. The carbon nanotubes are grown by plasma-enhanced chemical vapor deposition (PECVD). Unlike the matted and tangled carbon nanotubes grown by thermal CVD, the carbon nanotubes grown by PECVD are perpendicular and freestanding because an electric field perpendicular to the substrate is used in PECVD. Next, the free space between the carbon nanotubes is filled with SiO2 by means of CVD from tetraethylorthosilicate (TEOS), thereby forming an array of carbon nanotubes embedded in SiO2. Chemical mechanical polishing (CMP) is then performed to remove excess SiO2 and form a flat-top surface in which the outer ends of the carbon nanotubes are exposed. Optionally, depending on the application, metal lines to connect selected ends of carbon nanotubes may be deposited on the top surface. The top part of Figure 2 is a scanning electron micrograph (SEM) of carbon nanotubes grown, as described above, on catalytic spots of about 100 nm diameter patterned by electron-beam lithography. These and other nanotubes were found to have lengths ranging from 2 to 10 m and diameters ranging from 30 to 200 nm, the exact values of length depending on growth times and conditions and the exact values of diameter depending on the diameters and thicknesses of the catalyst spots. The bottom part of Figure 2 is an SEM of an embedded array of carbon nanotubes after CMP.

Li, Jun↗

Iron-Rich Carbonates as the Potential Source of Evolved CO2 Detected by the Sample Analysis at Mars (SAM) Instrument in Gale Crater

The Sample Analysis at Mars (SAM) instrument detected at least 4 distinct CO2 release during the pyrolysis of a sample scooped from the Rocknest (RN) eolian deposit. The highest peak CO2 release temperature (478-502 C) has been attributed to either a Fe-rich carbonate or nano-phase Mg-carbonate. The objective of this experimental study was to evaluate the thermal evolved gas analysis (T/EGA) characteristics of a series of terrestrial Fe-rich carbonates under analog SAM operating conditions to compare with the RN CO2 releases. Natural Fe-rich carbonates (<53 microns) with varying Fe amounts (Fe(0.66)X(0.34)- to Fe(0.99)X(0.01)-CO3, where X refers to Mg and/or Mn) were selected for T/EGA. The carbonates were heated from 25 to 715 C (35 C/min) and evolved CO2 was measured as a function of temperature. The highest Fe containing carbonates (e.g., Fe(0.99)X(0.01)-CO3) yielded CO2 peak temperatures between 466-487 C, which is consistent with the high temperature RN CO2 release. The lower Fe-bearing carbonates (e.g., Fe(0.66)X(0.34)CO3) did not have peak CO2 release temperatures that matched the RN peak CO2 temperatures; however, their entire CO2 releases did occur within RN temperature range of the high temperature CO2 release. Results from this laboratory analog analysis demonstrate that the high temperature RN CO2 release is consistent with Fe-rich carbonate (approx.0.7 to 1 wt.% FeCO3). The similar RN geochemistry with other materials in Gale Crater and elsewhere on Mars (e.g., Gusev Crater, Meridiani) suggests that up to 1 wt. % Fe-rich carbonate may occur throughout the Gale Crater region and could be widespread on Mars. The Rocknest Fe-carbonate may have formed from the interaction of reduced Fe phases (e.g., Fe2+ bearing olivine) with atmospheric CO2 and transient water. Alternatively, the Rocknest Fe-carbonate could be derived by eolian processes that have eroded distally exposed deep crustal material that possesses Fe-carbonate that may have formed through metamorphic and/or metasomatic processes.

Sutter, B.↗

Disturbance and the Carbon Balance of US Forests: A Quantitative Review of Impacts from Harvests, Fires, Insects, and Droughts

Disturbances are a major determinant of forest carbon stocks and uptake. They generally reduce land carbon stocks but also initiate a regrowth legacy that contributes substantially to the contemporary rate of carbon stock increase in US forestlands. As managers and policy makers increasingly look to forests for climate protection and mitigation, and because of increasing concern about changes in disturbance intensity and frequency, there is a need for synthesis and integration of current understanding about the role of disturbances and other processes in governing forest carbon cycle dynamics, and the likely future of this and other sinks for atmospheric carbon. This paper aims to address that need by providing a quantitative review of the distribution, extent and carbon impacts of the major disturbances active in the US. We also review recent trends in disturbances, climate, and other global environmental changes and consider their individual and collective contributions to the US carbon budget now and in the likely future. Lastly, we identify some key challenges and opportunities for future research needed to improve current understanding, advance predictive capabilities, and inform forest management in the face of these pressures. Harvest is found to be the most extensive disturbance both in terms of area and carbon impacts, followed by fire, windthrow and bark beetles, and lastly droughts. Collectively these lead to the gross loss of about 200 Tg C y(exp -1) in live biomass annually across the conterminous US. At the same time, the net change in forest carbon stocks is positive (190 Tg C y(exp -1)), indicating not only forest resilience but also an apparently large response to growth enhancements such as fertilization by CO2 and nitrogen. Uncertainty about disturbance legacies, disturbance interactions, likely trends, and global change factors make the future of the US forest carbon sink unclear. While there is scope for management to enhance carbon sinks in US forests, tradeoffs with other values and uses are likely to significantly limit practical implementation. Continued and expanded remote sensing and field-based monitoring capabilities and manipulative experimentation are needed to improve understanding of the US forest carbon sink, and assess how disturbance processes are responding to the pressures of global environmental change. In addition, continued development and application of holistic, decision support tools that consider a range of forest values are needed to enable managers and policy makers to use the best available information for guiding forest resources now and into the future.

Williams, Christopher A.↗

Sensing the Ocean Biological Carbon Pump from Space: A Review of Capabilities, Concepts, Research Gaps and Future Developments

The element carbon plays a central role in climate and life on Earth. It is capable of moving among the geosphere, cryosphere, atmosphere, biosphere and hydrosphere. This flow of carbon is referred to as the Earth's carbon cycle. It is also intimately linked to the cycling of other elements and compounds. The ocean plays a fundamental role in Earth's carbon cycle, helping to regulate atmospheric CO2 concentration. The ocean biological carbon pump (OBCP), defined as a set of processes that transfer organic carbon from the surface to the deep ocean, is at the heart of the ocean carbon cycle. Monitoring the OBCP is critical to understanding how the Earth's carbon cycle is changing. At present, satellite remote sensing is the only tool available for viewing the entire surface ocean at high temporal and spatial scales. In this paper, we review methods for monitoring the OBCP with a focus on satellites. We begin by providing an overview of the OBCP, defining and describing the pools of carbon in the ocean, and the processes controlling fluxes of carbon between the pools, from the surface to the deep ocean, and among ocean, land and atmosphere. We then examine how field measurements, from ship and autonomous platforms, complement satellite observations, provide validation points for satellite products and lead to a more complete view of the OBCP than would be possible from satellite observations alone. A thorough analysis is then provided on methods used for monitoring the OBCP from satellite platforms, covering current capabilities, concepts and gaps, and the requirement for uncertainties in satellite products. We finish by discussing the potential for producing a satellite-based carbon budget for the oceans, the advantages of integrating satellite-based observations with ecosystem models and field measurements, and future opportunities in space, all with a view towards bringing satellite observations into the limelight of ocean carbon research.

Robert J. W. Brewin↗

Advancing Satellite-Constrained Modeled Air-Sea CO 2 Fluxes With a Focus on the Strength of the Southern Ocean Carbon Sink

Challenge and Motivation: The ocean plays a critical role in mitigating climate change by removing approximately a quarter of annual anthropogenic CO 2 emissions from the atmosphere. Model-based estimates point to the Southern Ocean as a key marine region, responsible for approximately 40 % of the anthropogenic carbon uptake by the global ocean. However, the contemporary strength of the Southern Ocean carbon sink has recently come into question. On the one hand, airborne-based observations of atmospheric CO 2 gradients indicate that the Southern Ocean represents a strong net sink of atmospheric CO 2 , consistent in magnitude with atmospheric inversion estimates and surface-ocean partial pressure of CO 2 (pCO 2 )-based products. On the other hand, estimates of pCO 2 based on in situ pH measurements taken by biogeochemical profiling floats yield strong wintertime outgassing fluxes that greatly reduce the Southern Ocean’s annually integrated CO 2 uptake. This uncertainty in the strength of the Southern Ocean air-sea CO 2 flux and its role in the global carbon cycle hinders our ability to constrain global carbon fluxes, one of the major goals of NASA’s Carbon Monitoring System (CMS). Opportunity: The NASA Ocean Biogeochemical Model (NOBM) produces near-global pCO 2 and air-sea CO 2 flux estimates that are currently included into the NASA’s Goddard Earth Observing System (GEOS) models in support of the CMS effort to monitor global carbon fluxes. The NOBM assimilates ocean color data to improve the representation of biogeochemical fluxes and overcome spatial and temporal gaps in the space-based retrievals. Here, we propose to advance the satellite-constrained flux estimates by investigating the uncertainties in the Southern Ocean air-sea CO 2 flux produced by the NOBM, and assess the value that remote sensing ocean color data can have in providing improved estimates of carbon fluxes in the ocean. Our proposed work includes the delivery of refined in situ float-based carbon fluxes to serve as a constraint on the model-based estimates. Taking advantage of the model’s integration of satellite ocean color data to represent multiple phytoplankton groups, we propose to deliver maps of biogenic carbon export specific to each modeled phytoplankton type and investigate the role of ecological plankton complexity in regulating marine carbon uptake and export. Goals: (a) Delivery of seasonally-adjusted float-based Southern Ocean air-sea CO 2 fluxes: We will produce updated and improved float-based air-sea CO 2 fluxes that will serve as a bias-reduced float-based constraint to evaluate our model-based estimates of the NOBM. (b) Investigation of uncertainties in Southern Ocean air-sea CO 2 flux from the NOBM: Modeled air-sea carbon fluxes will be evaluated against the updated float product as well as ship- and airborne-based data to identify uncertainties and potential model deficiencies. (c) Delivery of model-based carbon export partitioning by phytoplankton functional types (PFTs): We will produce depth-resolved maps of particulate organic export production integrated for all phytoplankton groups and allocated to each individual PFT in the model. The expected significance of this goal is to quantify the role that the functional-oriented diversity in phytoplankton groups represented in the NOBM plays in regulating air-sea CO 2 fluxes in the Southern Ocean.

Lionel A. Arteaga↗

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↗

Leaf 13 C data constrain the uncertainty of the carbon dynamics of temperate forest ecosystems

Stable carbon isotope discrimination occurred in plant biophysical and biogeochemical processes can help understand plant physiology and soil biogeochemistry with respect to carbon cycling. Here, we incorporated the photosynthetic carbon isotope discrimination into a process-based land surface model (iTEM) to test if stable carbon isotope composition (δ 13 C) can impose additional constraint on model parameters. Sequential data assimilation was implemented at six eddy covariance flux tower sites using carbon flux observations including gross primary productivity (GPP) and net ecosystem exchange (NEE) with and without considering foliar δ 13 C (δ 13 C f ) measurement constraints, respectively. Our model-data fusion showed that δ 13 C f can provide useful constraint on photosynthetic (V cmax25 , the maximum rate of carboxylation at 25°C) and stomatal (g1, the slope of stomatal function) parameters as well as the posterior carbon fluxes. When including δ 13 C f measurement, g1 spatially varies among the six sites and is significantly correlated with annual precipitation. We incorporated the statistical relationship between g1 and annual precipitation into iTEM, which is then used to quantify the regional carbon dynamic in temperate forest ecosystems of the Northern Hemisphere. Compared with the simulation only conditioned on carbon flux observations, regional carbon flux estimations performed slightly better against the FLUXCOM products and the uncertainties of modeled carbon fluxes were reduced by 27%. Our study demonstrated that δ 13 C f data constrains carbon flux uncertainties across space.

54 ENVIRONMENTAL SCIENCES↗

Improved CO 2 utilization efficiency using membrane carbonation in outdoor raceways

Membrane carbonation, the delivery of CO 2 by diffusion through non-porous hollow fiber membranes, was successfully integrated into outdoor raceways (5.6 m 2 , 900 L) and operated continuously for up to 45 days. Biomass productivity associated with membrane carbonation was similar to using traditional sparging, but the average carbon utilization efficiencies for membrane carbonation was 3-fold higher than for sparging when 100% CO 2 was delivered to both systems. Here, when the pH setpoint was 8.5, growth on ammonium bicarbonate using membrane carbonation achieved a carbon utilization efficiency of 106 ± 45% due to uptake of some carbon from bicarbonate. Using nitrate as the N source had a 78 ± 55% carbon utilization efficiency, due to dissolved inorganic carbon accumulation as the medium alkalinity increased. Lowering the pH setpoint to 8.0 created a carbon-rich environment that decreased the carbon utilization efficiency to 51 ± 27% due to CO 2 off-gassing, but it still was 3-fold higher than with sparging.

54 ENVIRONMENTAL SCIENCES↗

Carbon footprint prediction considering the evolution of alternative fuels and cargo: A case study of Yangtze river ships

For reducing carbon emissions in the shipping sector, application of alternative low-carbon and zero-carbon fuels is the consensus. However, requirements of economic development cannot be ignored while focusing on emission reduction. Cargo development is an important prerequisite. Considering the cargo growth as a novelty, a method to calculate the annual carbon emissions of different alternative fuel-powered ships in different cargo growth prospects and power scenarios is proposed. With respect to the time dimension, the relationship between alternative fuels, cargo, and carbon reduction is revealed. The Yangtze River bulk carrier case was studied and the life cycle carbon emission analysis of diesel, LNG hybrid, LNG, hydrogen, methanol, and ammonia were carried out. The annual carbon curves of the high, steady, and low cargo growth prospects were obtained for different scenarios of the power system structure. The results show that LNG hybrid, LNG and methanol fuels are currently the suitable choices. Their life cycle carbon emissions were reduced by 31.5–38.1% compared with those of diesel power. The carbon emissions of green hydrogen and green ammonia were reduced by 78.8% and 91.3%, respectively, compared with those of hydrogen and ammonia. The carbon reduction results of green fuels in their initial application were explored which are at 0.6–10.8%. In addition, there is a balanced annual growth rate, whose annual carbon curve will be steady under its corresponding scenario of power system structure, which could help the ship owners plan their future.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Enriched Background Isotope Study (EBIS): Analysis of 14C-Enriched Carbon Cycle in Soils and Litter at Forested Oak Ridge and AmeriFlux Sites, 2001-2011

These data provide a record of the multi-year, multi-institutional Enriched Background Isotope Studies (EBIS) projects that ran from 2000 through 2011. Elevated levels of 14C enriched CO2 in the air and soil atmosphere as well as leaf, stem, and root tissues were observed on the Oak Ridge Reservations (ORR) during the summer of 1999, and were attributed to local incinerator activities on and/or near the ORR (Trumbore et al. 2002). The isolated enrichment of the background levels of 14C in local forest ecosystem represented a unique opportunity to study unresolved carbon cycling processes such as the contribution of leaf versus root litter contributions to soil carbon accumulation, the rate of vertical transport of carbon into deep soil storage pools, and the differential contribution of physicochemical versus faunal driven processes to soil carbon cycling and sequestration. Leaf litter from the local enriched forest was transplanted to selected sites on the ORR and to selected AmeriFlux study sites to study soil C cycling across a range of soils and climates. The EBIS research projects provide data on C flux from litter sources to mineral soil sinks for United States eastern hardwood forests necessary for testing process hypotheses and judging efficacy of soil C cycling models. Experimental results from this study are being used to parameterize and refine existing carbon dynamics models, the quantification of the long-term fate of ecosystem carbon inputs and as a means to judge the potential for ecosystem carbon sequestration via enhance litter inputs to soil. EBIS observations support conclusions that intra- and inter-annual soil carbon cycling in hardwood forest soils should be characterized as a least a two-compartment system where surface leaf-litter and belowground root turnover represent primary carbon sources for organic-layer and mineral-soil carbon cycles, respectively. EBIS experiments were conducted to complete enriched litterfall maniplations in upland forests on Ultisol and Inceptisol soils of the Oak Ridge Reservation, Oak Ridge, Tennessee. We also collected additional14C-enriched materials for new experimental applications, and applied those materials to multiple AmeriFlux sites over a range of climatic, edaphic and biological conditions. The research provided data for addressing DOE's goal of understanding mechanisms controlling C flux, and for the improvement of models to be applied to policy discussions regarding the safe levels of greenhouse gases for the earth's system. There are 5 data files provided in comma separated (*.csv) format for vegetation, field litter, soil and air [C] and C isotope data from the EBIS studies and associated environmental data.

54 ENVIRONMENTAL SCIENCES↗

Carbon emission responsive building control: A case study with an all-electric residential community in a cold climate

In the United States, buildings account for 35% of total energy-related carbon dioxide emissions, making them important contributors to decarbonization. Carbon intensities in the power grid are time-varying and can fluctuate significantly within hours, so shifting building loads in response to the carbon intensities can reduce a building’s operational carbon emissions. This paper presents a rule-based carbon responsive control framework that controls the setpoints of thermostatically controlled loads responding to the grid’s carbon emission signals in real time. Based on this framework, four controllers are proposed with different combinations of carbon accounting methods and control rules. To evaluate their performance, we performed simulation studies using models of a 27-home, all-electric, net zero energy residential community located in Basalt, Colorado, United States. The carbon intensity data of four future years from the Cambium data set are adopted to account for the evolving resource mix in the power grid. Various performance metrics, including energy consumption, carbon emission, energy cost, and thermal discomfort, were used to evaluate the performance of the controllers. Sensitivity analysis was also conducted to determine how the control thresholds and intervals affect the controllers’ performance. Simulation results indicate that the carbon responsive controllers can reduce the homes’ annual carbon emissions by 6.0% to 20.5%. However, the energy consumption increased by 0.9% to 6.7%, except in one scenario where it decreased by 2.2%. Compared to the baseline, the change in energy cost was between –2.9% and 3.4%, and thermal discomfort was also maintained within an acceptable range. The little impact on energy cost and thermal discomfort indicates there are no potential roadblocks for customer acceptance when rolling out the controllers in utility programs.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Initial assessment of alternative carbon fiber geometries for design of cost-effective compressive performance: Size effect studies

Carbon fiber provides opportunity to reduce weight in structural composites, including wind turbine blades, due to the material's superior specific stiffness and specific strength compared to alternatives. Despite these advantages, cost and compressive performance are considered weaknesses for carbon fiber products available today. Studies to produce low-cost carbon fiber alternatives, including the use of textile-derived precursor systems, have shown progress and merit through the DOE/ORNL low-cost carbon fiber initiatives. Here, this work focuses on enabling increases in compressive strength through design of the carbon fiber geometry, applicable to both textile and conventional precursor systems, while also providing opportunities to reduce carbon fiber processing costs. Fiber-resin interface and fiber alignment are among the most frequently cited factors controlling composite compressive performance. However, it is believed that there is opportunity in traditionally unexplored routes to increasing compressive strength through alteration of the carbon fiber geometry by increasing the fiber area moment of inertia and/or the fiber perimeter and interfacial area. This paper presents initial results from manufacturing carbon fiber materials to assess the impacts of carbon fiber size on tested composite compressive performance with projected neutral or even beneficial impact on fiber and composite manufacturing economics. Carbon fiber systems with increasing size illustrate a favorable correlation for compressive performance greater than predicted from a micromechanical failure model. The manufacturing and mechanical test results support the hypothesis of this work that alterations to fiber geometry can be used to produce improvements of the compressive strength of carbon fiber reinforced polymers and provide incentive for related work in designing alternative shapes to further enhance compressive performance.

42 ENGINEERING↗

Simulating policy interventions in the interfirm diffusion of low-carbon technologies: An agent-based evolutionary game model

Policy interventions are frequently used by authorities around the world to mitigate carbon emissions. However, economic systems are essentially complex adaptive systems, which often exhibit unexpected responses to exogenous interventions and leave intervenors in a dilemma, even if the interventions are elaborately designed. To explore the behaviors of the diffusion system regarding low-carbon technologies, this study builds an agent-based model (ABM) to simulate enterprises' reactions to multiple policy interventions aimed at spurring low-carbon technology diffusion. The simulated enterprises are in a complex network where they play evolutionary games with their neighbors, which enables the model to possess two critical features of economic systems: adaptiveness and equilibrium. The model reveals a dilemma of policy interventions: intuitively, carbon taxes, asymmetric penalties (only imposed on un-low-carbon enterprises) and subsidies can improve the diffusion, which is consistent with previous research; counter-intuitively, all these policies turn out to be inefficient or even harmful to low-carbon enterprises because of the diffusion system's high adaptiveness. Specifically, when carbon taxes and penalties increase, both the low-carbon and un-low-carbon enterprises end up with the equilibrium of equivalent but lower profits. In contrast, all the enterprises earn equivalent but more profits even though subsidies are only given to the low-carbon enterprises, which implies that the un-low-carbon enterprises (indirectly) grab a portion of the subsidies and accordingly weaken the incentive effect of subsidies. These system behaviors are summarized as "equalizing effect" because the system tends to equalize the impact of both positive and negative interventions among all enterprises even though the policy interventions are asymmetrically imposed on one type of the enterprises. The findings also indicate that policies implemented to enlarge green market sizes can help policymakers bypass the dilemma.

Agent-based modeling↗