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NASA NTRS2009

Silica-Aerogel Composites Opacified with La(0.7)Sr(0.3)MnO3

As part of an effort to develop improved lightweight thermal-insulation tiles to withstand temperatures up to 1,000 C, silica aerogel/fused-quartz-fiber composite materials containing La0.7Sr0.3MnO3 particles as opacifiers have been investigated as potentially offering thermal conductivities lower than those of the otherwise equivalent silica-aerogel composite materials not containing La(0.7)Sr(0.3)MnO3 particles. The basic idea of incorporating opacifying particles into silica-aerogels composite to reduce infrared radiative contributions to thermal conductivities at high temperatures is not new: it has been reported in a number of previous NASA Tech Briefs articles. What is new here is the selection of La(0.7)Sr(0.3)MnO3 particles as candidate opacifiers that, in comparison with some prior opacifiers (carbon black and metal nanoparticles), are more thermally stable. The preparation of a composite material of the present type includes synthesis of the silica-aerogel component in a sol-gel process. The La(0.7)Sr(0.3)MnO3 particles, made previously in a separate process, are mixed into the sol, which is then cast onto fused-quartz-fiber batting. Then the aerogel-casting solution is poured into the mold, where it permeates the silica fiber felt. After the sol has gelled, the casting is aged and then subjected to supercritical drying to convert the gel to the final aerogel form. The separate process for making the La(0.7)Sr(0.3)MnO3 particles begins with the slow addition of corresponding proportions of La(CH3COOH)3, Mn(CH3COOH)3, and Sr(NO3)2 to a solution of H2O2 in H2O. The solution is then peptized by drop-wise addition of NH4OH to obtain a sol. Next, the sol is dried in an oven at a temperature of 120 C to obtain a glassy solid. The solid is calcined at 700 C to convert it to La(0.7)Sr(0.3)MnO3. Then La(0.7)Sr(0.3)MnO3 particles are made by ball-milling the calcined solid. The effectiveness of La(0.7)Sr(0.3)MnO3 particles as opacifiers and thermal-conductivity reducers depends on the statistical distribution of particle sizes as well as the relative proportions of La(0.7)Sr(0.3)MnO3 and aerogel. For experiments performed thus far, samples of aerogel/fiber composites were formulated to have, variously, silica target density of 0.07 or 0.14 g/cu cm and to contain 30 percent of La(0.7)Sr(0.3)MnO3 in average particle size of 0.3 or 3 microns. The thermal conductivities of the samples containing the 3 micron La(0.7)Sr(0.3)MnO3 particles were found to be lower than those of the samples containing the 0.3 micron La(0.7)Sr(0.3)MnO3 particles. The optimum particle size is believed to be between 1 and 5 microns.

Rhine, Wendell↗
NASA NTRS2010

Process for Making a Noble Metal on Tin Oxide Catalyst

To produce a noble metal-on-metal oxide catalyst on an inert, high-surface-area support material (that functions as a catalyst at approximately room temperature using chloride-free reagents), for use in a carbon dioxide laser, requires two steps: First, a commercially available, inert, high-surface-area support material (silica spheres) is coated with a thin layer of metal oxide, a monolayer equivalent. Very beneficial results have been obtained using nitric acid as an oxidizing agent because it leaves no residue. It is also helpful if the spheres are first deaerated by boiling in water to allow the entire surface to be coated. A metal, such as tin, is then dissolved in the oxidizing agent/support material mixture to yield, in the case of tin, metastannic acid. Although tin has proven especially beneficial for use in a closed-cycle CO2 laser, in general any metal with two valence states, such as most transition metals and antimony, may be used. The metastannic acid will be adsorbed onto the high-surface-area spheres, coating them. Any excess oxidizing agent is then evaporated, and the resulting metastannic acid-coated spheres are dried and calcined, whereby the metastannic acid becomes tin(IV) oxide. The second step is accomplished by preparing an aqueous mixture of the tin(IV) oxide-coated spheres, and a soluble, chloride-free salt of at least one catalyst metal. The catalyst metal may be selected from the group consisting of platinum, palladium, ruthenium, gold, and rhodium, or other platinum group metals. Extremely beneficial results have been obtained using chloride-free salts of platinum, palladium, or a combination thereof, such as tetraammineplatinum (II) hydroxide ([Pt(NH3)4] (OH)2), or tetraammine palladium nitrate ([Pd(NH3)4](NO3)2).

Davis, Patricia↗
NASA NTRS2012

The Influence of Large Solar Proton Events on the Atmosphere

Solar proton events (SPEs) can cause changes in constituents in the Earth s polar middle atmosphere. A number of large SPEs have occurred over the past 50 years and tend to happen most frequently near solar maximum. The highly energetic protons cause ionizations, excitations, dissociations, and dissociative ionizations of the background constituents. Complicated ion chemistry leads to HOx (H, OH, HO2) production and dissociation of N2 leads to NOy (N, NO, NO2, NO3, N2O5, HNO3, HO2NO2, ClONO2, BrONO2) production. Both the HOx and NOy increases can result in changes to ozone in the stratosphere and mesosphere. The HOx increases lead to short-lived (~days) ozone decreases in the mesosphere and upper stratosphere. The NOy increases lead to long-lived (~several months) stratospheric ozone changes because of the long lifetime of NOy constituents in this region. UARS HALogen Occultation Experiment (HALOE) instrument observations showed SPE-caused polar stratospheric NOx (NO+NO2) increases over 10 ppbv in September 2000 due to the very large SPE of July 2000, which are reasonably well simulated with the Whole Atmosphere Community Climate Model (WACCM). WACCM-computed SPE-caused polar stratospheric ozone decreases >10% continued for up to 5 months past the largest events in the past 50 years, however, SPE-caused total ozone changes were not found to be statistically significant. Small polar middle atmospheric temperature changes of <4 K have also been predicted to occur as a result of the larger SPEs. The polar atmospheric effects of large SPEs during solar cycle 23 and 24 will be emphasized in this presentation.

Jackman, Charles H.↗
NASA NTRS2008

pH Responsive Microcapsules for Corrosion Control

The best coatings for corrosion protection provide not only barriers to the environment, but also a controlled release of a corrosion inhibitor, as demanded by the presence of corrosion or mechanical damage. NASA has developed pH sensitive microcapsules (patent pending) that can release their core contents when corrosion starts. The objectives of the research presented here were to encapsulate non-toxic corrosion inhibitors, to incorporate the encapsulated inhibitors into paint formulations, and to test the ability of the paints to control corrosion. Results showed that the encapsulated corrosion inhibitors, specifically Ce(NO3)3 , are effective to control corrosion over long periods of time when incorporated at relatively high pigment volume concentrations into a paint formulation.

Calle, Luz Marina↗
NASA NTRS2013

Characterization of Heat Melt Compactor (HMC) Product Water

The Heat Melt Compactor (HMC) is designed to sterilize and process wastes produced during space missions. Benefits of the HMC include reduction of biohazards to the crew, reduction in volume of wastes that would otherwise require storage, production of radiation shielding tiles, and recovery of water and other resources. Water reuse is critical onboard spacecrafts; it reduces the need for resupply missions and saves valuable storage space. The main sources of water in HMC batches are food, beverages, shampoo, disinfecting wipes, toothpaste, and diapers. Water reclaimed by the HMC was analyzed for concentrations of Na+, NH4+, K+, Mg2+, Ca2+, Cl-­‐, NO2-­‐, Br-­‐, NO3-­‐, PO43-­‐, SO42-­‐, total organic carbon (TOC), total inorganic carbon (TIC), % total solids, and pH. The data are discussed in relation to the current water input characteristics established for the International Space Station Water Processor Assembly system. Batches with higher than average amounts of food produced HMC product water with higher sulfate content, and batches with higher proportions of disinfectant wipes and food yielded HMC product water with higher ammonium concentration. We also compared theoretical chemical composition of HMC product water based on food labels and literature values to experimental results.

Heat Melt Compactor↗
NASA NTRS2015

Expanding Fungal Diets Through Synthetic Algal-Fungal Mutualism

Fungi can synthesize numerous molecules with important properties, and could be valuable production platforms for space exploration and colonization. However, as heterotrophs, fungi require reduced carbon. This limits their efficiency in locations such as Mars, where reduced carbon is scarce. We propose a system to induce mutualistic symbiosis between the green algae Chlamydomonas reinhardtii and the filamentous fungi Neurospora crassa. This arrangement would mimic natural algal-fungal relationships found in lichens, but have added advantages including increased growth rate and genetic tractability. N. crassa would metabolize citrate (C6H5O7 (sup -3)) and release carbon dioxide (CO2) that C. reinhardtii would assimilate into organic sugars during photosynthesis. C. reinhardtii would metabolize nitrate (NO3−) and release ammonia (NH3) as a nitrogen source for N. crassa. A N. crassa mutant incapable of reducing nitrate will be used to force this interaction. This system eliminates the need to directly supply its participants with carbon dioxide and ammonia. Furthermore, the release of oxygen by C. reinhardtii via photosynthesis would enable N. crassa to respire. We hope to eventually create a system closer to lichen, in which the algae transfers not only nitrogen but reduced carbon, as organic sugars, to the fungus for growth and production of valuable compounds.

Fungi↗
NASA NTRS2015

Evaluating Ammonium, Nitrate and Sulfate Aerosols in 3-Dimensions

The effect aerosols have on climate and air quality is a func-on of their chemical composi-on, concentra-on and spa-al distribu-on. These parameters are controlled by emissions, heterogeneous and homogeneous chemistry, where thermodynamics plays a key role, transport, which includes stratospheric-­‐ tropospheric exchange, and deposi-onal sinks. In this work we demonstrate the effect of some of these processes on the SO4‐NH4­‐NO3 system using the GISS ModelE2 Global Circula-on Model (GCM).

Aerosols↗
NASA NTRS2015

Inconsistent Strategies to Spin up Models in CMIP5: Implications for Ocean Biogeochemical Model Performance Assessment

During the fifth phase of the Coupled Model Intercomparison Project (CMIP5) substantial efforts were made to systematically assess the skill of Earth system models. One goal was to check how realistically representative marine biogeochemical tracer distributions could be reproduced by models. In routine assessments model historical hindcasts were compared with available modern biogeochemical observations. However, these assessments considered neither how close modeled biogeochemical reservoirs were to equilibrium nor the sensitivity of model performance to initial conditions or to the spin-up protocols. Here, we explore how the large diversity in spin-up protocols used for marine biogeochemistry in CMIP5 Earth system models (ESMs) contributes to model-to-model differences in the simulated fields. We take advantage of a 500-year spin-up simulation of IPSL-CM5A-LR to quantify the influence of the spin-up protocol on model ability to reproduce relevant data fields. Amplification of biases in selected biogeochemical fields (O2, NO3, Alk-DIC) is assessed as a function of spin-up duration. We demonstrate that a relationship between spin-up duration and assessment metrics emerges from our model results and holds when confronted with a larger ensemble of CMIP5 models. This shows that drift has implications for performance assessment in addition to possibly aliasing estimates of climate change impact. Our study suggests that differences in spin-up protocols could explain a substantial part of model disparities, constituting a source of model-to- model uncertainty. This requires more attention in future model intercomparison exercises in order to provide quantitatively more correct ESM results on marine biogeochemistry and carbon cycle feedbacks.

histories↗
NASA NTRS2016

Microbial Habitability in Gale Crater: Sample Analysis at Mars (SAM) Instrument Detection of Microbial Essential Carbon and Nitrogen

Chemical analyses of Mars soils and sediments from previous landed missions have demonstrated that Mars surface materials possessed major (e.g., P, K, Ca, Mg, S) and minor (e.g., Fe, Mn, Zn, Ni, Cl) elements essential to support microbial life. However, the detection of microbial essential organic-carbon (C) and nitrate have been more elusive until the Mars Science Laboratory (MSL) rover mission. Nitrate and organic-C in Gale Crater, Mars have been detected by the Sample Analysis at Mars (SAM) instrument onboard the MSL Curiosity rover. Eolian fines and drilled sedimentary rock samples were heated in the SAM oven from approximately 30 to 860 degrees Centigrade where evolved gases (e.g., nitrous oxide (NO) and CO2) were released and analyzed by SAM’s quadrupole mass spectrometer (MS). The temperatures of evolved NO was assigned to nitrate while evolved CO2 was assigned to organic-C and carbonate. The CO2 releases in several samples occurred below 450 degrees Centigrade suggesting organic-C dominated in those samples. As much as 7 micromoles NO3-N per gram and 200 micromoles CO2-C per gram have been detected in the Gale Crater materials. These N and C levels coupled with assumed microbial biomass (9 x 10 (sup -7) micrograms per cell) C (0.5 micrograms C per micrograms cell) and N (0.14 micrograms N per micrograms cell) requirements, suggests that less than 1 percent and less than 10 percent of Gale Crater C and N, respectively, would be required if available, to accommodate biomass requirements of 1 by 10 (sup 5) cells per gram sediment. While nitrogen is the limiting nutrient, the potential exists that sufficient N and organic-C were present to support limited heterotrophic microbial populations that may have existed on ancient Mars.

Sutter, B.↗
NASA NTRS2017

Daily Ambient Air Pollution Metrics for Five Cities: Evaluation of Data Fusion-Based Estimates and Uncertainties

Spatiotemporal characterization of ambient air pollutant concentrations is increasingly relying on the combination of observations and air quality models to provide well-constrained, spatially and temporally complete pollutant concentration fields. Air quality models, in particular, are attractive, as they characterize the emissions, meteorological, and physiochemical process linkages explicitly while providing continuous spatial structure. However, such modeling is computationally intensive and has biases. The limitations of spatially sparse and temporally incomplete observations can be overcome by blending the data with estimates from a physically and chemically coherent model, driven by emissions and meteorological inputs. We recently developed a data fusion method that blends ambient ground observations and chemical transport-modeled (CTM) data to estimate daily, spatially resolved pollutant concentrations and associatedcorrelations. In this study, we assess the ability of the data fusion method to produce daily metrics (i.e., 1-hr max, 8-hr max, and 24-hr average) of ambient air pollution that capture spatiotemporal air pollution trends for 12 pollutants (CO, NO2, NOx, O3, SO2, PM (sub10), PM (sub 2.5), and five PM (sub 2.5) components) across five metropolitan areas (Atlanta, Birmingham, Dallas, Pittsburgh, and St. Louis), from 2002 to 2008. Three sets of comparisons are performed: (1) the CTM concentrations are evaluated for each pollutant and metropolitan domain, (2) the data fusion concentrations are compared with the monitor data, (3) a comprehensive cross-validation analysis against observed data evaluates the quality of the data fusion model simulations across multiple metropolitan domains. The resulting daily spatial field estimates of air pollutant concentrations and uncertainties are not only consistent with observations, emissions, andmeteorology, but substantially improve CTM-derived results for nearly all pollutants and all cities, with the exception of NO2 for Birmingham. The greatest improvements occur for O3 and PM (sub 2.5). Squared spatiotemporal correlation coefficients range between simulations and observations determined using cross-validation across all cities for air pollutants of secondary and mixed origins are R-squared equal to 0.88-0.93 (O3), 0.81-0.89 (SO4), 0.67-0.83 (PM (sub 2.5)), 0.52-0.72 (NO3), 0.43-0.80 (NH4), 0.32-0.51 (OC), and 0.14-0.71 (PM (sub 10)). Results for relatively homogeneous pollutants of secondary origin, tend to be better than those for more spatially heterogeneous (larger spatial gradients) pollutants of primary origin (NOx, CO, SO2 and EC). Generally, background concentrations and spatial concentration gradients reflect interurban airshed complexity and the effects of regional transport, whereas daily spatial pattern variability shows intra urban consistency in the fused data. With sufficiently high CTM spatial resolution, traffic-related pollutants exhibit gradual concentration gradients that peak toward the urban centers. Ambient pollutant concentration uncertainty estimates for the fused data are both more accurate and smaller than those for either the observations or the model simulations alone.

spatiotemporal fusion↗
NASA NTRS2017

Evolved Gas Analyses of Sedimentary Rocks and Eolian Sediment in Gale Crater, Mars: Results of the Curiosity Rover's Sample Analysis at Mars Instrument from Yellowknife Bay to the Namib Dune

The sample analysis at Mars instrument evolved gas analyzer (SAM-EGA) has detected evolved water, H2, SO2, H2S, NO, CO2, CO, O2, and HCl from two eolian sediments and nine sedimentary rocks from Gale Crater, Mars. These evolved gas detections indicate nitrates, organics, oxychlorine phase, and sulfates are widespread with phyllosilicates and carbonates occurring in select Gale Crater materials. Coevolved CO2 (160 +/- 248-2373 +/- 820 μgC(CO2)/g) and CO (11 +/- 3-320 +/- 130 μgC(CO)/g) suggest that organic C is present in Gale Crater materials. Five samples evolved CO2 at temperatures consistent with carbonate (0.32 +/- 0.05-0.70 +/- 0.1 wt % CO3). Evolved NO amounts to 0.002 +/- 0.007-0.06 +/- 0.03 wt % NO3. Evolution of O2 suggests that oxychlorine phases (chlorate/perchlorate) (0.05 +/- 0.025-1.05 +/- 0.44 wt % ClO4) are present, while SO2 evolution indicates the presence of crystalline and/or poorly crystalline Fe and Mg sulfate and possibly sulfide. Evolved H2O (0.9 +/- 0.3-2.5 +/- 1.6 wt % H2O) is consistent with the presence of adsorbed water, hydrated salts, interlayer/structural water from phyllosilicates, and possible inclusion water in mineral/amorphous phases. Evolved H2 and H2S suggest that reduced phases occur despite the presence of oxidized phases (nitrate, oxychlorine, sulfate, and carbonate). SAM results coupled with CheMin mineralogical and Alpha-Particle X-ray Spectrometer elemental analyses indicate that Gale Crater sedimentary rocks have experienced a complex authigenetic/diagenetic history involving fluids with varying pH, redox, and salt composition. The inferred geochemical conditions were favorable for microbial habitability and if life ever existed, there was likely sufficient organic C to support a small microbial population.

Sutter, B.↗
NASA NTRS2019

Evolved Gas Analyses of Sedimentary Rocks and Eolian Sediment in Gale Crater, Mars: Results of the Curiosity Rover's Sample Analysis at Mars Instrument.

The Sample Analysis at Mars instrument evolved gas analyzer (SAM-EGA) has detected evolved water, SO2, NO, CO2, CO, O2, and HCl from two eolian sediments and nine sedimentary rocks from Gale Crater, Mars. The SAM-EGA heats samples to 870°C and measures evolved gas releases as function of temperature. These evolved gas detections indicate nitrates, organics, oxychlorine phase, and sulfates are widespread with phyllosilicates and carbonates occurring in select Gale Crater materials. CO2 and CO evolved at similar temperatures suggesting that as much as 2373 ± 820 μgC/g may occur as organic carbon in the Gale Crater rock record while relatively higher temperature CO2 detections are consistent with carbonate (<0.70 ± 0.1 wt % CO3). Evolved NO amounts up to 0.06 ± 0.03 wt % NO3 have been detected while O2 detections suggests chlorates and/or perchlorates (0.05 to 1.05 wt % ClO4) are present. Evolution of SO2 indicated the presence of crystalline and/or poorly crystalline Fe and Mg sulfate and possibly sulfide. Evolved H2O (0.9 - 2.5 wt% H2O) was consistent with the presence of adsorbed water, hydrated salts, interlayer/structural water from phyllosilicates, and possible inclusion water in mineral/amorphous phases. Evolved H2S detections suggest that reduced phases occur despite the presence of oxidized phases (nitrate, oxychlorine, sulfate, and carbonate). SAM results coupled with CheMin mineralogical and Alpha-Particle X-ray Spectrometer elemental analyses indicate that Gale Crater sedimentary rocks have experienced a complex authigenetic/diagenetic history involving fluids with varying pH, redox, and salt composition. The inferred geochemical conditions were favorable for microbial habitability and if life ever existed, there was likely sufficient organic C to support a small microbial population.

Sutter, Brad↗
NASA NTRSDate not supplied

SAGE III/ISS v5.3 Level 2 Data Product Changes and Improvements

The Stratospheric Aerosol and Gas Experiment on the International Space Station (SAGE III/ISS) is an occultation instrument that acquires measurements of aerosols and gases within the Earth’s stratosphere and upper troposphere. SAGE III/ISS provides level 2 solar species products for aerosol extinction (9 channels), nitrogen dioxide (NO2), ozone (O3), and water vapor (H2O). The level 2 products currently provide three O3 profiles based on differing retrievals. The first O3 profile is based on measurements at short wavelengths within the Hartley-Huggins band (MesO3), the second O3 profile is based on measurements made at visible wavelengths within the Chappius band (MLR O3), and the final profile is found using a more SAGE II like approach (AO3). The SAGE III/ISS also provides level 2 lunar species products for ozone (O3), nitrogen dioxide (NO2), and nitrogen trioxide (NO3). Version 5.3 of the SAGE III/ISS retrieval algorithm introduces improvements that affect the level 2 data products. The largest change to the solar algorithm is the implementation of disturbance monitoring package (DMP) corrections to improve pointing accuracy. The DMP is comprised of a miniature inertial measurement unit that measures rotation in inertial space using ring laser gyroscopes oriented about three orthogonal axes which can be used to correct pointing errors caused by mechanical disturbances. A major change common to solar and lunar algorithms is meteorological input from the coarser 42 level Modern-Era Retrospective analysis for Research and Applications, Version 2 (MERRA-2) model data to the 72 level MERRA-2 model data. The final major change involves improving the automated quality assurance (QA) algorithm to recover events that were withheld from the public release because differences between the AO3 and MLR O3 for some events after the eruption of Tonga–Hunga Haʻapai. Other changes for v5.3 include minor bug fixes as well as restoration of some data quality flags that were removed in v5.21. This presentation presents the impacts of these changes as well as overall observations of interest from v5.3 level 2 data products.

Carter Hulsey↗
NASA NTRSDate not supplied

SAGE III/ISS v5.3 Level 2 Data Product Changes and Improvements

The Stratospheric Aerosol and Gas Experiment on the International Space Station (SAGE III/ISS) is an occultation instrument that acquires measurements of aerosols and gases within the Earth’s stratosphere and upper troposphere. SAGE III/ISS provides level 2 solar species products for aerosol extinction (9 channels), nitrogen dioxide (NO2), ozone (O3), and water vapor (H2O). The level 2 products currently provide three O3 profiles based on differing retrievals. The first O3 profile is based on measurements at short wavelengths within the Hartley-Huggins band (MesO3), the second O3 profile is based on measurements made at visible wavelengths within the Chappius band (MLR O3), and the final profile is found using a more SAGE II like approach (AO3). The SAGE III/ISS also provides level 2 lunar species products for ozone (O3), nitrogen dioxide (NO2), and nitrogen trioxide (NO3). Version 5.3 of the SAGE III/ISS retrieval algorithm introduces improvements that affect the level 2 data products. The largest change to the solar algorithm is the implementation of disturbance monitoring package (DMP) corrections to improve pointing accuracy. The DMP is comprised of a miniature inertial measurement unit that measures rotation in inertial space using ring laser gyroscopes oriented about three orthogonal axes which can be used to correct pointing errors caused by mechanical disturbances. A major change common to solar and lunar algorithms is meteorological input from the coarser 42 level Modern-Era Retrospective analysis for Research and Applications, Version 2 (MERRA-2) model data to the 72 level MERRA-2 model data. The final major change involves improving the automated quality assurance (QA) algorithm to recover events that were withheld from the public release because differences between the AO3 and MLR O3 for some events after the eruption of Tonga–Hunga Haʻapai. Other changes for v5.3 include minor bug fixes as well as restoration of some data quality flags that were removed in v5.21. This presentation presents the impacts of these changes as well as overall observations of interest from v5.3 level 2 data products.

Carter Hulsey↗
NASA NTRS2020

Source Apportionment of Aerosol at a Coastal Site and Relationships with Precipitation Chemistry: A Case Study over the Southeast United States

This study focuses on the long-term aerosol and precipitation chemistry measurements from colocated monitoring sites in Southern Florida between 2013 and 2018. A positive matrix factorization (PMF) model identified six potential emission sources impacting the study area. The PMF model solution yielded the following source concentration profiles: (i) combustion; (ii) fresh sea salt; (iii) aged sea salt; (iv) secondary sulfate; (v) shipping emissions; and (vi) dust. Based on these results, concentration-weighted trajectory maps were developed to identify sources contributing to the PMF factors. Monthly mean precipitation pH values ranged from 4.98 to 5.58, being positively related to crustal species and negatively related to SO42−. Sea salt dominated wet deposition volume-weighted concentrations year-round without much variability in its mass fraction in contrast to stronger seasonal changes in PM2.5 composition where fresh sea salt was far less influential. The highest mean annual deposition fluxes were attributed to Cl−, NO3−, SO42−, and Na+ between April and October. Nitrate is strongly correlated with dust constituents (unlike sea salt) in precipitation samples, indicative of efficient partitioning to dust. Interrelationships between precipitation chemistry and aerosol species based on long-term surface data provide insight into aerosol–cloud–precipitation interactions.

positive matrix factorization↗
NASA NTRSDate not supplied

An Ensemble Investigation of the Causes for Regional Air-Quality Model Critical Load Exceedances Prediction Variability in European and North American Domains Using Diagnostics From Phase 4 of the Air Quality Model Evaluation International Initiative

We summarize tentative findings from multi air quality model ensembles for the years 2009 and 2010 in Europe (EU), and 2010 and 2016 in North America (NA), under AQMEII-4. The model predictions of sulphur and nitrogen deposition were used to estimate exceedances of critical loads for acidification and eutrophication, to show the extent to which the ensemble members agree in the magnitude and the trend of ecologically meaningful impacts. Model exceedance variability was analyzed using AQMEII-4 diagnostics. Evaluation against concentration and wet deposition observations, coupled with these diagnostics, identified specific process representations as the causes for variability between model predictions and for reduced model performance. All models predicted reductions in ecosystem acidification impacts in North America between the years 2010 and 2016, in accord with SO2 emissions reduction legislation which started in 2010 (SO2 SIP) However, all models in EU and NA domains had net negative biases for wet deposition of sulphur and nitrogen relative to observations. The wet S deposition average mean bias for the NA ensemble was -0.17 eq ha-1 d-1, and for the EU ensemble -1.15 eq ha-1 d-1. The NA daily wet deposition average mean bias for NH4+ was -0.37 eq ha-1d-1; EU -1.19 eq ha-1 d-1. The daily NA wet NO3- deposition average mean bias was -0.24 eq ha-1d-1; EU -0.69 eq ha-1 d-1. The members of the ensemble diverged (factor of 10) in their North American predictions for Ndep and consequently their eutrophication exceedances. The models with the highest eutrophication predictions also predicted the highest levels of gas-phase ammonia dry deposition (standard deviation of ammonia dry deposition flux across ensemble members was larger than the ensemble average). These models also had negative biases of predicted ammonia concentrations; average mean biases of -0.63 (satellite NH3) and -0.85 ppbv (surface NH3) compared to ensemble averages of -0.30 and -0.34 ppbv. Diagnostics showed that these differences resulted from the manner in which bidirectional ammonia fluxes were parameterized within these models. The second largest source of NA eutrophication prediction variability were models with positive biases in particulate ammonium and nitrate concentrations, and higher particle nitrogen deposition levels ( particle ammonium concentration bias +0.35 ug m-3; ensemble bias +0.15 ug m-3). We believe two factors may have led to these latter overestimates: higher levels of fine mode particle nitrate formation compared to other models (due to the use of an inorganic heterogeneous chemistry algorithm which did not take base cation chemistry into account), and updates to particle dry deposition velocities carried out in the absence of concurrent updates to wet scavenging algorithms. The relative importance of dry gas, dry particulate, and wet deposition towards total sulphur and nitrogen deposition totals differed between EU and North American domains, though all models had negative biases in wet deposition as noted above. Parallel and subsequent work suggests that multiphase hydrometeor scavenging may improve model wet deposition performance. An increased research focus is recommended for four model processes: multiphase hydrometeor scavenging, ammonia bidirectional fluxes, base cation chemistry and emissions, and particle dry deposition.

regional air-quality model↗
NASA NTRSDate not supplied

A Simulated High CO 2 Spaceflight Environment Increases Plant Preference for Ammonium as a Nitrogen Source.

Future long-duration missions will require a sustainable supply of food to support human crews. The spaceflight cabin environment often contains very high concentrations of CO 2 due to release of CO 2 by astronauts that is not completely scrubbed from the cabin, and it is therefore crucial to understand plant responses to elevated CO 2 (eCO 2 ) environments. Much focus has been given to changes in plant photosynthetic and performance parameters in response to eCO 2 , but the effects of eCO 2 on nitrogen (N) uptake are poorly understood. Shoot nitrate reduction may be reduced at eCO 2 , likely due to less reductant available for nitrate reduction because of reduced photorespiration and increased carbon fixation 1. Relative growth rate can be reduced at eCO 2 when N is provided only as nitrate and can be unaffected when N is supplied as ammonium 1. However, N uptake in response to eCO 2 has, to our knowledge, not yet been studied. An increased ‘preference’ for plants to take up N as ammonium at eCO 2 could have important implications for growth in the space environment, where N is currently only supplied as nitrate. In this study, novel stable isotope approaches were used in conjunction with hydroponics and isotope ratio mass spectrometry to determine the effect of eCO 2 on N preference for ammonium or nitrate in spring barley and lettuce when both N forms are provided equally. Several varieties of spring barley displayed increased ammonium preference at eCO 2 (720 ppm) compared to ambient CO 2 (410 ppm), though this was not true for all varieties 2. In most cases, increases in ammonium preference were driven by increases in ammonium uptake at eCO 2 and not decreases in nitrate uptake. Current research is assessing whether similar responses are observed in the candidate space crop lettuce, at levels of CO 2 like those observed on ISS (3000 ppm), and these results will also be presented. This work will enable the development of optimized nutrient regimes for candidate crops in space environments and the selection of crop varieties adapted to eCO 2 environments. Plants adapted to ammonium nutrition may play a role in future plant-based bioregenerative life support systems with higher ammonium concentrations due to waste recycling 3. Moreover, this research will further our understanding of plant responses to the eCO 2 environment brought about by climate change, allowing the development of future-proof crops that will help to maintain food security. References: 1. Bloom (2015). The increasing importance of distinguishing among plant nitrogen sources. Current Opinion in Plant Biology 25, 10-16. 2. Fountain (2023). Understanding interactions of barley (Hordeum vulgare) with soil nitrogen cycling activity and links to plant nitrogen preference. Ph.D. Thesis, The University of Sheffield. 3. Schiefloe et al. (2023). From urine to food and oxygen: effects of high and low NH4+:NO3- ratio on lettuce cultivated in a gas-tight hydroponic facility. Frontiers in Plant Science 14:1229476.

nitrogen↗