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At least 1,099 records · Page 61
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Site demonstration and performance evaluation of MPC for a large chiller plant with TES for renewable energy integration and grid decarbonization

Thermal energy storage (TES) for a cooling plant is a crucial resource for load flexibility. Traditionally, simple, heuristic control approaches, such as the storage priority control which charges TES during the nighttime and discharges during the daytime, have been widely used in practice, and shown reasonable performance in the past benefiting both the grid and the end-users such as buildings and district energy systems. However, the increasing penetration of renewables changes the situation, exposing the grid to a growing duck curve, which encourages the consumption of more energy in the daytime, and volatile renewable generation which requires dynamic planning. The growing pressure of diminishing greenhouse gas emissions also increases the complexity of cooling TES plant operations as different control strategies may apply to optimize operations for energy cost or carbon emissions. This paper presents a model predictive control (MPC), site demonstration and evaluation results of optimal operation of a chiller plant, TES and behind-meter photovoltaics for a campus-level district cooling system. The MPC was formulated as a mixed-integer linear program for better numerical and control properties. Compared with baseline rule-based controls, the MPC results show reductions of the excess PV power by around 25%, of the greenhouse gas emission by 10%, and of peak electricity demand by 10%.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2020

Light-absorbing impurities accelerating glacial melting in southeastern Tibetan Plateau

Deposition of light-absorbing particles on glacier surfaces poses a series of adverse impacts on the cryospheric environment, climate and human health. Broad attention of the scientific community has been paid on insoluble light-absorbing impurities (ILAIs) in snow and ice on glaciers over the Tibetan Plateau (TP). However, systematic investigation of ILAIs in snowpack of glaciers on the TP is scarce. In this study, the properties and darkening effect of ILAIs in snowpack on glaciers are extensively investigated in the southeast of TP. Results show that ILAIs concentrations in multiple types of snow and ice samples were significantly different. Snowpit depths varied substantially from one profile to another during May and June 2016. The average concentrations of ILAIs in snowpits increase as snow melting progresses. Black carbon (BC) and dust cause snow albedo reduction more in snow with larger grain size Re. Based on a radiative transfer model calculation, the average albedo reduction induced by BC in the snowpack was 0.141 ± 0.02, and associated daily maximum radiative forcing (RF) was 72.97 ± 12.7 W m-2. BC is a controlling light-absorbing factor in snowpack and causes substantial albedo reduction and thus the associated daily maximum RF. The maximum reduction of snow cover duration was 4.56 ± 0.71 days caused by BC and dust in snowpack in southeastern TP. The average mass absorption cross-section (MAC) of BC from multiple snowpits was 3.26 ± 0.46 m2 g-1, which represents a typical value of MAC in snow on glaciers, but it is type-dependent of snow/ice samples. Tropospheric aerosols vertically extended up to 8 km over the TP and its surrounding areas, which indicates the transport of aerosols from remote sources through elevated pathways. A large amount of carbon stored in the brittle glaciers can be potentially released with meltwater runoff under a warming climate. This study provides a new insight for investigating carbonaceous and light-absorbing particles in glacierization areas.

Niu, Hewen↗
DOE OSTI2024

Surface Decoration of Platinum Catalysts by ZrO 2– x Nanoclusters for Durable Fuel Cell Applications

Improving the activity and durability of carbon-supported platinum catalysts for the oxygen-reduction reaction (ORR) in acidic electrolytes is crucial to reducing the high overpotentials and power loss over time in proton-exchange membrane fuel cells (PEMFCs). We found that platinum nanoparticle catalyst deposited on an engineered carbon support in the presence of zirconium enabled higher ORR activity and 25% better retention in electrochemically active surface area (ECSA), thereby improving durability. The use of zirconium precursor in the carbon synthesis process led to the formation of atomically dispersed Zr and ZrO 2 nanoparticles on the support. Upon Pt deposition and subsequent heat treatment, the ZrO 2 particles preferentially rearranged on and around the platinum nanoparticles in a chemically reduced form as zirconium suboxide (ZrO 2-x ) surface-decorated nanoclusters, which mitigated Pt nanoparticle coarsening. Finally, analysis of the here-to-fore unknown catalyst structure as well as its performance and durability in a PEM fuel cell membrane electrode assembly (MEA) is discussed.

25 ENERGY STORAGE↗
DOE OSTI2022

A Novel Process for Carbon Dioxide Conversion to Fuel

In this project, TDA developed a new mixed metal oxide-based sorbent that converts CO2 (captured from coal fired power plants) to CO, which can then be combined with renewable H2 generated by water electrolysis or H2 from steam methane reforming to produce different liquid fuels. TDA’s absorbent-based CO2 conversion process uses a redox process, which splits the catalytic reforming of methane with CO2 reaction into two stages: CO2 reduction to CO and CH4 reforming into H2 and CO which eliminates the equilibrium limitations. The CO produced in the two-stage reactor system can then be further reacted with renewable H2 to produce methanol, naphtha, diesel, or gasoline. We worked with the Advanced Power & Energy Program (APEP) of University of California, Irvine (UCI) to design and develop the liquid fuel synthesis process that is built around this new material. We demonstrated the techno-economic viability of the new sorbent based redox process to convert CO2 into synthesis gas by demonstrating continuous carbon dioxide reduction in a prototype test system for over 585 hours while converting up to 10 kg CO2/day. With the successful completion of the R&D effort, the technology is now ready for a larger pilot-scale demonstration and the technology readiness has been raised from TRL 3 to TRL 5. In collaboration with UCI, we completed a high-fidelity process design and economic analysis. The required sale price (RSP) for gasoline (Case 1 NG-MTG) is $4.91/gal and naphtha and diesel (Case 2 NG-FT) are $4.23/gal and $6.07/gal, respectively, on a 2011 dollar basis. To put these costs in perspective, the California prices in current dollars (with its strict specifications) for regular grade gasoline from last year to current year have varied from a low of $3.10/gal in January 2021 to a high of $5.76/gal in March 2022, while prices for diesel from last year to current year have varied from a low of $3.40/gal in January 2021 to a high of $6.41/gal in May 2022 according to the U.S. Energy Information Agency data. It should be noted that the gasoline and diesel produced by these designs of Case 1 and Case 2 would be of very high quality and both nitrogen and sulfur free. These RSPs are based on a cost of imported electricity of $64/MWh based on the low-end current wind generated electricity cost (Genevieve 2011). This cost is by far the largest component of the variable costs used in computing the RSPs. A sensitivity analysis of these RSPs to the cost of imported electricity shows that the cost of the imported electricity has a significant effect on the RSPs. The life cycle analysis (LCA) shows that the total cradle-to-gate CO2 emissions for both liquid fuels (diesel and gasoline) were negative, indicating that overall more CO2 is consumed than released during production of the fuel from CO2 feed stack for both cases (-296 kgCO2 per MT gasoline for Case 1 and -705 kgCO2 per MT diesel for Case 2). On a cradle-to-grave comparison, the use of diesel produced using TDA’s process (2,457 kgCO2 per MT diesel) would release 37.6% less CO2 compared to petroleum based diesel (3,937 kgCO2 per MT diesel) while the use of gasoline produced using TDA’s process (2,792 kgCO2 per MT gasoline) would release 29.3% less CO2 compared to petroleum based gasoline (3,946 kgCO2 per MT gasoline). With the successful completion of the R&D effort, the technology is now ready for a bench-scale demonstration and the technology readiness has been raised from TRL 3 (Analytical and experimental critical function and/or characteristic proof of concept) to TRL 5 (Laboratory scale similar system validation in relevant environment).

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2022

Molecular Coatings Improve the Selectivity and Durability of CO 2 Reduction Chalcogenide Photocathodes

The quest for solar-driven conversion of carbon dioxide to chemicals and fuels hinges upon the identification of an efficient, durable, and selective photocathode. Chalcogenide p-type semiconductors exemplified by chalcopyrite Cu(In,Ga)Se 2 (CIGS) have been effectively deployed as photocathodes. However, selectivity toward CO 2 reduction and durability of the commonly used CdS adlayer remain primary challenges. Here, we demonstrate that for the wide band gap CuGa 3 Se 5 chalcopyrite absorber these challenges are well addressed by an organic coating generated in situ from an N,N'-(1,4-phenylene)bispyridinium ditriflate salt in the electrolyte. The molecular additive provides a 30-fold increase in selectivity toward CO2R products compared to the unmodified system and lowers Cd corrosion at least 10-fold. This dual functionality highlights the promise of hybrid solid-state-molecular photocathodes for enabling durable and efficient solar fuel systems.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Geochemical constraints on bacteriophage infectivity in terrestrial environments

Abstract Lytic phages can be potent and selective inhibitors of microbial growth and can have profound impacts on microbiome composition and function. However, there is uncertainty about the biogeochemical conditions under which phage predation modulates microbial ecosystem function, particularly in terrestrial systems. Ionic strength is critical for infection of bacteria by many phages, but quantitative data is limited on the ion thresholds for phage infection that can be compared with environmental ion concentrations. Similarly, while carbon composition varies in the environment, we do not know how this variability influences the impact of phage predation on microbiome function. Here, we measured the half-maximal effective concentrations (EC50) of 80 different inorganic ions for the infection of E. coli with two canonical dsDNA and ssRNA phages, T4 and MS2, respectively. Many alkaline earth metals and alkali metals enabled lytic infection but the ionic strength thresholds varied for different ions between phages. Additionally, using a freshwater nitrate-reducing microbiome, we found that the ability of lytic phages to influence nitrate reduction end-products depended upon the carbon source as well as ionic strength. For all phage:host pairs, the ion EC50s for phage infection exceeded the ion concentrations found in many terrestrial freshwater systems. Thus, our findings support a model where phages most influence terrestrial microbial functional ecology in hot spots and hot moments such as metazoan guts, drought influenced soils, or biofilms where ion concentration is locally or transiently elevated and nutrients are available to support the growth of specific phage hosts.

Carlson, Hans K. (ORCID:0000000215835313)↗
DOE OSTI2024

Advanced Sensors for In-Situ Amine Degradation Monitoring in Post-Combustion Carbon Capture

In order to improve the long-term performance of post-combustion carbon capture technologies, improvements to the detection of solvent degradation or reduction in CO2 capture efficiency are necessary. A pair of sensors were deployed to the National Carbon Capture Center’s (NCCC) to monitor CO2 capture and solvent degradation. The CO2 sensors were located to measure before capture and after capture concentrations of CO2 to measure the capture efficiency of the solvent system. Amine degradation sensors were located at four locations along the main solvent lines corresponding to CO2 loading and temperature: hot rich, cold rich, hot lean, and cold lean. Experimental results from laboratory tests using the sensors are shown, along with prototype designs that were deployed to the field site.

Brister, Matthew↗
NASA NTRS1982

Performance of the coned-face end seal with regard to energy conservation

The effects of face coning on seal performance are evaluated with particular regard to the energy saving potential of convex conedface end seals as indicated by torque reduction. Experiments were conducted using a conventional carbon flat-face pusher-type seal, a coned-face pusher-type seal, coned-face bellows-type seal, and a modified coned-face pusher-type seal intended for dynamically unstable operation, with shaft rotation at up to 8000 rpm, pressures of up to 2758 kPa, and a petroleum-based turbine oil as lubricant. Torque at the seal interface is found to be reduced by 42% when the standard flat-face seal is replaced by a coned seal, although the leakage of the cone-face seal was 11 times greater. Reduction of seal balance from 76.1 to 51.3% resulted in an additional 44% reduction in torque, although at the expense of excessive leakage, but did not produce unstable operation. Face temperatures were reduced by 33-56 C and wear was also reduced greatly on the cone face seals. Seal performance is noted to be in agreement with analytical calculations.

Sehnal, J.↗
DOE OSTI2023

Final Technical Report

The project goal is to demonstrate low-cost, interlocking, and carbon-storing insulation materials with thermal insulation of R5/inch, flexural modulus > 10 MPa, low material price < $ 0.5/ft2 wall area (materials cost for ½” thick panel), and net embodied carbon of 0.8t net CO2e/t (60% reduction compared to gypsum), respectively, which can meet the cost and performance targets of department of energy (DOE)’s 2050 climate target. To achieve this goal, the project plans three tasks, and each has a specific objective: 1) Modular design and engineering analysis of interlocking insulation panel blocks using biogenic materials (cellulose, straw, etc.): with the consideration of potential assembling and recycling. 2) Scalable manufacturing of biogenic-based interlocking insulation panels: scale up the modular panel production using ambient pressure drying and surface superhydrophobic modification at 1ft*1ft with the potential for further scalable mass production of 4ft*4ft. 3) Code-compliant testing, recycling and carbon footprint analysis of manufactured interlocking insulation panels examined using ASTM standards of thermal insulation (ASTM C518), mechanical properties (ASTM C1161), and water vapor transmission (ASTM E96).

Ren, Shenqiang↗
NASA NTRS1989

Ozone trends in Atlanta, Georgia - Have emission controls been effective?

Nine years of summertime ozone data from the Atlanta metropolitan area are analyzed and compared to local emissions of volatile organic carbon and nitrogen oxides. Trends from 1979 to 1987 were studied for the number of days per year ozone exceeded the NAAQS standard, the second-highest ozone level observed per year, and the first quartile summertime average ozone observed, as well as the mean difference between the ozone level observed downwind and upwind of the city. Because this last parameter is sensitive to chemical factors but relatively insensitive to the number of days each year with meteorological conditions conducive to ozone formation, its trend may be best suited for determining how effective emission controls have been in reducing O3 in the Atlanta area. In spite of the fact that sizeable reductions have been claimed for volatile organic carbon emissions over the past several years, the data give no indication that ozone levels have decreased and in fact, imply that summertime ozone production may have increased. The results imply that either emissions have not decreased as much as has been claimed or that ozone is not sensitive to anthropogenic volatile organic carbon emissions.

Lindsay, Ronald W.↗
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↗
NASA NTRS2022

Climate Change-Induced Peatland Drying in Southeast Asia

When organic peat soils are sufficiently dry, they become flammable. In Southeast Asian peatlands, widespread deforestation and associated drainage create dry conditions that, when coupled with El Niño-driven drought, result in catastrophic fire events that release large amounts of carbon and deadly smoke to the atmosphere. While the effects of anthropogenic degradation on peat moisture and fire risk have been extensively demonstrated, climate change impacts to peat flammability are poorly understood. These impacts are likely to be mediated primarily through changes in soil moisture. Here, we used neural networks (trained on data from the NASA Soil Moisture Active Passive satellite) to model soil moisture as a function of climate, degradation, and location. The neural networks were forced with regional climate model projections for 1985–2005 and 2040–2060 climate under RCP8.5 forcing to predict changes in soil moisture. We find that reduced precipitation and increased evaporative demand will lead to median soil moisture decreases about half as strong as those observed during recent El Niño droughts in 2015 and 2019. Based on previous studies, such reductions may be expected to accelerate peat carbon emissions. Our results also suggest that soil moisture in degraded areas with less tree cover may be more sensitive to climate change than in other land use types, motivating urgent peatland restoration. Climate change may play an important role in future soil moisture regimes and by extension, future peat fire in Southeast Asian peatlands.

VIIRS↗
DOE OSTI2021

Nanocolumnar Pt:Ni Alloy Thin Films by High Pressure Sputtering for Oxygen Reduction Reaction

Self-supported nanocolumnar Pt:Ni thin films (TFs) with varying Pt:Ni atomic ratios and Pt mass loadings were produced on a microporous layer (MPL)-like surface composed of carbon particles by high pressure sputtering and examined as oxygen reduction reaction (ORR) electrocatalysts for polymer electrolyte membrane fuel cells. Cauliflower-like microstructures were observed from scanning electron microscopy imaging. Various Pt:Ni atomic ratios were obtained by simply changing the relative deposition power between Pt and Ni source and investigated by X-ray diffraction and quartz crystal microbalance analysis. Additionally, electrochemical characterization of the Pt:Ni-TF/MPL-like-layer/glassy-carbon samples was conducted through benchtop cyclic voltammetry and rotating disk electrode measurements. The electrochemically active surface area (ECSA) was found to be between 22–42 m 2 g -1 for different Pt:Ni atomic ratios. Lower Pt mass loadings exhibited a higher ECSA and the catalytic activity of all Pt:Ni ratios increased with the increase in Pt mass loading. The ORR activity of the Pt:Ni-TFs increased in the order of 3:1 < 1:1 < 1:3 with exhibiting a specific activity of 1781 μA cm -2 and mass activity of 0.66 A mg -1 for the Ni-rich film with 1:3 ratio. The catalytic performance of Pt:Ni-TFs were higher than traditional high surface area carbon supported Pt nanoparticles, elemental Pt nanorods, and Pt-Ni nanorods.

08 HYDROGEN↗
DOE OSTI2022

Examining the effects of chemical cleaning, leaching, and partial dissolution on zinc and cadmium isotope fractionation in marine carbonates

The application of zinc (Zn) and cadmium (Cd) isotopes as palaeo-proxies in carbonate sediment is rapidly expanding due to their potential for tracing changes in biological productivity in the modern and past oceans. However, there are limited investigations into the chemical cleaning methods required to produce the most consistent and accurate data for these novel isotope systems. This could impact their use as palaeo-proxies to reconstruct ocean-atmosphere-climate interactions throughout Earth's history. To address this concern and expand the utility of the Zn and Cd stable isotope systems as palaeo-productivity tracers, the performance of two standard chemical cleaning protocols for acquiring robust and reliable Zn and Cd isotope datasets were assessed. These include (i) the Cd-cleaning method that uses a reductive step to selectively leach contaminating secondary iron (Fe)-manganese (Mn) (oxyhydr)oxide coatings from the carbonate surface, and an oxidative step that is used to remove post-depositional organic matter and sulphide precipitates; and (ii) the magnesium/calcium cleaning protocol that includes an oxidative step only, leaving secondary Fesingle bondMn (oxyhydr)oxide coatings largely intact. Well-preserved Holocene-, and Mesozoic-aged carbonate sediments were used to test the reliability of these two chemical cleaning methods. The Holocene samples comprised not only aliquots of bulk sediment, but also individual species of planktic and benthic foraminifera. Our results show that the best practice chemical cleaning method for retrieving consistent and accurate Zn and Cd isotope, and Zn/Ca and Cd/Ca datasets for carbonate sediments, requires both reductive and oxidative cleaning following the Cd-cleaning method. This differs from most methodological approaches applied to date that remove the reductive step from the chemical cleaning protocol and apply an oxidative step only, or no chemical cleaning at all. Inclusion of the reductive step in the chemical cleaning method typically shifts δ 66 Zn by ~0.1‰ lower and δ 114 Cd by 0.3‰ higher in the solid phase, while Zn/Ca and Cd/Ca typically decrease 2-fold. The benthic foraminifera, C. wuellerstorfi, that live in ocean bottom waters where the seawater Zn and Cd isotope composition is homogeneous display evidence of Zn and Cd isotope fractionation between seawater and carbonate on the order of 0.08 ± 0.08‰ (2SE, n = 4) and -0.25 ± 0.13‰ (2SE, n = 4), respectively, in agreement with experimental constraints. Furthermore, evidence of Zn isotope fractionation effects are recorded in a naturally-dissolved carbonate sediment, together with laboratory-controlled carbonate dissolution experiments. Based on these results, we recommend the Cd-cleaning method and the application of Zn and Cd isotope fractionation factors to accurately reconstruct past seawater Zn and Cd isotope compositions from carbonate sediments.

58 GEOSCIENCES↗
DOE OSTI2021

Monolithic Photoelectrochemical CO 2 Reduction Producing Syngas at 10% Efficiency

We report increasing anthropogenic carbon dioxide emissions have prompted the search for photoelectrochemical (PEC) methods of converting CO 2 to useful commodity products, including fuels. Ideally, such PEC approaches will be sustained using only sunlight, water, and CO 2 as energetic and reactant inputs. However, low peak conversion efficiencies (< 5%) have made commercialization of fully-integrated PEC devices prohibitive. Here, a 4 cm 2 monolithic PEC device exceeding 10% solar-to-fuel efficiency with principal fuel products of carbon monoxide and hydrogen is reported. The corresponding solar-to-CO and solar-to-H 2 efficiencies are 7% and 3.5%, respectively. Screening of a range of operating conditions reveals a tunable product mixture of H 2 and CO using a gold electrocatalyst. Accordingly, it is shown that device optimization yields a H 2 -to-CO ratio of 1:2 commonly present in synthesis gas (syngas). Notably, the modularity and facile fabrication of this device permit the incorporation of a broad array of materials for various applications. For example, the electrocatalyst may easily be swapped to target a different set of products.

36 MATERIALS SCIENCE↗
NASA NTRS2012

Global Air Quality and Health Co-benefits of Mitigating Near-term Climate Change Through Methane and Black Carbon Emission Controls

Tropospheric ozone and black carbon (BC), a component of fine particulate matter (PM < or = 2.5 microns in aerodynamic diameter; PM2.5), are associated with premature mortality and they disrupt global and regional climate. Objectives: We examined the air quality and health benefits of 14 specific emission control measures targeting BC and methane, an ozone precursor, that were selected because of their potential to reduce the rate of climate change over the next 20-40 years. Methods: We simulated the impacts of mitigation measures on outdoor concentrations of PM2.5 and ozone using two composition-climate models, and calculated associated changes in premature PM2.5‑ and ozone-related deaths using epidemiologically derived concentration-response functions. Results: We estimated that, for PM2.5 and ozone, respectively, fully implementing these measures could reduce global population-weighted average surface concentrations by 23-34% and 7-17% and avoid 0.6-4.4 and 0.04-0.52 million annual premature deaths globally in 2030. More than 80% of the health benefits are estimated to occur in Asia. We estimated that BC mitigation measures would achieve approximately 98% of the deaths that would be avoided if all BC and methane mitigation measures were implemented, due to reduced BC and associated reductions of nonmethane ozone precursor and organic carbon emissions as well as stronger mortality relationships for PM2.5 relative to ozone. Although subject to large uncertainty, these estimates and conclusions are not strongly dependent on assumptions for the concentration-response function. Conclusions: In addition to climate benefits, our findings indicate that the methane and BC emission control measures would have substantial co-benefits for air quality and public health worldwide, potentially reversing trends of increasing air pollution concentrations and mortality in Africa and South, West, and Central Asia. These projected benefits are independent of carbon dioxide mitigation measures. Benefits of BC measures are underestimated because we did not account for benefits from reduced indoor exposures and because outdoor exposure estimates were limited by model spatial resolution.

air quality↗
DOE OSTI2022

Life-cycle greenhouse gas emissions reduction potential for corn ethanol refining in the USA

This study evaluates how low-carbon production technologies applicable to ethanol plants may reduce the life-cycle greenhouse gas emission (GHG) intensities of corn ethanol production in the USA. Results indicate that options focusing on incremental energy efficiency (e.g., combined heat and power) and yield improvements have a limited impact on GHG reductions. To achieve deep decarbonization (>50% GHG reduction compared to current corn ethanol production), a fuel switch from natural gas (NG) to alternative low-carbon fuels is needed. Replacing 50% of NG demand at ethanol plants with syngas from biomass through gasification or renewable natural gas from animal waste could achieve significant GHG reductions (11.7–23.5 g CO 2 e/MJ ethanol). Adding multiple technologies, including carbon capture and storage, to existing ethanol plants may further reduce GHG emissions to –18.4 g CO 2 e MJ –1 ethanol (including land-use change emissions), which is 120% lower than the carbon intensity of pure gasoline. These results could inform how the ethanol industry could move toward net-zero ethanol production.

09 BIOMASS FUELS↗