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DOE OSTI2023

Microbial sensitivity to temperature and sulfate deposition modulates greenhouse gas emissions from peat soils

Abstract Peatlands are among the largest natural sources of atmospheric methane (CH 4 ) worldwide. Microbial processes play a key role in regulating CH 4 emissions from peatland ecosystems, yet the complex interplay between soil substrates and microbial communities in controlling CH 4 emissions as a function of global change remains unclear. Herein, we performed an integrated analysis of multi‐omics data sets to provide a comprehensive understanding of the molecular processes driving changes in greenhouse gas (GHG) emissions in peatland ecosystems with increasing temperature and sulfate deposition in a laboratory incubation study. We sought to first investigate how increasing temperatures (4, 21, and 35°C) impact soil microbiome–metabolome interactions; then explore the competition between methanogens and sulfate‐reducing bacteria (SRBs) with increasing sulfate concentrations at the optimum temperature for methanogenesis. Our results revealed that peat soil organic matter degradation, mediated by biotic and potentially abiotic processes, is the main driver of the increase in CO 2 production with temperature. In contrast, the decrease in CH 4 production at 35°C was linked to the absence of syntrophic communities and the potential inhibitory effect of phenols on methanogens. Elevated temperatures further induced the microbial communities to develop high growth yield and stress tolerator trait‐based strategies leading to a shift in their composition and function. On the other hand, SRBs were able to outcompete methanogens in the presence of non‐limiting sulfate concentrations at 21°C, thereby reducing CH 4 emissions. At higher sulfate concentrations, however, the prevalence of communities capable of producing sufficient low‐molecular‐weight carbon substrates for the coexistence of SRBs and methanogens was translated into elevated CH 4 emissions. The use of omics in this study enhanced our understanding of the structure and interactions among microbes with the abiotic components of the system that can be useful for mitigating GHG emissions from peatland ecosystems in the face of global change.

AminiTabrizi, Roya↗

NASA NTRS2017

Multi-Wavelength Laser Transmitter for the Two-Step Laser Time-of-Flight Mass Spectrometer

Missions to diverse Outer Solar System bodies will require investigations that can detect a wide range of organics in complex mixtures, determine the structure of selected molecules, and provide powerful insights into their origin and evolution. Previous studies from remote spectroscopy of the Outer Solar System showed a diverse population of macromolecular species that are likely to include aromatic and conjugated hydrocarbons with varying degrees of methylation and nitrile incorporation. In situ exploration of Titan's upper atmosphere via mass and plasma spectrometry has revealed a complex mixture of organics. Similar material is expected on the Ice Giants, their moons, and other Outer Solar System bodies, where it may subsequently be deposited onto surface ices. It is evident that the detection of organics on other planetary surfaces provides insight into the chemical and geological evolution of a Solar System body of interest and can inform our understanding of its potential habitability. We have developed a prototype two-step laser desorption/ionization time-of-flight mass spectrometer (L2MS) instrument by exploiting the resonance-enhanced desorption of analyte. We have successfully demonstrated the ability of the L2MS to detect hydrocarbons in organically-doped analog minerals, including cryogenic Ocean World-relevant ices and mixtures. The L2MS instrument operates by generating a neutral plume of desorbed analyte with an IR desorption laser pulse, followed at a delay by a ultraviolet (UV) laser pulse, ionizing the plume. Desorption of the analyte, including trace organic species, may be enhanced by selecting the wavelength of the IR desorption laser to coincide with IR absorption features associated with vibration transitions of minerals or organic functional groups. In this effort, a preliminary laser developed for the instrument uses a breadboard mid-infrared (MIR) desorption laser operating at a discrete 3.475 μm wavelength, and a breadboard UV ionization laser operating at a wavelength of 266 nm. The MIR wavelength was selected to overlap the C-H stretch vibrational transition of certain aromatic hydrocarbons, and the UV wavelength provides additional selectivity to aromatic species via UV resonance-enhanced multiphoton ionization effects. The use of distinct laser wavelengths allows efficient coupling to the vibrational and electronic spectra of the analyte in independent desorption and ionization steps, mitigating excess energy that can lead to fragmentation during the ionization process and leading to selectivity that can aid in data interpretation.

Yu, Anthony W.↗

DOE OSTI2024

Surface-to-Interior Transport Timescales and Ventilation Patterns in a Time-Dependent Circulation Driven by Sustained Climate Warming

Abstract The effect of climate warming in response to rising atmospheric CO 2 on the ventilation of the ocean remains uncertain. Here we make theoretical advances in elucidating the relationship between ideal age and transit time distribution (TTD) in a time-dependent flow. Subsequently, we develop an offline tracer-transport model to characterize the ventilation patterns and time scales in the time-evolving circulation for the 1850–2300 period as simulated with the Community Earth System Model version 1 (CESMv1) under a business-as-usual warming scenario. We found that by 2300 2.1% less water originates from the high-latitude deep water formation regions (both hemispheres) compared to 1850. In compensation, there is an increase in the water originating from the subantarctic. We also found that slowing meridional overturning circulation causes a gradual increase in mean age during the 1850–2300 period, with a globally averaged mean-age increase of ∼110 years in 2300. Where and when the water will be re-exposed to the atmosphere depends on the post-2300 circulation. For example, if we assume that the circulation persists in its year-2300 state (scenario 1), the mean interior-to-surface transit time in year 1850 is ∼1140 years. In contrast, if we assume that the circulation abruptly recovers to its year-1850 state (scenario 2), the mean interior-to-surface transit time in 1850 is only ∼740 years. By 2300, these differences become even larger; in scenario 1, the mean interior-to-surface transit time increases by ∼200 years, whereas scenario 2 decreases by ∼80 years. The dependence of interior-to-surface transit time on the future ocean circulation produces an additional unavoidable uncertainty in the long-term durability of marine carbon dioxide removal strategies. Significance Statement The ocean’s circulation, when altered by climate warming, can affect its capacity to absorb heat and CO 2 , which are crucial for the global climate. In our study, we investigated how global warming, caused by rising CO 2 levels, might impact the ocean circulation—the way water moves from deep ocean to the surface and vice versa. We discovered that by 2300, if we continue on our current warming trajectory, the origins of water within the ocean will shift, with less coming from deep, cold zones near the poles and more from subantarctic regions. As a result, deep water will take longer time before it resurfaces than shallow water. How quickly this water travels from deep regions to the surface could change, depending on the state of future ocean circulation. If the circulation remains as predicted in 2300, this journey will take longer. Conversely, if it reverts to the pattern in 1850, the process will be quicker. This variability introduces added uncertainty to strategies aimed at mitigating climate change by storing CO 2 in the ocean. Our work highlights the intricate ways in which climate change can influence our oceans, potentially affecting our plans to mitigate global warming.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS2013

Influences of Regional Climate Change on Air Quality Across the Continental U.S. Projected from Downscaling IPCC AR5 Simulations

Projecting climate change scenarios to local scales is important for understanding, mitigating, and adapting to the effects of climate change on society and the environment. Many of the global climate models (GCMs) that are participating in the Intergovernmental Panel on Climate Change (IPCC) Fifth Assessment Report (AR5) do not fully resolve regional-scale processes and therefore cannot capture regional-scale changes in temperatures and precipitation. We use a regional climate model (RCM) to dynamically downscale the GCM's large-scale signal to investigate the changes in regional and local extremes of temperature and precipitation that may result from a changing climate. In this paper, we show preliminary results from downscaling the NASA/GISS ModelE IPCC AR5 Representative Concentration Pathway (RCP) 6.0 scenario. We use the Weather Research and Forecasting (WRF) model as the RCM to downscale decadal time slices (1995-2005 and 2025-2035) and illustrate potential changes in regional climate for the continental U.S. that are projected by ModelE and WRF under RCP6.0. The regional climate change scenario is further processed using the Community Multiscale Air Quality modeling system to explore influences of regional climate change on air quality.

Air quality control↗

DOE OSTI2021

Validation of the Sentinel-5 Precursor TROPOMI cloud data with Cloudnet, Aura OMI O 2 –O 2 , MODIS, and Suomi-NPP VIIRS

Accurate knowledge of cloud properties is essential to the measurement of atmospheric composition from space. In this work we assess the quality of the cloud data from three Copernicus Sentinel-5 Precursor (S5P) TROPOMI cloud products: (i) S5P OCRA/ROCINN_CAL (Optical Cloud Recognition Algorithm/Retrieval of Cloud Information using Neural Networks;Clouds-As-Layers), (ii) S5P OCRA/ROCINN_CRB (Clouds-as-Reflecting Boundaries), and (iii) S5P FRESCO-S (Fast Retrieval Scheme for Clouds from Oxygen absorption bands – Sentinel). Target properties of this work are cloud-top height and cloud optical thickness (OCRA/ROCINN_CAL), cloud height (OCRA/ROCINN_CRB and FRESCO-S), and radiometric cloud fraction (all three algorithms). The analysis combines (i) the examination of cloud maps for artificial geographical patterns, (ii) the comparison to other satellite cloud data (MODIS, NPP-VIIRS, and OMI O2–O2), and (iii) ground-based validation with respect to correlative observations (30 April 2018 to 27 February 2020) from the Cloudnet network of ceilometers, lidars, and radars. Zonal mean latitudinal variation of S5P cloud properties is similar to that of other satellite data. S5P OCRA/ROCINN_CAL agrees well with NPP VIIRS cloud-top height and cloud optical thickness and with Cloudnet cloud-top height, especially for the low (mostly liquid) clouds. For the high clouds, S5P OCRA/ROCINN_CAL cloud-top height is below the cloud-top height of VIIRS and of Cloudnet, while its cloud optical thickness is higher than that of VIIRS. S5P OCRA/ROCINN_CRB and S5P FRESCO cloud height are well below the Cloudnet cloud mean height for the low clouds but match on average better with the Cloudnet cloud mean height for the higher clouds. As opposed to S5P OCRA/ROCINN_CRB and S5P FRESCO, S5P OCRA/ROCINN_CAL is well able to match the lowest CTH mode of the Cloudnet observations. Peculiar geographical patterns are identified in the cloud products and will be mitigated in future releases of the cloud data products.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS2011

Understanding Effective Diameter and Its Application to Terrestrial Radiation in Ice Clouds

The cloud property known as "effective diameter" or "effective radius", which in essence is the cloud particle size distribution (PSD) volume at bulk density divided by its projected area, is used extensively in atmospheric radiation transfer, climate modeling and remote sensing. This derives from the assumption that PSD optical properties can be uniquely described in terms of their effective diameter, D(sub e), and their cloud water content (CWC), henceforth referred to as the D(sub e)-CWC assumption. This study challenges this assumption, showing that while the D(sub e)-CWC assumption appears generally valid for liquid water clouds, it appears less valid for ice clouds in regions where (1) absorption is not primarily a function of either the PSD ice water content (IWC) or the PSD projected area, and (2) where wave resonance (i.e. photon tunneling) contributes significantly to absorption. These two regions often strongly coincide at terrestrial wavelengths when De less than ~60 m, which is where this D(sub e)-CWC assumption appears poorest. Treating optical properties solely in terms of D(sub e) and IWC may lead to errors up to 24%, 26% and 20% for terrestrial radiation in the window region regarding the absorption and extinction coefficients and the single scattering albedo, respectively. Outside the window region, errors may reach 33% and 42% regarding absorption and extinction. The magnitude and sign of these errors can change rapidly with wavelength, which may produce significant errors in climate modeling, remote sensing and other applications concerned with the wavelength dependence of radiation. Where the D(sub e)-CWC assumption breaks down, ice cloud optical properties appear to depend on D(sub e), IWC and the PSD shape. Optical property parameterizations in climate models and remote sensing algorithms based on historical PSD measurements may exhibit errors due to previously unknown PSD errors (i.e. the presence of ice artifacts due to the shattering of larger ice particles on the probe inlet tube during sampling). More recently developed cloud probes are designed to mitigate this shattering problem. Using realistic PSD shapes for a given temperature (and/or IWC) and cloud type may minimize errors associated with PSD shape in ice optics parameterizations and remote sensing algorithms. While this topic was investigated using two ice optics schemes (the Yang et al., 2005 database and the modified anomalous diffraction approximation, or MADA), a physical understanding of the limitations of the D(sub e)-IWC assumption was made possible by using MADA. MADA allows one to approximate the contribution of photon tunneling to absorption relative to other optical processes, which reveals that part of the error regarding the D(sub e)-IWC assumption can be associated with tunneling. By relating the remaining error to the radiation penetration depth in bulk ice (DELTA L) due to absorption, the domain where the D(sub e)-IWC assumption is weakest was described in terms of D(sub e) and DELTA L.

Mitchell, D. L.↗

NASA NTRS2024

Aera-Mip: Emission Pathways, Remaining Budgets, and Carbon Cycle Dynamics Compatible With 1.5 and 2 °C Global Warming Stabilization

While international climate policies now focus on limiting global warming to well below 2 °C or pursuing a 1.5 °C level of global warming, the climate modelling community has not provided an experimental design in which all Earth system models (ESMs) converge and stabilize at the same prescribed global warming levels. This gap hampers accurate estimations based on comprehensive ESMs of the carbon emission pathways and budgets needed to meet such agreed warming levels and of the associated climate impacts under temperature stabilization. Here, we apply the Adaptive Emission Reduction Approach (AERA) with ESMs to provide such simulations in which all models converge at 1.5 and 2.0 °C warming levels by adjusting their emissions over time. These emission-driven simulations provide a wide range of emission pathways and resulting atmospheric CO 2 projections for a given warming level, uncovering uncertainty ranges that were previously missing in the traditional Coupled Model Intercomparison Project (CMIP) scenarios with prescribed greenhouse gas concentration pathways. Meeting the 1.5 °C warming level requires a 40 % (full model range: 7 % to 76 %) reduction in multi-model mean CO 2 -forcing-equivalent (CO 2 -fe) emissions from 2025 to 2030, a 98 % (57 % to 127 %) reduction from 2025 to 2050, and a stabilization at 1.0 (−1.7 to 2.9) PgC yr−1 from 2100 onward after the 1.5 °C global warming level is reached. Meeting the 2.0 °C warming level requires a 47 % (8 % to 92 %) reduction in multi-model mean CO 2 -fe emissions until 2050 and a stabilization at 1.7 (−1.5 to 2.7) PgC yr−1 from 2100 onward. The on-average positive emissions under stabilized global temperatures are the result of a decreasing transient climate response to cumulative CO 2 -fe emissions over time under stabilized global warming. This evolution is consistent with a slightly negative zero emissions commitment – initially assumed to be zero – and leads to an increase in the post-2025 CO 2 -fe emission budget by a factor of 2.2 (−0.8 to 6.9) by 2150 for the 1.5 °C warming level and a factor of 1.4 (0.9 to 2.4) for the 2.0 °C warming level compared to its first estimate in 2025. The median CO 2 -only carbon budget by 2150, relative to 2020, is 800 GtCO 2 for the 1.5 °C warming level and 2250 GtCO 2 for the 2.0 °C warming level. These median values exceed the median IPCC AR6 estimates by 60 % for the 1.5 °C warming level and 67 % for 2.0 °C. Some of the differences may be explained by the choice of the mitigation scenario for non-CO 2 radiative agents. Our simulations highlight shifts in carbon uptake dynamics under stabilized temperature, such as a cessation of the carbon sinks in the North Atlantic and in tropical forests. On the other hand, the Southern Ocean remains a carbon sink centuries after temperatures stabilize. Overall, this new type of warming-level-based emission-driven simulation offers a more coherent assessment across climate models and opens up a wide range of possibilities for studying both the carbon cycle and climate impacts, such as extreme events, under climate stabilization.

Adaptive Emission Reduction Approach↗

NASA NTRS1993

Adaptive digital beamforming for a CDMA mobile communications payload

In recent years, Spread-Spectrum Code Division Multiple Access (CDMA) has become a very popular access scheme for mobile communications due to a variety of reasons: excellent performance in multipath environments, high scope for frequency reuse, graceful degradation near saturation, etc. In this way, a CDMA system can support simultaneous digital communication among a large community of relatively uncoordinated users sharing a given frequency band. Nevertheless, there are also important problems associated with the use of CDMA. First, in a conventional CDMA scheme, the signature sequences of asynchronous users are not orthogonal and, as the number of active users increases, the self-noise generated by the mutual interference between users considerably degrades the performance, particularly in the return link. Furthermore, when there is a large disparity in received powers - due to differences in slant range or atmospheric attenuation - the non-zero cross-correlation between the signals gives rise to the so-called near-far problem. This leads to an inefficient utilization of the satellite resources and, consequently, to a drastic reduction in capacity. Several techniques were proposed to overcome this problem, such as Synchronized CDMA - in which the signature sequences of the different users are quasi-orthogonal - and power control. At the expense of increased network complexity and user coordination, these techniques enable the system capacity to be restored by equitably sharing the satellite resources among the users. An alternative solution is presented based upon the use of time-reference adaptive digital beamforming on board the satellite. This technique enables a high number of independently steered beams to be generated from a single phased array antenna, which automatically track the desired user signal and null the unwanted interference source. In order to use a time-reference adaptive antenna in a communications system, the main challenge is to obtain a reference signal highly correlated with the desired user signal and uncorrelated with the interferences. CDMA lends itself very easily to the generation of such a reference signal, thanks to the a priori knowledge of the user's signature sequence. First, the integration of an adaptive antenna in an asynchronous CDMA system is analyzed. The adaptive antenna system can provide increased interference rejection - much higher than that afforded by the code alone - and, since CDMA is mainly interference limited, any reduction in interference converts directly and linearly into an increase in capacity. Analyses and computer simulations are presented that show how an asynchronous CDMA system incorporating adaptive beamforming can provide at least as much capacity as a synchronous system. More importantly, the proposed concept allows the near-far effect to be mitigated without requiring a tight coordination of the users in terms of transmitted power control or network synchronization. The system is extremely robust to the near-far effect because the signals reaching the satellite from directions other than that of the desired user - which are likely to have different power levels - are adaptively canceled by the antenna. Finally, a payload architecture is presented that illustrates the practical implementation of this concept. This digital payload architecture demonstrates that with the advent of high performance CMOS digital processing, the on-board implementation of complex DSP techniques - in particular Digital Beamforming - has become possible, being most attractive for Mobile Satellite Communications.

Munoz-Garcia, Samuel G.↗

DOE OSTI2024

Improved Diagnosis of Precipitation Type with LightGBM Machine Learning

Abstract Existing precipitation-type algorithms have difficulty discerning the occurrence of freezing rain and ice pellets. These inherent biases are not only problematic in operational forecasting but also complicate the development of model-based precipitation-type climatologies. To address these issues, this paper introduces a novel light gradient-boosting machine (LightGBM)-based machine learning precipitation-type algorithm that utilizes reanalysis and surface observations. By comparing it with the Bourgouin precipitation-type algorithm as a baseline, we demonstrate that our algorithm improves the critical success index (CSI) for all examined precipitation types. Moreover, when compared with the precipitation-type diagnosis in reanalysis, our algorithm exhibits increased F1 scores for snow, freezing rain, and ice pellets. Subsequently, we utilize the algorithm to compute a freezing-rain climatology over the eastern United States. The resulting climatology pattern aligns well with observations; however, a significant mean bias is observed. We interpret this bias to be influenced by both the algorithm itself and assumptions regarding precipitation processes, which include biases associated with freezing drizzle, precipitation occurrence, and regional synoptic weather patterns. To mitigate the overall bias, we propose increasing the precipitation cutoff from 0.04 to 0.25 mm h −1 , as it better reflects the precision of precipitation observations. This adjustment yields a substantial reduction in the overall bias. Finally, given the strong performance of LightGBM in predicting mixed precipitation episodes, we anticipate that the algorithm can be effectively utilized in operational settings and for diagnosing precipitation types in climate model outputs. Significance Statement Freezing rain can have significant impacts on transportation and infrastructure, making accurate prediction of precipitation types crucial. In this study, we use a machine learning method known as LightGBM to predict precipitation types. We show that the new algorithm performs better than the existing methods for all precipitation types examined. Additionally, we compute a freezing-rain climatology over the eastern United States. Although the resulting climatology pattern corresponds well to observations, the algorithm overpredicts freezing-rain occurrence. We argue that this bias can be substantially reduced by increasing the precipitation cutoff from 0.04 to 0.25 mm h −1 . Overall, this work highlights the potential of the LightGBM algorithm for both weather forecasting and diagnosing precipitation types in climate models.

Meteorology & Atmospheric Sciences↗

NASA NTRS2016

Liquid Oxygen/Liquid Methane Integrated Power and Propulsion

The proposed paper will cover ongoing work at the National Aeronautics and Space Administration (NASA) Johnson Space Center (JSC) on integrated power and propulsion for advanced human exploration. Specifically, it will present findings of the integrated design, testing, and operational challenges of a liquid oxygen / liquid methane (LOx/LCH4) propulsion brassboard and Solid Oxide Fuel Cell (SOFC) system. Human-Mars architectures point to an oxygen-methane economy utilizing common commodities, scavenged from the planetary atmosphere and soil via In-Situ Resource Utilization (ISRU), and common commodities across sub-systems. Due to the enormous mass gear-ratio required for human exploration beyond low-earth orbit, (for every 1 kg of payload landed on Mars, 226 kg will be required on Earth) increasing commonality between spacecraft subsystems such as power and propulsion can result in tremendous launch mass and volume savings. Historically, propulsion and fuel cell power subsystems have had little interaction outside of the generation (fuel cell) and consumption (propulsion) of electrical power. This was largely due to a mismatch in preferred commodities (hypergolics for propulsion; oxygen & hydrogen for fuel cells). Although this stove-piped approach benefits from simplicity in the design process, it means each subsystem has its own tanks, pressurization system, fluid feed system, etc. increasing overall spacecraft mass and volume. A liquid oxygen / liquid methane commodities architecture across propulsion and power subsystems would enable the use of common tankage and associated pressurization and commodity delivery hardware for both. Furthermore, a spacecraft utilizing integrated power and propulsion could use propellant residuals - propellant which could not be expelled from the tank near depletion due to hydrodynamic considerations caused by large flow demands of a rocket engine - to generate power after all propulsive maneuvers are complete thus utilizing previously wasted mass. Such is the case for human and robotic planetary landers. Although many potential benefits through integrated power & propulsion exist, integrated operations have yet to be successfully demonstrated and many challenges have already been identified the most obvious of which is the large temperature gradient. SOFC chemistry is exothermic with operating temperatures in excess of 1,000 K; however, any shared commodities will be undoubtedly stored at cryogenic temperatures (90-112 K) for mass efficiency reasons. Spacecraft packaging will drive these two subsystems in close proximity thus heat leak into the commodity tankage must be minimized and/or mitigated. Furthermore, commodities must be gasified prior to consumption by the SOFC. Excess heat generated by the SOFC could be used to perform this phase change; however, this has yet to be demonstrated. A further identified challenge is the ability of the SOFC to handle the sudden power spikes created by the propulsion system. A power accumulator (battery) will likely be necessary to handle these sudden demands while the SOFC thermally adjusts. JSC's current SOFC test system consists of a 1 kW fuel cell designed by Delphi. The fuel cell is currently undergoing characterization testing at the NASA JSC Energy Systems Test Area (ESTA) after which a Steam Methane Reformer (SMR) will be integrated and the combined system tested in closed-loop. The propulsion brassboard is approximately the size of what could be flown on a sounding rocket. It consists of one 100 lbf thrust "main" engine developed for NASA by Aerojet and two 10 lbf thrusters to simulate a reaction control system developed at NASA JSC. This system is also under development and initial testing at ESTA. After initial testing, combined testing will occur which will provide data on the fuel cell's ability to sufficiently handle the power spikes created by the propulsion system. These two systems will also be modeled using General-Use Nodal Network Solver (GUNNS) software. Once anchored with test data, this model will be used to extrapolate onto other firing profiles and used to size the power accumulator.

Banker, Brian↗

NASA NTRS2021

Impact of Regional Northern Hemisphere Mid-latitude Anthropogenic Sulfur Dioxide Emissions on Local and Remote Tropospheric Oxidants

The unintended consequences of reductions in regional anthropogenic sulfur dioxide (SO2) emissions implemented to protect human health are poorly understood. SO2 decreases began in the 1970s in the US and Europe and are expected to continue into the future, while recent emissions decreases in China are also projected to continue. In addition to the well-documented climate effects (warming) from reducing aerosols, tropospheric oxidation is impacted via aerosol modification of photolysis rates and radical sinks. Impacts on the hydroxyl radical and other trace constituents directly affect climate and air quality metrics such as surface ozone levels. We use the Geophysical Fluid Dynamics Laboratory Atmospheric Model version 3 nudged towards National Centers for Environmental Prediction (NCEP) reanalysis wind velocities to estimate the impact of SO2 emissions from the US, Europe, and China by differencing a control simulation with an otherwise identical simulation in which 2015 anthropogenic SO2 emissions are set to zero over one of the regions. Springtime sulfate aerosol changes occur both locally to the emission region and also throughout the Northern Hemispheric troposphere, including remote oceanic regions and the Arctic. Hydroperoxy (HO2) radicals are directly removed via heterogeneous chemistry on aerosol surfaces, including sulfate, in the model, and we find that sulfate aerosol produced by SO2 emissions from the three individual northern mid-latitude regions strongly reduces both HO2 and hydroxyl (OH) by up to 10 % year-round throughout most of the troposphere north of 30∘ N latitude. Regional SO2 emissions significantly increase nitrogen oxides (NOx) by about 5 %–8 % throughout most of the free troposphere in the Northern Hemisphere by increasing the NOx lifetime as the heterogeneous sink of HO2 on sulfate aerosol declines. Despite the NOx increases, tropospheric ozone decreases at northern mid-latitudes by 1 %–4 % zonally averaged and by up to 5 ppbv in summertime surface air over China, where the decreases in HO2 and OH suppress O3 production. Since 2015 anthropogenic SO2 emissions in China exceed those in the US or Europe, the oxidative response is greatest for the China perturbation simulation. Chemical effects of aerosols on oxidation (reactive uptake) dominate over radiative effects (photolysis rates), the latter of which are only statistically significant locally for the large perturbation over China. We find that the SO2 emissions decrease in China, which has yet to be fully realized, will have the largest impact on oxidants and related species in the Northern Hemisphere free troposphere compared to future decreases in Europe or the US. Our results bolster previous calls for a multipollutant strategy for air pollution mitigation to avoid the unintended consequence of aerosol removal leading to surface ozone increases that offset or mask surface ozone gains achieved by regulation of other pollutants, especially in countries where current usage of high-sulfur emitting fuels may be phased out in the future.

anthropogenic sulfur dioxide emissions↗

NASA NTRS2000

BOREAS AFM-12 1-km AVHRR Seasonal Land Cover Classification

The Boreal Ecosystem-Atmosphere Study (BOREAS) Airborne Fluxes and Meteorology (AFM)-12 team's efforts focused on regional scale Surface Vegetation and Atmosphere (SVAT) modeling to improve parameterization of the heterogeneous BOREAS landscape for use in larger scale Global Circulation Models (GCMs). This regional land cover data set was developed as part of a multitemporal one-kilometer Advanced Very High Resolution Radiometer (AVHRR) land cover analysis approach that was used as the basis for regional land cover mapping, fire disturbance-regeneration, and multiresolution land cover scaling studies in the boreal forest ecosystem of central Canada. This land cover classification was derived by using regional field observations from ground and low-level aircraft transits to analyze spectral-temporal clusters that were derived from an unsupervised cluster analysis of monthly Normalized Difference Vegetation Index (NDVI) image composites (April-September 1992). This regional data set was developed for use by BOREAS investigators, especially those involved in simulation modeling, remote sensing algorithm development, and aircraft flux studies. Based on regional field data verification, this multitemporal one-kilometer AVHRR land cover mapping approach was effective in characterizing the biome-level land cover structure, embedded spatially heterogeneous landscape patterns, and other types of key land cover information of interest to BOREAS modelers.The land cover mosaics in this classification include: (1) wet conifer mosaic (low, medium, and high tree stand density), (2) mixed coniferous-deciduous forest (80% coniferous, codominant, and 80% deciduous), (3) recent visible bum, vegetation regeneration, or rock outcrops-bare ground-sparsely vegetated slow regeneration bum (four classes), (4) open water and grassland marshes, and (5) general agricultural land use/ grasslands (three classes). This land cover mapping approach did not detect small subpixel-scale landscape features such as fens, bogs, and small water bodies. Field observations and comparisons with Landsat Thematic Mapper (TM) suggest a minimum effective resolution of these land cover classes in the range of three to four kilometers, in part, because of the daily to monthly compositing process. In general, potential accuracy limitations are mitigated by the use of conservative parameterization rules such as aggregation of predominant land cover classes within minimum horizontal grid cell sizes of ten kilometers. The AFM-12 one-kilometer AVHRR seasonal land cover classification data are available from the Earth Observing System Data and Information System (EOSDIS) Oak Ridge National Laboratory (ORNL) Distributed Active Archive Center (DAAC). The data files are available on a CD-ROM (see document number 20010000884).

Steyaert, Lou↗

NASA NTRS2009

Aerojet - Attitude Control Engines

All the engines were both qualification and acceptance tested at Marquardt s facilities. After we won the Apollo Program contract, we went off and built two vacuum test facilities, which simulated altitude continuous firing for as long as we wanted to run an engine. They would run days and days with the same capability we had on steam ejection. We did all of the testing in both for the qualification and the acceptance test. One of them was a large ball, which was an eighteen-foot diameter sphere, evacuated again with a big steam ejector system that could be used for system testing; that s where we did the Lunar Excursion Module testing. We put the whole cluster in there and tested the entire cluster at the simulated altitude conditions. The lowest altitude we tested at - typically an acceptance test - was 105,000 feet simulated altitude. The big ball - because people were interested in what they called goop formation, which is an unburned hydrazine product migrating to cold surfaces on different parts of spacecraft - was built to address those kinds of issues. We ran long-life tests in a simulated space environment with the entire inside of the test cell around the test article, liquid nitrogen cooled, so it could act as getter for any of the exhaust products. That particular facility could pull down to about 350,000 feet (atmosphere) equivalent altitude, which was pushing pretty close to the thermodynamic triple point of the MMH. It was a good test facility. Those facilities are no longer there. When the guys at Marquardt sold the company to what eventually became part of Aerojet, all those test facilities were cut off at the roots. I think they have a movie studio there at this point. That part of it is truly not recoverable, but it did some excellent high-altitude, space-equivalent testing at the time. Surprisingly, we had very few problems while testing in the San Fernando Valley. In the early 1960s, nobody had ever seen dinitrogen tetroxide (N2O4), so that wasn't too big a deal. We really did only make small, red clouds. In all the hundreds of thousands of tests and probably well over one million firings that I was around that place for, in all that thirty-something years, we had a total of one serious injury associated with rocket engine testing and propellants. Because we were trying to figure out what propellants would really be good, we tried all of the fun stuff like the carbon tetrafluoride, chlorine pentafluoride, and pure fluorine. The materials knowledge wasn't all that great at the time. On one test, the fluorine we had didn't react well with the copper they were using for tubing, and it managed to cause another unscheduled disassembly of the facility. It was very serious. It's like one of those Korean War stories. The technician happened to be walking past the test facility when it decided to blow itself up. A piece of copper tubing pierced one cheek and came out the other. That was the only serious accident in all of the engines handled in all those years. Now, we did have a problem with the EPA later because they figured out what the brown clouds were about. We built a whole bunch of exhaust mitigation scrubbers to take care of engine testing in the daytime. In general, we operated the big shuttle (RCS) engine, the 870- pounder at nominal conditions; they scrubbed the effluents pretty well. If you operated that same 870-pound force engine at a level where you get a lot of excess oxidizer, yeah, there s a brown cloud. But, you know, it doesn't show up well in the dark. They did do some of that. But, that s gone; it was addressed one way or another. RELEASED -

Pfeifer, Gerald R.↗

DOE OSTI2024

Recovery of Natural Gas Equipment Emissions into Gas Compression Engines for the Reduction of Potential Greenhouse Gas Emissions

Since the turn of the millennium, the United States (U.S.) oil and natural gas (ONG) industry has nearly doubled its natural gas production rate. As a result, the ONG industry has recently come under increasing scrutiny for its contributions to greenhouse gas (GHG) emissions. Consequently, various solutions to this problem have been proposed and formulated to reduce the impacts of GHG emissions on the environment. West Virginia University (WVU) have found it important to research the impacts of recovering vented gas streams into prime-mover engines. The U.S. Department of Energy (DOE) and National Energy Technology Laboratory (NETL) have granted WVU funding to research and develop a “Methane Mitigator” (M2) - a “Scalable Vent Mitigation Strategy to Simultaneously Reduce Methane Emissions and Fuel Consumption from the Compression Industry.” One of the main areas of interest for this research was the collection of emissions from natural gas equipment into a Caterpillar G3508J natural gas compression engine. The parameters being analyzed from the engine were brake-specific emissions and power output. The emissions sources considered for this research were pneumatic controllers (PCs), reciprocating compressor vents, and the engine’s open crankcase breather. The compressor vent and PC emissions were simulated using a mass flow controller (MFC) and flowed into the engine using two separate methods: (1) directly into the air intake, and (2) through a retrofitted closed crankcase ventilation system (CCV), serving as a buffer volume. The crankcase emissions were quantified without the CCV, and the impact on exhaust emissions from circulating the crankcase gases into the intake was measured. The simulated compressor vent and PC flows from the MFC had limited effect on the steady state operation of the engine and resulting performance. When the simulated flows were fed directly into the engine’s air intake, the changes within the engine’s continuous performance and emission parameters were larger but lasted for shorter durations. Conversely, when the simulated flows were fed into the CCV before entering the air intake, the changes in the engine’s performance and emission parameters were less pronounced for continuous analysis but lasted for longer durations. In either case, the continuous emission changes in both emissions and performance varied in size depending on the test scenario being run, but the cycle average changes in emissions and performance showed little impact overall compared to the engine’s baseline operation. As a result, the inclusion of a CCV shows a decrease in baseline carbon dioxide equivalent (CO2-eq.) engine emissions (from combined exhaust and open crankcase) of almost 4%. Likewise, the CCV inclusion reduced baseline total methane (CH4) from combined exhaust and open crankcase by upwards of 16%. These atmospheric emissions only decreased further with the inclusions of collected PC and compressor vent flows. The resulting changes in time-averaged rated exhaust behavior (or lack thereof) prove that the proposed M2 system could likely be deployed at sites with modern lean-burn natural gas engines as a viable option for reducing and eliminating potential GHG sources that would have otherwise been unutilized as energy sources.

03 NATURAL GAS↗

DOE OSTI2024

Capturing carbon dioxide from air with charged-sorbents

Emissions reduction and greenhouse gas removal from the atmosphere are both necessary to achieve net-zero emissions and limit climate change. There is thus a need for improved sorbents for the capture of carbon dioxide from the atmosphere, a process known as direct air capture. In particular, low-cost materials that can be regenerated at low temperatures would overcome the limitations of current technologies. In this work, we introduce a new class of designer sorbent materials known as ‘charged-sorbents’. These materials are prepared through a battery-like charging process that accumulates ions in the pores of low-cost activated carbons, with the inserted ions then serving as sites for carbon dioxide adsorption. We use our charging process to accumulate reactive hydroxide ions in the pores of a carbon electrode, and find that the resulting sorbent material can rapidly capture carbon dioxide from ambient air by means of (bi)carbonate formation. Unlike traditional bulk carbonates, charged-sorbent regeneration can be achieved at low temperatures (90–100 °C) and the sorbent’s conductive nature permits direct Joule heating regeneration using renewable electricity. Given their highly tailorable pore environments and low cost, we anticipate that charged-sorbents will find numerous potential applications in chemical separations, catalysis and beyond.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2021

Methane Mitigation Thermoelectric Generator (MMTEG) (Final Scientific/ Technical Report)

Gas Technology Institute (GTI) has completed a $1.815M (plus $500K cost share), 54-month Co-operative agreement with the Department of Energy’s National Energy Technology Laboratory to develop a Methane Mitigation Thermoelectric Generator (MMTEG) system for gas field applications. This novel system uses fugitive gas to produce electrical power and consists of Thermoelectric Generators (TEG) driven by a linear burner, an air compressor, an accumulator, valves, batteries, and power electronics. The electrical power generated by the system is used to compress air and, in turn, the air is used to operate the pneumatic valves at the well site instead of using natural gas (NG) which would then be vented. The team completed the project objectives which included (1) Design, fabricate and test an integrated 6We nominal MMTEG prototype system, (2) Design a “retrofit kit” MMTEG system capable of being field tested at a gas well production site, and (3) build and test the field MMTEG system in a laboratory environment. Multiple system options were developed prior to selecting a “Passive” system which meets cost, NG savings, and greenhouse gas (GHG) reduction targets although not as efficient as initially planned. The MMTEG system is built primarily from commercial off-the-shelf parts (in some cases re-purposed) including the heat exchanger, heat rejection, electronic components, and also the TEGs. The team developed and implemented a novel system including the control system developed by Morrison Applied Sciences (MAS). The team completed incremental demonstrations of the hardware prior to the MMTEG system demonstration. A one-year simulation of the air delivery and battery charging subsystems was completed prior to the integration into the MMTEG system. In addition, the team simulated two-years of thermal cycles for integrated Burner/TEG/heat rejection subsystem. Finally, the entire MMTEG system was assembled, and troubleshooting was completed over a two-week period. Next, the MMTEG system was tested to simulate over 15 weeks of entire system operation over approximately four weeks in an accelerated test fashion with minimal intervention (such as changing fuel tanks). The MMTEG system met the key goals of a unit cost of under $1500 while saving 97% of NG expended today (including leakage) on average by pneumatic systems venting to the atmosphere. The MMTEG system reduced GHG emissions by 1000X (using the methane intensification factor of 28 relative to CO2). GTI is currently pursuing a field test of the MMTEG system. Interfacing with producers has provided additional insight into system improvements. Planned improvements include additional weather protection and control system improvements including the implementation of a long- range radio capability to notify operators if there is a fault.

03 NATURAL GAS↗

DOE OSTI2024

The circular bioeconomy: a driver for system integration

Background: Human and earth system modeling, traditionally centered on the interplay between the energy system and the atmosphere, are facing a paradigm shift. The Intergovernmental Panel on Climate Change’s mandate for comprehensive, cross-sectoral climate action emphasizes avoiding the vulnerabilities of narrow sectoral approaches. Our study explores the circular bioeconomy, highlighting the intricate interconnections among agriculture, forestry, aquaculture, technological advancements, and ecological recycling. Collectively, these sectors play a pivotal role in supplying essential resources to meet the food, material, and energy needs of a growing global population. We pose the pertinent question of what it takes to integrate these multifaceted sectors into a new era of holistic systems thinking and planning. Results: The foundation for discussion is provided by a novel graphical representation encompassing statistical data on food, materials, energy flows, and circularity. This representation aids in constructing an inventory of technological advancements and climate actions that have the potential to significantly reshape the structure and scale of the economic metabolism in the coming decades. In this context, the three dominant mega-trends—population dynamics, economic developments, and the climate crisis—compel us to address the potential consequences of the identified actions, all of which fall under the four categories of substitution, efficiency, sufficiency, and reliability measures. Substitution and efficiency measures currently dominate systems modeling. Including novel bio-based processes and circularity aspects might require only expanded system boundaries. Conversely, paradigm shifts in systems engineering are expected to center on sufficiency and reliability actions. Effectively assessing the impact of sufficiency measures will necessitate substantial progress in inter- and transdisciplinary collaboration, primarily due to their non-technological nature. In addition, placing emphasis on modeling the reliability and resilience of transformation pathways represents a distinct and emerging frontier that highlights the significance of an integrated network of networks. Conclusions: Existing and emerging circular bioeconomy practices can serve as prime examples of system integration. These practices facilitate the interconnection of complex biomass supply chain networks with other networks encompassing feedstock-independent renewable power, hydrogen, CO 2 , water, and other biotic, abiotic, and intangible resources. Elevating the prominence of these connectors will empower policymakers to steer the amplification of synergies and mitigation of tradeoffs among systems, sectors, and goals.

09 BIOMASS FUELS↗

DOE OSTI2020

Advanced Anode for Internal Reforming and Thermal Management in Solid Oxide Fuel Cells

Solid oxide fuel cell (SOFC) is an efficient and clean electrical power generation system compared to conventional combustion based technologies with energy efficiency reaching as high as 85-90% in co-generation mode (electricity and heat). Other advantages of SOFCs are hybridization, modularity of construction, small CO 2 foot print per kWh of generated electricity and fuel flexibility. Hydrocarbons present in the gaseous fuel is utilized in SOFCs by internal or external reforming. There are two different internal reforming concepts: Direct Internal Reforming (DIR) and Indirect Internal Reforming (IIR). For DIR operation, the endothermic reforming reaction and the exothermic reaction from the oxidation reaction are operated together in the single unit eliminating the requirement for a separate fuel reformer. This configuration also simplifies the overall system design, making SOFC more attractive and efficient means of producing electrical power. The main advantage of the DIR type of operation is that the H 2 or CO consumption by the electrochemical reaction could directly promote the conversion of methane at the anode side of the fuel cell resulting in high conversion and high efficiency. The DIR operation, however, requires an anode material that has desired dual catalytic (hetero and electro) properties for reforming reaction and electrochemical reactions. The anode materials also need to remain resistant to carbon formation at the operating temperature and atmosphere with stable cell performance. Another requirement is to match the reforming reactions and electrochemical reactions to avoid local cooling or overheating, which can result in mechanical failure due to thermally induced stresses. Direct internal reforming (DIR) of hydrocarbon fuels simplifies the overall SOFC system design making it more attractive and efficient for producing electrical power. Low cost alloy anodes for distributed internal reforming of methane and other hydrocarbon fuels offer increased fuel-flexibility, reliability, and long term performance stability of solid oxide fuel cells (SOFC). The research program examined modification of the chemical compositions and microstructure of high entropy alloy (HEA) anode materials using thermochemical calculations and process simulation and modeling to achieve distributed reforming over the entire anode to eliminate hot zones. Cell fabrication and testing of the HEA anodes using button cell configuration has been performed to demonstrate the advantages of new anode over traditional Ni-YSZ anodes for distributed reforming and carbon free operation. Technical accomplishments include identification and synthesis of HEA carbon-resistant anode, demonstration of reduction in reforming rate confirmed by GC and modelling data validating effectiveness for thermal management in cell/stacks, electrochemical testing of HEA anode in single cell (HEA-GDC||YSZ||LSM-YSZ) and Characterization of pretest and posttest anode materials by TEM and SEM-EDS confirming carbon-free operation.

30 DIRECT ENERGY CONVERSION↗