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At least 541 records · Page 30

Photochemical modeling of the Antarctic stratosphere: Observational constraints from the airborne Antarctic ozone experiment and implications for ozone behavior

The rapid decrease in O3 column densities observed during Antarctic spring has been attributed to several chemical mechanisms involving nitrogen, bromine, or chlorine species, to dynamical mechanisms, or to a combination of the above. Chlorine-related theories, in particular, predict greatly elevated concentrations of ClO and OClO and suppressed abundances of NO2 below 22 km. The heterogeneous reactions and phase transitions proposed by these theories could also impact the concentrations of HCl, ClNO3 and HNO3 in this region. Observations of the above species have been carried out from the ground by the National Ozone Expedition (NOZE-I, 1986, and NOZE-II, 1987), and from aircrafts by the Airborne Antarctic Ozone Experiment (AAOE) during the austral spring of 1987. Observations of aerosol concentrations, size distribution and backscattering ratio from AAOE, and of aerosol extinction coefficients from the SAM-II satellite can also be used to deduce the altitude and temporal behavior of surfaces which catalyze heterogeneous mechanisms. All these observations provide important constraints on the photochemical processes suggested for the spring Antarctic stratosphere. Results are presented for the concentrations and time development of key trace gases in the Antarctic stratosphere, utilizing the AER photochemical model. This model includes complete gas-phase photochemistry, as well as heterogeneous reactions. Heterogeneous chemistry is parameterized in terms of surface concentrations of aerosols, collision frequencies between gas molecules and aerosol surfaces, concentrations of HCl/H2O in the frozen particles, and probability of reaction per collision (gamma). Values of gamma are taken from the latest laboratory measurements. The heterogeneous chemistry and phase transitions are assumed to occur between 12 and 22 km. The behavior of trace species at higher altitudes is calculated by the AER 2-D model without heterogeneous chemistry. Calculations are performed for solar illumination conditions typical of 60, 70, and 80 S, from July 15 to October 31.

Rodriguez, Jose M.↗

Sensitivity of Air Quality to Potential Future Climate Change and Emissions in the United States and Major Cities

Simulated present and future air quality is compared for the years 2006e2010 and 2048e2052 over the contiguous United States (CONUS) using the Community Multi-scale Air Quality (CMAQ) model. Regionally downscaled present and future climate results are developed using GISS and the Weather Research Forecasting (WRF) model. Present and future emissions are estimated using MARKAL 9R model. O3 and PM(sub 2.5) sensitivities to precursor emissions for the years 2010 and 2050 are calculated using CMAQDDM (Direct Decoupled Method). We find major improvements in future U.S. air quality including generally decreased MDA8 (maximum daily 8-hr average O3) mixing ratios and PM(sub 2.5) concentrations and reduced frequency of NAAQS O3 standard exceedances in most major U.S. cities. The Eastern and Pacific U.S. experience the largest reductions in summertime seasonal average MDA8 (up to 12 ppb) with localized decreases in the 4th highest MDA8 of the year, decreasing by up to 25 ppb. Results from a Climate Penalty (CP) scenario isolate the impact of climate change on air quality and show that future climate change tends to increase O3 mixing ratios in some regions of the U.S., with climate change causing increases of over 10 ppb in the annual 4th highest MDA8 in Los Angeles. Seasonal average PM(sub 2.5) decreases (2-4 microgram m(exp -3)) over the Eastern U.S. are accounted for by decreases in sulfate and nitrate concentrations resulting from reduced mobile and point source emissions of NO(sub x) and SO(sub x).

Projecting emissions↗

Remote Sensing Reflectance and Inherent Optical Properties in the Mid-mesohaline Chesapeake Bay

We used an extensive set of bio-optical data and radiative transfer (RT) model simulations of radiation fields to investigate relationships between inherent optical properties and remotely sensed quantities in the optically complex, mid-mesohaline Chesapeake Bay waters. Field observations showed that the chlorophyll algorithms used by the MODIS (MODerate resolution Imaging Spectroradiometer) ocean color sensor (i.e. Chlor_a, chlor_MODIS, chlor_a_3 products) do not perform accurately in these Case 2 waters. This is because, when applied to waters with high concentrations of chlorophyll, all MODIS algorithms are based on empirical relationships between chlorophyll concentration and blue-green wavelength remote sensing reflectance (Rrs) ratios that do not account for the typically strong blue-wavelength absorption by non-covarying, dissolved and non-algal particulate components. Stronger correlation was observed between chlorophyll concentration and Rrs ratios in the red (i.e. Rrs(677)/Rrs(554)) where dissolved and non-algal particulate absorption become exponentially smaller. Regionally-specific algorithms that are based on the phytoplankton optical properties in the red wavelength region provide a better basis for satellite monitoring of phytoplankton blooms in these Case 2 waters. Good optical closure was obtained between independently measured Rrs spectra and the optical properties of backscattering, b(sub b), and absorption, a, over the wide range of in-water conditions observed in the Chesapeake Bay. Observed variability in the quantity f/Q (proportionality factor in the relationship between Rrs and the water inherent optical properties ratio b(sub b)/(a+b(sub b)) was consistent with RT model calculations for the specific measurement geometry and water bio-optical characteristics. Data and model results showed that f/Q values in these Case 2 coastal waters are not considerably different from those estimated in previous studies for Case 1 waters. Variation in surface backscattering significantly affected Rrs magnitude across the visible spectrum and was most strongly correlated (R(sup 2)=0.88) with observed variability in Rrs at 670 nm. Surface values of particulate backscattering were strongly correlated with non-algal particulate absorption, a(sub nap), in the blue wavelengths (R(sup 2)=0.83). These results, along with the measured values of backscattering fraction magnitude and non-algal particulate absorption spectral slope, suggest that suspended non-algal particles with high inorganic content are the major water constituents regulating b(sub b) variability in the mid-mesohaline Chesapeake Bay. Remote retrieval of surface b(sub b) and (a(sub nap), from Rrs(670) can be used in regionally-specific satellite algorithms to separate contribution by non-algal particles and dissolved organic matter to total light absorption in the blue, and monitor non-algal suspended particle concentration and distribution in these Case 2 waters.

Tzortziou, Maria↗

Massive peatland carbon banks vulnerable to rising temperatures

Peatlands contain one-third of the world’s soil carbon (C). If destabilized, decomposition of this vast C bank could accelerate climate warming; however, the likelihood of this outcome remains unknown. Here, we examine peatland C stability through five years of whole-ecosystem warming and two years of elevated atmospheric carbon dioxide concentrations (eCO 2 ). Warming exponentially increased methane (CH 4 ) emissions and enhanced CH 4 production rates throughout the entire soil profile; although surface CH 4 production rates remain much greater than those at depth. Additionally, older deeper C sources played a larger role in decomposition following prolonged warming. Most troubling, decreases in CO 2 :CH 4 ratios in gas production, porewater concentrations, and emissions, indicate that the peatland is becoming more methanogenic with warming. We observed limited evidence of eCO 2 effects. Our results suggest that ecosystem responses are largely driven by surface peat, but that the vast C bank at depth in peatlands is responsive to prolonged warming.

54 ENVIRONMENTAL SCIENCES↗

Bolide impacts and the oxidation state of carbon in the earth's early atmosphere

A one-dimensional photochemical model was used to examine the effect of bolide impacts on the oxidation state of earth's primitive atmosphere. The impact rate should have been high prior to 3.8 Ga before present, based on evidence derived from the moon. Impacts of comets or carbonaceous asteroids should have enhanced the atmospheric CO/CO2 ratio by bringing in CO ice and/or organic carbon that can be oxidized to CO in the impact plume. Ordinary chondritic impactors would contain elemental iron that could have reacted with ambient CO2 to give CO. Nitric oxide (NO) should also have been produced by reaction between ambient CO2 and N2 in the hot impact plumes. High NO concentrations increase the atmospheric CO/CO2 ratio by increasing the rainout rate of oxidized gases. According to the model, atmospheric CO/CO2 ratios of unity or greater are possible during the first several hundred million years of earth's history, provided that dissolved CO was not rapidly oxidized to bicarbonate in the ocean.

Kasting, James F.↗

Bolide impacts and the oxidation state of carbon in the Earth's early atmosphere

A one-dimensional photochemical model was used to examine the effect of bolide impacts on the oxidation state of Earth's primitive atmosphere. The impact rate should have been high prior to 3.8 Ga before present, based on evidence derived from the Moon. Impacts of comets or carbonaceous asteroids should have enhanced the atmospheric CO/CO2 ratio by bringing in CO ice and/or organic carbon that can be oxidized to CO in the impact plume. Ordinary chondritic impactors would contain elemental iron that could have reacted with ambient CO2 to give CO. Nitric oxide (NO) should also have been produced by reaction between ambient CO2 and N2 in the hot impact plumes. High NO concentrations increase the atmospheric CO/CO2 ratio by increasing the rainout rate of oxidized gases. According to the model, atmospheric CO/CO2 ratios of unity or greater are possible during the first several hundred million years of Earth's history, provided that dissolved CO was not rapidly oxidized to bicarbonate in the ocean. Specifically, high atmospheric CO/CO2 ratios are possible if either: (1) the climate was cool (like today's climate), so that hydration of dissolved CO to formate was slow, or (2) the formate formed from CO was efficiently converted into volatile, reduced carbon compounds, such as methane. A high atmospheric CO/CO2 ratio may have helped to facilitate prebiotic synthesis by enhancing the production rates of hydrogen cyanide and formaldehyde. Formaldehyde may have been produced even more efficiently by photochemical reduction of bicarbonate and formate in Fe(++)-rich surface waters.

Non-NASA Center↗

The 1st generation low cost point focus solar concentrator

A point focus solar concentrator that, given a high volume of production, will optimize the ratio of performance to cost is considered. The concentrator design approach has evolved by a systematic process of examining the operating requirements particular to the solar application, minimizing material content through detail structural design and structurally efficient subsystem features, and utilizing materials and processes compatible with high volume production techniques. The design approach, the rationale for the configuration and subsystem selections, and the development status are described.

Zimmerman, J.↗

Retrieval of Marine Water Constituents Using Atmospherically Corrected AVIRIS Hyperspectral Data

This paper reports on the validation of bio-optical models in estuarine and nearshore (case 2) waters of New Jersey-New York to retrieve accurate water-leaving radiance spectra and chlorophyll concentration from the Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) imaging spectrometer data. MODTRAN-4 was applied to remove the effects of the atmosphere so as to infer the water-leaving radiance. The study area - Hudson/Raritan of New York and New Jersey (Figure 1) is an extremely complex estuarine system where tidal and wind-driven currents are modified by freshwater discharges from the Hudson, Raritan, Hackensack, and Passaic rivers. Over the last century, the estuarine water quality has degraded in part due to eutrophication, which has disrupted the preexisting natural balance, resulting in phytoplankton blooms of both increased frequency and intensity, increasing oxygen demand, and leading to episodes of hypoxia. As the end result, a thematic map of chlorophyll-a concentration was generated using an atmospherically corrected AVIRIS ratio image. This thematic map serves as an indication of phytoplankton concentration. Such maps are important input into the geographic information system (GIS) for use as a management tool for monitoring water resources.

Bagheri, Sima↗

Resource availability governs polyhydroxyalkanoate (PHA) accumulation and diversity of methanotrophic enrichments from wetlands

Aquatic environments account for half of global CH 4 emissions, with freshwater wetlands being the most significant contributors. These CH 4 fluxes can be partially offset by aerobic CH 4 oxidation driven by methanotrophs. Additionally, some methanotrophs can convert CH 4 into polyhydroxyalkanoate (PHA), an energy storage molecule as well as a promising bioplastic polymer. In this study, we investigate how PHA-accumulating methanotrophic communities enriched from wetlands were shaped by varying resource availability (i.e., C and N concentrations) at a fixed C/N ratio. Cell yields, PHA accumulation, and community composition were evaluated in high (20% CH 4 and 10 mM NH 4 + ) and low resource (0.2% CH 4 and 0.1 mM NH 4 + ) conditions simulating engineered and environmental settings, respectively. High resource availability decreased C-based cell yields, while N-based cell yields remained stable, suggesting nutrient exchange patterns differed between methanotrophic communities at different resource concentrations. PHA accumulation was only observed in high resource enrichments, producing approximately 12.6% ± 2.4% (m/m) PHA, while PHA in low resource enrichments remained below detection. High resource enrichments were dominated by Methylocystis methanotrophs, while low resource enrichments remained significantly more diverse and contained only a minor population of methanotrophs. This study demonstrates that resource concentration shapes PHA-accumulating methanotrophic communities. Together, this provides useful information to leverage such communities in engineering settings as well as to begin understanding their role in the environment.

59 BASIC BIOLOGICAL SCIENCES↗

Machine Learning-Enhanced Multiphase CFD for Carbon Capture Modeling Run Data

Repository for the data generated as part of the 2023-2024 ALCC project "Machine Learning-Enhanced Multiphase CFD for Carbon Capture Modeling." The data was generated with MFIX-Exa's CFD-DEM model. The problem of interest is gravity driven, particle-laden, gas-solid flow in a triply-periodic domain of length 2048 particle diameters with an aspect ratio of 4. The mean particle concentration ranges from 1% to 40% and the Archimedes number ranges from 18 to 90. The particle-to-fluid density ratio, particle-particle restitution and friction coefficients and domain aspect ratio are held constant at values of 1000, 0.9, 0.25 and 4, respectively. This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231 using NERSC award ALCC-ERCAP0025948.

AMReX↗

Wavelength-shifted Cherenkov radiators

The scintillation and Cherenkov responses of plastic Cherenkov radiators containing different wavelength-shifting fluors in varying concentrations have been studied in beams of low energy protons and pions. For cosmic ray applications, where large Cherenkov to scintillation ratios are desired, the optimum fluor concentrations are 0.000025 by weight or less.

Krider, E. P.↗

Partitioning in REE-saturating minerals - Theory, experiment, and modelling of whitlockite, apatite, and evolution of lunar residual magmas

Compositions, including REEs determined by ion microprobe, of apatite and whitlockite in lunar rock assemblages rich in incompatible trace elements, are presented. Concentrations of REEs in lunar whitlockites are high, ranging from about 1.2 to 2.1 REEs (lanthanides + Y) per 56 oxygens. This slightly exceeds the level of two REE atoms per 56 oxygens at which the dominant substitution theoretically becomes saturated. This saturation effect leads to whitlockite REE(3+) D values at typical lunar whitlockite REE concentrations which are 30-40 percent lower than the D values at low concentrations. The halogen-to-phosphorous ratio in lunar melts is a key factor determining the REE distribution with crystalline assemblages. As long as P and REE concentrations of melts are in KREEP-like proportions, one or both of the phosphates will saturate in melts at similar REE concentrations.

Jolliff, Bradley L.↗

Observations of gas-phase products from the nitrate-radical-initiated oxidation of four monoterpenes

Abstract. Chemical ionization mass spectrometry with the nitrate reagent ion (NO3- CIMS) was used to investigate the products of the nitrate radical (NO3) initiated oxidation of four monoterpenes in laboratory chamber experiments. α-Pinene, β-pinene, Δ-3-carene, and α-thujene were studied. The major gas-phase species produced in each system were distinctly different, showing the effect of monoterpene structure on the oxidation mechanism and further elucidating the contributions of these species to particle formation and growth. By comparing groupings of products based on the ratios of elements in the general formula CwHxNyOz, the relative importance of specific mechanistic pathways (fragmentation, termination, and radical rearrangement) can be assessed for each system. Additionally, the measured time series of the highly oxidized reaction products provide insights into the ratio of relative production and loss rates of the high-molecular-weight products of the Δ-3-carene system. The measured effective O:C ratios of reaction products were anticorrelated with new particle formation intensity and number concentration for each system; however, the monomer : dimer ratios of products had a small positive trend. Gas-phase yields of oxidation products measured by NO3- CIMS correlated with particle number concentrations for each monoterpene system, with the exception of α-thujene, which produced a considerable amount of low-volatility products but no particles. Species-resolved wall loss was measured with NO3- CIMS and found to be highly variable among oxidized reaction products in our stainless steel chamber.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Extraction, Scrub, and Strip Test Results for the Salt Waste Processing Facility Caustic Side Solvent Extraction Solvent Sample

An Extraction, Scrub, and Strip (ESS) test was performed on a sample of Salt Waste Processing Facility (SWPF) Caustic-Side Solvent Extraction (CSSX) solvent and salt simulant to determine cesium distribution ratios (D (Cs) ), and cesium concentration in the strip effluent (SE) and decontaminated salt solution (DSS) streams; this data will be used by Parsons to help determine if the solvent is qualified for use at the SWPF. The ESS test showed acceptable performance of the solvent for extraction, scrub, and strip operations. The extraction D (Cs) measured 13.2, exceeding the required value of 8. This value is consistent with results from previous ESS tests using similar solvent formulations. Similarly, scrub and strip cesium distribution ratios fell within acceptable ranges

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Metal fluxes at the sediment–water interface in a free water surface constructed wetland

Metal biogeochemistry in the sediment, water, and the sediment–water interface (SWI) was studied in a free water surface constructed wetland. Concentrations of labile copper (Cu), zinc (Zn), sulfate, chloride, and dissolved organic carbon (DOC) were measured with the diffusive gradients in thin film (DGT) and peeper. A good agreement between peeper- and DGT-measured metals was observed for Cu (regression r 2 = 0.3, 95% CI of the slopes > 0), but not for Zn (95% CI of the slopes overlapped with 0), which was attributed to the different complexed compounds between Cu and Zn in porewater. The depth profile of labile metals in sediment porewater varied with time and was consistent with the solid-phase metal deposition, showing higher concentrations in the surface layer (3 to –3 cm) than in the bottom layer (–4 to –13 cm). The depth-averaged labile Cu and Zn concentrations measured by DGT were 1.0 and 3.1 µg/L, and labile sulfate, chloride, and DOC concentrations measured by peeper were 1.8, 3.6, and 2.1 mg/L, respectively. A sharp decrease in sulfate occurred in September when sulfate concentrations became the lowest among sampling months. This was caused by the seasonal sulfur cycles in the wetland, where the dominant sulfur reaction is sulfate reduction in warm seasons and sulfide oxidation in cold seasons. Different metal-removal mechanisms were observed in the two wetland cells; sulfur dynamics controlled the removal processes in the cell without frequent disturbance but failed to influence metal removal in the cell with frequent disturbance due to the interruption of anoxic layers. The flux ratios that compare labile element concentrations between the water column and the SWI (R-Cu, R-Zn, R-DOC, R-sulfate, and R-chloride) were generated to determine metal diffusive fluxes at the interface. Labile Zn was mostly transported from the water to the SWI during all seasons (R-Zn < 1 for all months except January). Labile Cu moved from the SWI to the water during the warm months (R-Cu < 1), which was explained by the bioturbation-induced transport of organic matter based on the positive correlations between R-Cu and R-DOC. In general, sediment can serve either as a sink or a source depending on the environmental conditions, metal speciation, and presence of living organisms. Here, metal flux at the SWI is a key component in the biogeochemical cycling of a constructed wetland.

54 ENVIRONMENTAL SCIENCES↗

Cloud area determination from AVIRIS data using water vapor channels near 1 micron

Fractional cloud area is derived from spectral images collected by the Airborne Visible-IR Imaging Spectrometer (AVIRIS). The derivation is made by ratioing radiances near the 0.94- and the 1.14-microns water vapor band centers against those in the intermediate atmospheric window regions. The derivation makes use of the facts that (1) the reflectances of most ground targets vary approximately linearly with wavelength in the 0.94- and the 1.14-micron water vapor band absorption regions, and (2) the peak absorptions of the water vapor band over cloudy areas are smaller than those over nearby clear surface areas because of the rapidly decreasing atmospheric water vapor concentration with height. The band ratioing technique effectively discriminates among clouds and surface areas having similar reflectance values.

Gao, Bo-Gai↗

The sources and diurnal variations of submicron aerosols in a coastal–rural environment near Houston, US

Aerosol properties were characterized at a rural site southwest of Houston from May to September 2022 during the intensive operation periods (IOPs) of the Tracking Aerosol Convection Interactions ExpeRiment (TRACER). Backward trajectory analysis reveals three major air mass types: marine air mass from the Gulf, urban air mass influenced by urban emissions, and regional air mass. Marine aerosols typically show a bimodal size distribution and have the lowest particle number and mass concentrations of PM 1 (particulate matter with an aerodynamic diameter of less than 1 µm), while aerosols from air masses strongly influenced by urban emissions exhibit the highest concentrations. Organic aerosol (OA) accounts for more than 50 % of PM 1 for urban and regional air masses, whereas sulfate is comparable to OA in marine air masses. Positive matrix factorization (PMF) analysis of aerosol mass spectra identifies 6 OA factors: hydrocarbon-like OA (HOA), OA from the oxidation of monoterpenes (MT-SOA), OA from the reactive uptake of isoprene epoxydiols by acidic sulfate particles (isoprene-SOA), oxygenated OA arising from shipping emissions (shipping-OOA), and two oxygenated OA factors with high O : C ratios (OOA1 and OOA2). OOA2 has the highest O : C ratio and exhibits elevated mass concentration in the afternoon. Similar diurnal variation of highly oxidized OA factors was commonly observed in the Houston area during previous studies and attributed to the SOA formation by photochemistry and mixing from aloft. Here, using air mass backward trajectories and a 1-D box model, we show the diurnal trend of OOA2 mass concentration is instead driven by changes in air mass arriving at the rural site. The air mass changes are likely caused by the shift between land breezes and sea/bay breezes. Within the same air mass type (e.g., either urban or marine air mass), OOA2 mass concentration is largely independent of wind direction and shows essentially no diurnal variation, suggesting OOA2 is related to aged OA with minimal influence by local emissions. This study helps identify the major sources of OA in the Houston region and highlights the impacts of both atmospheric chemistry and meteorology on aerosol properties in the coastal–rural environment.

54 ENVIRONMENTAL SCIENCES↗

Abundant Extraterrestrial Amino Acids in the Primitive CM Carbonaceous Chondrite Asuka 12236

The Asuka (A)-12236 meteorite has recently been classified as a CM carbonaceous chondrite of petrologic type 3.0/2.9 and is among the most primitive CM meteorites studied to date. Here, we report the concentrations, relative distributions, and enantiomeric ratios of amino acids in water extracts of the A-12236 meteorite and another primitive CM chondrite Elephant Moraine(EET) 96029 (CM2.7) determined by ultra-high-performance liquid chromatography time-of-flight mass spectrometry. EET 96029 was highly depleted in amino acids and dominated by glycine, while a wide diversity of two- to six-carbon aliphatic primary amino acids were identified in A-12236, which had a total amino acid abundance of 360 ± 18 nmol g-1, with most amino acids present without hydrolysis (free). The amino acid concentrations of A-12236 were double those previously measured in the CM2.7 Paris meteorite, consistent with A-12236 being a highly primitive and unheated CM chondrite. The high relative abundance of α-amino acids in A-12236 are consistent with formation by a Strecker-cyanohydrin dominated synthesis during a limited early aqueous alteration phase on the CM meteorite parent body. The presence of predominantly free glycine, a near racemic mixture of alanine (D/L ~0.93 to 0.96), and elevated abundances of several terrestrially rare non-protein amino acids including α-amino isobutyric acid (α-AIB) and racemic isovaline, indicate that these amino acids in A-12236 are extraterrestrial in origin. Given a lack of evidence for biological amino acid contamination in A-12236, it is possible that some of the L-enantiomeric excesses (Lee ~34 to 64%) of the protein amino acids aspartic and glutamic acids and serine are indigenous to the meteorite; however, isotopic measurements are needed for confirmation. In contrast to more aqueously altered CMs of petrologic types ≤ 2.5, no L-isovaline excesses were detected in A-12236. This observation strengthens the hypothesis that extensive parent body aqueous activity is required to produce or amplify the large L-isovaline excesses that cannot be explained solely by exposure to circularly polarized radiation or other chiral symmetry breaking mechanisms prior to incorporation into the asteroid parent body.

Daniel P Glavin↗