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All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Intermediate soil acidification induces highest nitrous oxide emissions

Global potent greenhouse gas nitrous oxide (N 2 O) emissions from soil are accelerating, with increases in the proportion of reactive nitrogen emitted as N 2 O, i.e., N 2 O emission factor (EF). Yet, the primary controls and underlying mechanisms of EFs remain unresolved. Based on two independent but complementary global syntheses, and three field studies determining effects of acidity on N 2 O EFs and soil denitrifying microorganisms, we show that soil pH predominantly controls N 2 O EFs and emissions by affecting the denitrifier community composition. Analysis of 5438 paired data points of N 2 O emission fluxes revealed a hump-shaped relationship between soil pH and EFs, with the highest EFs occurring in moderately acidic soils that favored N 2 O-producing over N 2 O-consuming microorganisms, and induced high N 2 O emissions. Our results illustrate that soil pH has a unimodal relationship with soil denitrifiers and EFs, and the net N 2 O emission depends on both the N 2 O/(N 2 O + N 2 ) ratio and overall denitrification rate. These findings can inform strategies to predict and mitigate soil N 2 O emissions under future nitrogen input scenarios.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS2000

Introduction to the SONEX (Subsonic Assessment Ozone and Nitrogen Oxides Experiment) and POLINAT-2 (Pollution from Aircraft Emissions in the North Atlantic Flight Corridor) Special Issue

Emissions of atmospheric species from the engines of subsonic aircraft at cruise altitude (roughly, above seven kilometers) are of concern to scientists, the aviation industry and policymakers for two reasons. First, water vapor, soot and sulfur oxides, and related heterogeneous processes, may modify clouds and aerosols enough to perturb radiative forcing in the UT/LS (upper troposphere/lower stratosphere). A discussion of these phenomena appears in Chapter 3 of the IPCC Aviation Assessment (1999). An airborne campaign conducted to evaluate aviation effects on contrail, cirrus and cloud formation, is described in Geophysical Research Letters. The second concern arises from subsonic aircraft emissions of nitrogen oxides (NO + NO2 = NO(sub x)), CO, and hydrocarbons. These species may add to the background mixture of photochemically reactive species that form ozone. In the UT/LS, ozone is a highly effective greenhouse gas. The impacts of subsonic aircraft emissions on tropospheric NO(sub x) and ozone budgets have been studied with models that focus on UT chemistry [e.g. see discussions of individual models in Brasseur et al., 1998; Friedl et al., 1997; IPCC, 1999]. Depending on the model used, projected increases in the global subsonic aircraft fleet from 1992 to 2015 will lead to a 50-100 pptv increase in UT/LS NO. at 12 km (compared to 50-150 pptv background) in northern hemisphere midlatitudes. The corresponding 12-km ozone increase is 7-11 ppbv, or 5-10% (Chapter 4 in IPCC, 1999). Two major sources of uncertainties in model estimates of aviation effects are: (1) the often limited degree to which global models - the scale required to evaluate aircraft emissions - realistically simulate atmospheric transport and other physical processes; (2) limited UT/LS observations of trace gases with which to evaluate model performance. In response to the latter deficiency, a number of airborne campaigns aimed at elucidating the effect of aircraft on atmospheric nitrogen oxides and ozone were performed between 1990 and 1996 (see descriptions in Friedl et al., 1997; Brasseur et al., 1998).

Thompson, Anne M.↗
NASA NTRSDate not supplied

The Influence of Chemical Descriptors on the Reactivity of Potential Hypergolic Fuels With Hydrogen Peroxide

The state-of-the-art for storable hypergolic bipropellant systems is monomethylhydrazine (MMH) and mixed oxides of nitrogen (MON). While MMH and MON provide fast and highly reliable hypergolic ignition with excellent propulsive performance, they suffer from safety concerns impacting their production, cost, and supply to various test and launch facilities. In contrast, identifying and demonstrating low-toxicity fuels hypergolic with rocket grade hydrogen peroxide (H2O2) has been challenging with long ignition delay (IDT) and low propulsive performance affecting their deployment in flight systems. This work describes a preliminary observational study to assess the effects of molecular descriptors suspected to predict the reactivity and hypergolicity of compounds within the same chemical class (i.e., thioamide). The approach centered on evaluating functional groups, electrostatic potential, number of carbons, dipole moment, and adiabatic ionization energy. Thiourea is hypergolic with 89.2 wt.% H2O2 (minimum IDT of 21.9 ms) and was selected as a core fuel to study the reactivity of derived fuels with different functionalities. Additionally, the chemical properties were calculated with the Gaussian16 suite. The results showed that group substitution and generally increased number of carbons on thiourea increases IDT. It was observed that a more positively charged sulfur atom in the thioamide does not increase the reactivity towards H2O2. The dipole moment analysis revealed an overall trend of decreasing IDT due to increasing dipole moment. Finally, a lower adiabatic ionization energy related to increased IDTs for most cases. Additional chemical classes comprising a wider range of functionalities and electrophilic attributes are being investigated in on-going work.

Propellant↗
NASA NTRS2004

Florida Thunderstorms: A Faucet of Reactive Nitrogen to the Upper Troposphere

During the NASA Cirrus Regional Study of Tropical Anvils and Cirrus Layers-Florida Area Cirrus Experiment (CRYSTAL-FACE) enhanced mixing ratios of nitric oxide were measured in the anvils of thunderstorms and in clear air downwind of storm systems on flights of a Wl3-57F high-altitude aircraft. Mixing ratios greater than l0 - 20 times background were readily observed over distances of 25-120 km due to lightning activity. In many of the Florida storms deposition of NO occurred up to near the tropopause but major deposition usually occurred 1 - 2 km below the tropopause, or mostly within the visible anvil volume formed prior to storm decay. Observations from two storms of very different anvil size and electrical activity allowed estimates of the total mass of NO, vented to the middle and upper troposphere. Using the cloud-to ground (CG) flash accumulations from the National Lightning Detection Network, climatological intra-cloud (IC) to CG ratios, and assuming that CG and IC flashes were of equivalent efficiency for NO production, the ranges of production per flash for a moderate-sized and a large storm were (0.51 - 1.0) x l0(exp 26) and (2.3 - 3.1) x 10(exp 26) molecules NO/flash, respectively. Using the recently determined average global flash rate of 44 8, a gross extrapolation of these two storms to represent possible global annual production rates yield 1.6 - 3.2 and 7.3 - 9.9 Tg(N)/yr, respectively. If the more usual assumption is made that IC efficiency is l/l0th that of CG activity, the ranges of production for the moderate-sized and large storm were (1.3 - 2.7) x l0(exp 26) and (6.0 - 8.1) x l0(exp 26) molecules NO/CG flash, respectively. The estimates from the large storm may be high because there is indirect evidence that the IC/CG ratio was larger than would be derived from climatology. These two storms and others studied did not have flash rates that scaled as approx. H(sup 5) where H is the cloud top altitude. The observed CG flash accumulations and NO(x) mass production estimate for the month of July over the Florida area were compared with a representative 3D global Chemistry-Transport Model (CTMJ that uses the Price et al. lightning parameterization. For two land grid points representing the Florida peninsula the model compared well with the observations: CG flash rates were low by only a factor of approx. 2. When the model grid points included the coastal regions of Florida the flash accumulations were lower than observed by a factor of 3.4 - 4.6. It is recommended that models using the Price et al. parameterization allow any global coastal grid point to maintain the land rather than the marine flash rate parameterization. The convection in this CTM underestimated the actual cloud top heights over Florida by 1 - 2 km and thus the total lightning flash rates and the altitude range of reactive nitrogen deposition. Broad scale (20 - 120 km) median mixing ratios of NO within anvils over Florida were significantly larger than in storms previously investigated over Colorado and New Mexico.

Ridley, B.↗
DOE OSTI2023

Minimizing the impacts of the ammonia economy on the nitrogen cycle and climate

Ammonia (NH 3 ) is an attractive low-carbon fuel and hydrogen carrier. However, losses and inefficiencies across the value chain could result in reactive nitrogen emissions (NH 3 , NO x , and N 2 O), negatively impacting air quality, the environment, human health, and climate. A relatively robust ammonia economy (30 EJ/y) could perturb the global nitrogen cycle by up to 65 Mt/y with a 5% nitrogen loss rate, equivalent to 50% of the current global perturbation caused by fertilizers. Moreover, the emission rate of nitrous oxide (N 2 O), a potent greenhouse gas and ozone-depleting molecule, determines whether ammonia combustion has a greenhouse footprint comparable to renewable energy sources or higher than coal (100 to 1,400 gCO 2 e/kWh). The success of the ammonia economy hence hinges on adopting optimal practices and technologies that minimize reactive nitrogen emissions. We discuss how this constraint should be included in the ongoing broad engineering research to reduce environmental concerns and prevent the lock-in of high-leakage practices.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRSDate not supplied

Near Real-time Air Quality Forecasts Using the NASA GEOS Model

NASA's Global Modeling and Assimilation Office (GMAO) produces high-resolution global forecasts for weather, aerosols, and air quality. The NASA Global Earth Observing System (GEOS) model has been expanded to provide global near-real-time 5-day forecasts of atmospheric composition at unprecedented horizontal resolution of 0.25 degrees (~25 km). This composition forecast system (GEOS-CF) combines the operational GEOS weather forecasting model with the state-of-the-science GEOS-Chem chemistry module (version 12) to provide detailed analysis of a wide range of air pollutants such as ozone, carbon monoxide, nitrogen oxides, and fine particulate matter (PM2.5). Future developments for the next GEOS-CF version will be discussed, including the assimilation system is being expanded to include chemically reactive trace gases, specifically using the capabilities of the GEOS Constituent Data Assimilation System (CoDAS).

CoDAS↗
NASA NTRS1982

RF sputtered silicon and hafnium nitrides: Properties and adhesion to 440C stainless steel

Silicon nitride and hafnium nitride coatings were deposited by reactive RF sputtering on oxidized and unoxidized 440C stainless steel substrates. Sputtering was done in mixtures of argon and nitrogen gases from pressed powder silicon nitride and from hafnium metal targets. Depositions were at two background pressures, 8 and 20 mtorr, and at two different fractions (f) of nitrogen in argon, 0.25 and 0.60, for hafnium nitride and at f = 0.25 for silicon nitride. The coatings and the interface between the coating and substrates were investigated by X-ray diffractometry, scanning electron microscopy, energy dispersive X-ray analysis and Auger electron spectroscopy. A Knoop microhardness of 1650 + or - 100 kg/sq mm was measured for hafnium nitride and 3900 + or - 500 kg/sq mm for silicon nitride. The friction coefficients between a 440C rider and the coatings were measured under lubricated conditions. Scratch test results demonstrate that the adhesion of hafnium nitride to both oxidized and unoxidized 440C is superior to that of silicon nitride. Oxidized 440C is found to have increased adhesion, to both nitrides, over that of unoxidized 440C.

Grill, A.↗
NASA NTRS1983

RF-sputtered silicon and hafnium nitrides - Properties and adhesion to 440C stainless steel

Silicon nitride and hafnium nitride coatings were deposited by reactive RF sputtering on oxidized and unoxidized 440C stainless steel substrates. Sputtering was done in mixtures of argon and nitrogen gases from pressed powder silicon nitride and from hafnium metal targets. Depositions were at two background pressures, 8 and 20 mtorr, and at two different fractions (f) of nitrogen in argon, 0.25 and 0.60, for hafnium nitride and at f = 0.25 for silicon nitride. The coatings and the interface between the coating and substrates were investigated by X-ray diffractometry, scanning electron microscopy, energy dispersive X-ray analysis and Auger electron spectroscopy. A Knoop microhardness of 1650 + or 100 kg/sq mm was measured for hafnium nitride and 3900 + or 500 kg/sq mm for silicon nitride. The friction coefficients between a 440C rider and the coatings were measured under lubricated conditions. Scratch test results demonstrate that the adhesion of hafnium nitride to both oxidized and unoxidized 440C is superior to that of silicon nitride. Oxidized 440C is found to have increased adhesion, to both nitrides, over that of unoxidized 440C.

Grill, A.↗
DOE OSTI2020

Impacts of advanced diesel combustion operation and fuel formulation on soot nanostructure and reactivity

Advanced diesel combustion, accomplished via a single pulse fuel injection and high levels of exhaust gas recirculation (referred to as “PCCI”, partially-premixed charge compression ignition), is shown to be a path to reduce oxides of nitrogen and particulate matter simultaneously. This is well established in the literature. Less established is the extent to which such dilute combustion processes influence soot formation and affect soot that is emitted from diesel engines under such combustion modes. This work focuses on characterization of the nanostructure and oxidative reactivity of soot generated by a light-duty turbodiesel engine operating under a PCCI combustion mode, a dilute, low-temperature combustion process. Previous work on a type of PCCI combustion, referred to as high-efficiency clean combustion (HECC), showed soot samples having a fullerenic nanostructure, characterized by high levels of tortuosity of the fringe layers as seen in transmission electron micrograph images and as quantified using an image processing algorithm. Thermogravimetric analysis of the HECC mode soot samples showed that they displayed higher rates of oxidation than soot samples from a conventional diesel combustion mode. The present work returns to PCCI combustion, considering the timing of the main fuel injection, and the effects of operating on fuels rich in n-alkanes, particularly a fuel produced from a low temperature Fischer-Tropsch process (LTFT) and a renewable diesel fuel (RD) produced via hydrodeoxygenation of a plant oil. PCCI combustion conditions yield soot that shows higher reactivity compared to soot from the conventional combustion mode regardless of fuel type. LTFT and RD fuels produce soots with lower reactivity compared to ULSD. Soots produced from PCCI combustion have higher surface oxygen concentration and higher proportion of amorphous carbon. In addition, TEM images show that PCCI soots from all three fuels have smaller primary particle and particle aggregate sizes, and smaller graphene layers. These properties explain the higher reactivity of soot from PCCI combustion. The less reactive soots, which are produced from LTFT and RD fuel under conventional combustion, show internal burning during oxidation. However, soots with higher reactivity which are produced from late injection PCCI combustion and ULSD show shrinking core oxidation, most likely because of their overall amorphous structure.

42 ENGINEERING↗
DOE OSTI2026

Point defects and impurities in fluorite PuO 2

The native surface oxide of plutonium plays a critical role in ensuring the stability and safe storage of the underlying metal; consequently, understanding the role of defects and impurities in determining the properties of the oxide layer is critical. Here, in this study, we use hybrid density-functional theory calculations to evaluate the electronic structure and defect chemistry of PuO 2 , the most stable of the native oxide phases, including both native and extrinsic defects. We find that oxygen vacancies (𝑉 O ) form readily in PuO 2 , as do polarons. Electron polarons (𝜂 − ) are the lowest-energy acceptor species in PuO 2 , while the charge compensating donor species will shift from 𝑉 O under O-poor conditions to hole polarons (𝜂 + ) under O-rich conditions. Nitrogen and fluorine can substitute readily for oxygen atoms under O-poor conditions, while fluorine can also incorporate in an interstitial configuration (F$^−_i$) under more O-rich conditions. Carbon and chlorine incorporation in PuO 2 will be very limited. We also evaluate the kinetic barriers for oxygen-related defects, which we find to diffuse readily when present. Our results provide valuable insights into the critical role and variable chemistry of point defects and impurities in PuO 2 , which in turn have important implications for the safe storage of the underlying metal layer. In short, exposure of freshly prepared plutonium to reactive nitrogen- and fluorine-containing contaminants should be avoided, while carbon- or chlorine-containing contaminants are less likely to incorporate readily into the oxide.

Materials science↗
DOE OSTI2021

Singlet Oxygen Leads to Structural Changes to Chloroplasts during their Degradation in the Arabidopsis thaliana plastid ferrochelatase two Mutant

Abstract During stress, chloroplasts produce large amounts of reactive oxygen species (ROS). Chloroplasts also contain many nutrients, including 80% of a leaf’s nitrogen supply. Therefore, to protect cells from photo-oxidative damage and to redistribute nutrients to sink tissues, chloroplasts are prime targets for degradation. Multiple chloroplast degradation pathways are induced by photo-oxidative stress or nutrient starvation, but the mechanisms by which damaged or senescing chloroplasts are identified, transported to the central vacuole and degraded are poorly defined. Here, we investigated the structures involved with degrading chloroplasts induced by the ROS singlet oxygen (1O2) in the Arabidopsis thaliana plastid ferrochelatase two (fc2) mutant. Under mild 1O2 stress, most fc2 chloroplasts appeared normal, but had reduced starch content. A subset of chloroplasts was degrading, and some protruded into the central vacuole via ‘blebbing’ structures. A 3D electron microscopy analysis demonstrated that up to 35% of degrading chloroplasts contained such structures. While the location of a chloroplast within a cell did not affect the likelihood of its degradation, chloroplasts in spongy mesophyll cells were degraded at a higher rate than those in palisade mesophyll cells. To determine if degrading chloroplasts have unique structural characteristics, allowing them to be distinguished from healthy chloroplasts, we analyzed fc2 seedlings grown under different levels of photo-oxidative stress. A correlation was observed among chloroplast swelling, 1O2 signaling and the state of degradation. Finally, plastoglobule (PG) enzymes involved in chloroplast disassembly were upregulated while PGs increased their association with the thylakoid grana, implicating an interaction between 1O2-induced chloroplast degradation and senescence pathways.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Double Hydroxide Nanocatalysts for Urea Electrooxidation Engineered toward Environmentally Benign Products

Abstract Recent advancements in the electrochemical urea oxidation reaction (UOR) present promising avenues for wastewater remediation and energy recovery. Despite progress toward optimized efficiency, hurdles persist in steering oxidation products away from environmentally unfriendly products, mostly due to a lack of understanding of structure‐selectivity relationships. In this study, the UOR performance of Ni and Cu double hydroxides, which show marked differences in their reactivity and selectivity is evaluated. CuCo hydroxides predominantly produce N 2 , reaching a current density of 20 mA cm geo −2 at 1.04 V – 250 mV less than NiCo hydroxides that generate nitrogen oxides. A collection of in‐situ spectroscopies and scattering experiments reveal a unique in situ generated Cu (2‐x)+ ‐OO −• active sites in CuCo, which initiates nucleophilic substitution of NH 2 from the amide, leading to N‐N coupling between * NH on Co and Cu. In contrast, the formation of nitrogen oxides on NiCo is primarily attributed to the presence of high‐valence Ni 3+ and Ni 4+ , which facilitates N‐H activation. This process, in conjunction with the excessive accumulation of OH − ions on Jahn‐Teller (JT) distorted Co sites, leads to the generation of NO 2 − as the primary product. This work underscores the importance of catalyst composition and structural engineering in tailoring innocuous UOR products.

36 MATERIALS SCIENCE↗
DOE OSTI2024

A Comparative Experimental Analysis of Natural Gas Dual Fuel Combustion Ignited by Diesel and Poly OxyMethylene Dimethyl Ether

Dual-fuel low-temperature combustion is a possible solution for alleviating the tradeoff between oxides of nitrogen and soot emissions in conventional diesel combustion, albeit with poor combustion stability, high carbon monoxide, and unburned hydrocarbon emissions at low engine loads. The present work compares emissions and combustion (heat release and other metrics) of both diesel and poly-oxy methylene dimethyl ether as high-reactivity fuels to ignite natural gas while leveraging spray-targeted reactivity stratification, which involved multiple injections of the high-reactivity fuels. The experiments included six parametric sweeps of: (1) start of first injection, (2) start of second injection, (3) percentage of energy substitution of natural gas, (4) commanded injection duration ratio, (5) rail pressure, and (6) intake pressure. The experiments were performed on a 1.8 L heavy-duty single-cylinder research engine operating at a medium speed of 1339 rev/min. Not-to-exceed limits for the indicated oxides of nitrogen emissions, maximum pressure rise rate, and the coefficient of variation of the indicated mean effective pressure were set to 1 g/kWh, 10 bar/CAD, and 10%, respectively. The indicated emissions decreased and combustion improved significantly for both fueling combinations when the experimental procedure was applied.

Partridge, Kendyl Ryan↗
NASA NTRS1980

The enhanced oxidation of SO2 by NO2 on carbon particulates

The oxidation of SO2 on carbon particles in dry air and in air at 65% relative humidity (RH) was found to be greatly enhanced by the presence of gaseous NO2. Exposures of 20-80ppm SO2 + 10ppm NO2 on 1-mg samples of commercial carbon black were found to produce both sorption and desorption coverages (weight retained after desorption into N2) of over one order of magnitude greater than for corresponding SO2 exposures. Significant agglomeration and wetting were observed to occur progressively during exposures at 65% RH, and samples, even after 150-h exposure, rarely reached steady-state weight gain. The wetting may have regenerated fresh reactive carbon surface. Sorptions conducted in nitrogen atmospheres, rather than in air, appeared to produce slightly higher sorptions and weight retentions for equivalent exposure concentrations and times, indicating that NO2 served as the oxidizer and that molecular oxygen, or some trace constitutents in air, may have weakly inhibited the oxidation by NO2. Wet chemical analysis of the desorbed phase indicated that sulfate, presumably H2SO4 accounted for over half of the retained weight. Measurements of pH from water-quenched samples indicated a highly acidic surface phase, and suggested the oxidation process could proceed in an acidic environment.

Cofer, W. R., III↗
NASA NTRS2022

Mineral-Catalysed Formation of Marine NO and N 2 O on the Anoxic Early Earth

Microbial denitrification converts fixed nitrogen species into gases in extant oceans. However, it is unclear how such transformations occurred within the early nitrogen cycle of the Archean. Here 5we present experimental anoxic surface-catalyzed reduction of nitrite and nitrate via green rust and magnetite combined with diffusion and photochemical modeling. We find that in a Fe 2+ -rich marine environment, Fe minerals could have catalyzed abiotic denitrification reactions leading to the formation of nitric oxide (NO) and nitrous oxide (N 2 O). Nitrate did not exhibit reactivity in the presence of either mineral or aqueous Fe2+, however, both minerals induced rapid nitrite reduction 10to NO and N 2 O. While N 2 O escaped into the atmosphere (63% of nitrite-nitrogen, with green rust as catalyst), NO remained associated with precipitates (7%) serving as a potential shuttle to the benthic ocean.The modeling suggests that marine N 2 O emissions would have sustained 0.8-6 ppb of atmospheric N 2 O without a protective ozone layer. Our findings add detail to the as yet incompletely documented Archean nitrogen cycle, implying a globally distributed process driven 15by chemical kinetics similar to those of modern enzymatically mediated conversions.

Steffen Buessecker↗
NASA NTRS2015

The Icebreaker Mission to Search for Life on Mars

The search for evidence of life on Mars is the ultimate motivation for its scientific exploration. The results from the Phoenix mission indicate that the high N. latitude ice-rich regolith at low elevations is likely to be a recently habitable place on Mars [Stoker et al., 2010]. The near-surface ice likely provided adequate water activity during periods of high obliquity, 3 to 10 Myr ago. Carbon dioxide and nitrogen are present in the atmosphere, and nitrates may be present in the soil. Together with iron in basaltic rocks and perchlorate in the soil they provide carbon and energy sources, and oxidative power to drive metabolism. Furthermore, the presence of organics is possible, as thermally reactive perchlorate would have prevented their detection by Viking and Phoenix. The Mars Icebreaker Life mission [McKay et al., 2013] focuses on the following science goals: (1) Search for biomolecular evidence of life; (2) Search for organic matter from either exogeneous or endogeneous sources using methods that are not effected by the presence of perchlorate; (3) Characterize oxidative species that produced reactivity of soils seen by Viking; and 4) Assess the habitability of the ice bearing soils. The Icebreaker Life payload (Figure 1) includes a 1-m rotary percussive drill that brings cuttings samples to the surface where they are delivered to three instruments (Fig. 1), the Signs of Life Detector (SOLID) [Parro et al., 2011] for biomolecular analysis, Laser Desorption Mass Spectrometer (LDMS) [??? 2015]) for broad spectrum organic analysis, and Wet Chemistry Laboratory (WCL) [Hecht et al., 2009] for detecting soluble species of nutrients and reactive oxidants. The Icebreaker payload fits on the Phoenix spacecraft and can land at the well-characterized Phoe-nix landing site in 2020 in a Discovery-class mission.

Carbon dioxide and nitrogen↗
DOE OSTI2023

Harnessing redox proteomics to study metabolic regulation and stress response in lignin-fed Rhodococci

Abstract Background Rhodococci are studied for their bacterial ligninolytic capabilities and proclivity to accumulate lipids. Lignin utilization is a resource intensive process requiring a variety of redox active enzymes and cofactors for degradation as well as defense against the resulting toxic byproducts and oxidative conditions. Studying enzyme expression and regulation between carbon sources will help decode the metabolic rewiring that stymies lignin to lipid conversion in these bacteria. Herein, a redox proteomics approach was applied to investigate a fundamental driver of carbon catabolism and lipid anabolism: redox balance. Results A consortium of Rhodococcus strains was employed in this study given its higher capacity for lignin degradation compared to monocultures. This consortium was grown on glucose vs. lignin under nitrogen limitation to study the importance of redox balance as it relates to nutrient availability. A modified bottom–up proteomics workflow was harnessed to acquire a general relationship between protein abundance and protein redox states. Global proteomics results affirm differential expression of enzymes involved in sugar metabolism vs. those involved in lignin degradation and aromatics metabolism. As reported previously, several enzymes in the lipid biosynthetic pathways were downregulated, whereas many involved in β-oxidation were upregulated. Interestingly, proteins involved in oxidative stress response were also upregulated perhaps in response to lignin degradation and aromatics catabolism, which require oxygen and reactive oxygen species and generate toxic byproducts. Enzymes displaying little-to-no change in abundance but differences in redox state were observed in various pathways for carbon utilization (e.g., β‑ketoadipate pathway), lipid metabolism, as well as nitrogen metabolism (e.g., purine scavenging/synthesis), suggesting potential mechanisms of redox-dependent regulation of metabolism. Conclusions Efficient lipid production requires a steady carbon and energy flux while balancing fundamental requirements for enzyme production and cell maintenance. For lignin, we theorize that this balance is difficult to establish due to resource expenditure for enzyme production and stress response. This is supported by significant changes to protein abundances and protein cysteine oxidation in various metabolic pathways and redox processes.

09 BIOMASS FUELS↗
NASA NTRSDate not supplied

Dependence of Lightning Cloud-Top Optical Emissions on Channel Characteristics Using Boltzmann Radiative Transfer Modeling

With an estimated global flash rate of 46 lightning per second, a significant amount of lightning nitrogen oxides (LNOx) are produced within the climate system. In turn, LNOx affect the concentrations of ozone (O 3 , an important greenhouse gas) as well as the very reactive hydroxyl radicals (OH, that affect all greenhouse gases). Thus, space-based estimation of LNOx is highly sought [Koshak 2017; Koshak et al. (2015)]. Total lightning channel length, L , is a proxy for the total flash energy (and hence LNOx production). Geostationary lightning mappers provide cloud-top 2D views of the diffuse (i.e., blurry) optical images of lightning, thereby making it difficult to determine L (and other channel features). Transient Boltzmann radiative transfer modeling is applied here to investigate the dependence of the spatio-temporal pattern of cloud-top lightning optical emissions on L and other channel characteristics (e.g., orientation, propagation direction, amplitude, location, ...).

William J Koshak↗