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At least 307 records · Page 17

Three-D Simulation of the Origin of the Pollutant Ozone Maxima in the Great African Plume: New Meteorology, New Chemistry for TRACE-A

Burning in South Central Africa is primarily responsible for the vast buildup of ozone in the mid-Atlantic noticeable in the Belem, Brazil, ozonesondes, and also visible in analyses using the Total Ozone Mapping Spectrometer (TOMS). We report on full-scale chemistry simulations for the SAFARI/TRACE-A field period of September-October, 1992. These observational programs provided a wealth of comparison data, including spectacular depictions of the vertical structure of ozone and particulate pollution over Africa, South America, and the Equatorial Atlantic [Browell JGR, 1996, submitted] above and below the NASA DC-8 airplane path. These depictions provide strict tests on the ability of a 3-d simulation and its controlling input parameters, most notably the biomass burning emissions strength. We use meteorology from MM5 used as a synoptic assimilation model and our own GRACES Global Regional Air Chemistry Event Simulator. This report will focus on the unique meteorology of the Equatorial Atmosphere around the Gulf of Guinea during the TRACE-A period, which we describe as "the opening of the gate," "the Great African Plume," and the "African Recirculatory System." We expect to assess whether the ozone observed is primarily "transported African smog," the standard view, or whether "re-$NO_[x)$-ification" of the Central Atlantic troposphere (reduction of nitric acid to active nitrogen oxides in clouds or aerosol) may be required for "extended intercontinental ozone production." A status report on a second nitrogen problem, "lower-tropospheric missing NO(y)," in which we find a serious imbalance in the $NO_ {x }$ and $NO_{y}$ budgets when compared with similar atmospheric tracers, will be given. An elaboration of the concepts set off by quotation marks in this abstract will be given in the talk.

Chatfeild, Robert↗

Nitrogen Dioxide Trend over the United States: the View from the Ground, the View from Space

Emissions of nitrogen oxides (NOx) are decreasing over the US due to environmental policies and technological change. We use observations of tropospheric nitrogen dioxide (NO2) columns from the Ozone Monitoring Instrument (OMI) satellite instrument and surface NO2 in-situ measurements from the air quality system (AQS) to quantify the trends, and to establish the relationship between the trends in tropospheric column and surface concentration. Both observations show substantial downward trends from 2005 to 2013, with an average reduction of 35 percent according to OMI and 38 percent according to AQS. The annual reduction rates are largest in 2005-2009: -6.2 percent per year and -7 percent per year observed by OMI and AQS, respectively. We examine various factors affecting the estimated trend in OMI NO2 columns and in-situ NO2 observations. An improved understanding of trend offers valuable insights about effectiveness of emission reduction regulations on state and federal level.

Air pollution↗

Alternative strategies of nutrient acquisition and energy conservation map to the biogeography of marine ammonia-oxidizing archaea

Ammonia-oxidizing archaea (AOA) are among the most abundant and ubiquitous microorganisms in the ocean, exerting primary control on nitrification and nitrogen oxides emission. Although united by a common physiology of chemoautotrophic growth on ammonia, a corresponding high genomic and habitat variability suggests tremendous adaptive capacity. Here, we compared 44 diverse AOA genomes, 37 from species cultivated from samples collected across diverse geographic locations and seven assembled from metagenomic sequences from the mesopelagic to hadopelagic zones of the deep ocean. Comparative analysis identified seven major marine AOA genotypic groups having gene content correlated with their distinctive biogeographies. Phosphorus and ammonia availabilities as well as hydrostatic pressure were identified as selective forces driving marine AOA genotypic and gene content variability in different oceanic regions. Notably, AOA methylphosphonate biosynthetic genes span diverse oceanic provinces, reinforcing their importance for methane production in the ocean. Together, our combined comparative physiological, genomic, and metagenomic analyses provide a comprehensive view of the biogeography of globally abundant AOA and their adaptive radiation into a vast range of marine and terrestrial habitats.

59 BASIC BIOLOGICAL SCIENCES↗

Effect of feed composition on the production of off-gases during vitrification of simulated low-activity nuclear waste

During the vitrification of nuclear waste, hazardous and radioactive emissions are generated from the feed-to-glass conversion reactions, in addition to discharges from forced air bubbling and air inleakage. Although the major gaseous emissions are water vapor, nitrogen, and carbon dioxide, various monitored environmental pollutants are also released, such as nitrogen oxides or sulfur dioxide. In addition, reactions between organics and nitrates in the feed may also form products of incomplete combustion such as carbon monoxide and acetonitrile. Although off-gas emissions are commonly measured during both laboratory- and pilot-scale melter testing, no predictive tool is currently available to a priori estimate the composition of gaseous emissions during nuclear waste vitrification. This work forms a basis for the development of such predictive tool by measuring gas evolution from a broad range of simulated low-activity waste melter feeds using evolved gas analysis data and developing correlations between the feed and off-gas compositions. Using reaction stoichiometry and regression analysis, we demonstrate that next to the content of nitrogen and organic carbon in the feed, the gaseous emissions are affected by the feed reduction-oxidation conditions – the more the feed is reduced, the less nitrogen monoxide, and more carbon monoxide and acetonitrile evolves. In conclusion, the results presented in this work provide a first step towards reducing the amount of expensive physical melter testing and the regression analysis provides a simple tool for rapid optimization of feed composition with respect to off-gas composition.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

The oxidizing capacity of the earth's atmosphere - Probable past and future changes

A number of critical atmospheric chemical problems depend on the earth's oxidizing capacity, which is essentially the global burden of oxidants in the lower atmosphere. There is limited direct evidence for changes in the earth's oxidizing capacity since recent preindustrial times when, because of industrial and poulation growth, increasing amounts of O3 precursor trace gases (carbon monoxide, nitrogen oxides, and hydrocarbons) have been released into the atmosphere. The concentrations of O3 and possibly H2O2 have increased over large regions. Models predict that tropospheric O3 will increase about 0.3-1.0 percent per year over the next 50 years with both positive and negative trends possible for OH and H2O2. Models and the observational network for oxidants are improving, but validation of global models is still at an early stage.

Thompson, Anne M.↗

A Review on the Impact of SO 2 on the Oxidation of NO, Hydrocarbons, and CO in Diesel Emission Control Catalysis

A high-efficiency after-treatment technology has been required to meet the increasingly stringent regulations on the emissions of nitrogen oxides (NO x ), hydrocarbons (HCs), and carbon monoxide (CO) exhausts from diesel engine vehicles throughout the world. The diesel oxidation catalyst (DOC) is an indispensable part of a diesel-fueled exhaust system, which mainly functions in the oxidation of unburned HCs and CO to CO 2 and H 2 O (in the case of HCs) and a proportion of NO to NO 2 . However, the DOC will unavoidably be poisoned by trace gaseous SO 2 or accumulated sulfur on the catalyst under real operational conditions and hence impair the overall purification efficiency of the aftertreatment system. There have been significant research efforts from both academia and industry involving sulfur-relevant diesel oxidation chemistry and development of robust sulfur-resistant oxidation catalysts. In this review, we focus on recent advances in the study of SO 2 effects on the catalytic oxidation of NO, HCs, and CO over DOCs, with particular attention to the fundamentals beneath apparent observations of sulfur influence on PGM-based and non-noble metal-based catalysts in the different oxidation reactions. Regeneration methods and design rationale for sulfur-resistant catalysts are also covered. Several challenges in the future research regarding microscopic insights into the SO 2 -influencing mechanism and next-generation sulfur-resistant DOC design are highlighted toward real-world practice.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Analysis of North Atlantic Aircraft Data on Oxygenated Intermediate Species Using an Adapted Regional Chemistry-Transport Model

Our study is on the interaction of nitrogen oxides with organics as they are exported from their complex sources in Eastern North America. Both urban and specific industrial emissions contribute the nitrogen of the C-H-O-N compounds that affect the global atmosphere, helping determine both ozone and the self-cleaning radical chemistry of the troposphere mediated by the OH radical. Different industrial sources, urban, and natural emissions contribute the organic C. Peroxyacetyl nitrate, CH3C(double bonds O)OONO2 is the most interesting compound for which we can measure the outflow to the full depth of the Atlantic troposphere. As we adapt the 3-d chemical model to describe outflow for specific periods with sufficient accuracy, we are analyzing some valuable information in the NARE-97 complete airborne dataset. (NARE: North Atlantic Regional Experiment). Ames researchers find that there are substantial puzzles in the ratios of PAN/NO2. Peroxy acetyl nitrate provides one of the major long-distance export pathways for active nitrogen from Eastern North America. It should be closely linked with NO, (defined as the sum NO + NO2) by simple thermal association and decomposition reactions, at least when the ambient temperature is substantially above 5 C.

Chatfield, Robert↗

Transport and chemistry of isoprene and its oxidation products in deep convective clouds

Deep convective clouds can transport trace gases from the planetary boundary layer into the upper troposphere where subsequent chemistry may impact aerosol particle formation and growth. In this modelling study, we investigate processes that affect isoprene and its oxidation products injected into the upper troposphere by an isolated deep convective cloud in the Amazon. We run a photochemical box model with coupled cloud microphysics along hundreds of individual air parcel trajectories sampled from a cloud-resolving model simulation of a convective event. The box model simulates gas-phase chemical reactions, gas scavenging by liquid and ice hydrometeors, and turbulent dilution inside a deep convective cloud. The results illustrate the potential importance of gas uptake to anvil ice in regulating the intensity of the isoprene oxidation and associated low volatility organic vapour concentrations in the outflow. Isoprene transport and fate also depends on the abundance of lightning-generated nitrogen oxide radicals (NO x = NO + NO 2 ). If gas uptake on ice is efficient and lightning activity is low, around 30% of the boundary layer isoprene will survive to the cloud outflow after approximately one hour of transport, while all the low volatile oxidation products will be scavenged by the cloud hydrometeors. If lightning NO x is abundant and gas uptake by ice is inefficient, then all isoprene will be oxidised during transport or in the immediate outflow region, while several low volatility isoprene oxidation products will have elevated concentrations in the cloud outflow. Reducing uncertainties associated with the uptake of vapours on ice hydrometeors, especially HO 2 and oxygenated organics, is essential to improve predictions of isoprene and its oxidation products in deep convective outflows and their potential contribution to new particle formation and growth.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Laser-Induced Thermal Decomposition of Uranium Coordination Compounds with Non-oxidic Ligands to Produce Nitride and Carbide Materials

The production of ceramics from uranium coordination compounds can be achieved through thermal processing if an excess amount of the desired atoms (i.e., C or N), or reactive gaseous products (e.g., methane or nitrogen oxide) is made available to the reactive uranium metal core via decomposition/fragmentation of the surrounding ligand groups. Here, computational thermodynamic approaches were utilized to identify the temperatures necessary to produce uranium metal from some starting compounds—UI 4 (TMEDA) 2 , UCl 4 (TMEDA) 2 , UCl 3 (pyridine) x , and UI 3 (pyridine) 4 . Experimentally, precursors were irradiated by a laser under various gaseous environments (argon, nitrogen, and methane) creating extreme reaction conditions (i.e., fast heating, high temperature profile >2000 °C, and rapid cooling). Despite the fast dynamics associated with laser irradiation, the central uranium atom reacted with the thermal decomposition products of the ligands yielding uranium ceramics. Residual gas analysis identified vaporized products from the laser irradiation, and the final ceramic products were characterized by powder X-ray diffraction. The composition of the uranium precursor as well as the gaseous environment had a direct impact on the production of the final phases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Lightning NOx Production in the Tropics as Determined Using OMI NO2 Retrievals and WWLLN Stroke Data

Nitrogen oxide (NOx) production by lightning in the tropics is estimated using tropospheric NOx amounts (LNOx*) over deep convective grid boxes derived from OMI (Ozone Monitoring Instrument) nitrogen dioxide (NO2) slant columns and detection efficiency adjusted WWLLN (World Wide Lightning Location Network) flashes. The lightning NOx production efficiency (LNOx PE) in the tropics is determined for the austral and boreal summers of 2007 to 2011 by regressing regional mean daily values of LNOx* for individual seasons against daily flash totals during flash windows prior to the OMI overpass. LNOx PE is determined to be approximately two times larger over marine locations than over continental locations possibly because marine flashes are more energetic. Overall, the mean LNOx PE for the tropics is calculated to be 170 ± 100 mol per flash with values over the tropical Pacific (low flash rate region) being largest. The main contributors to uncertainties in PE are uncertainties in WWLLN flash detection efficiency, upper tropospheric NOx lifetime in the near field of convection, and air mass factor biases.

Dale J. Allen↗

Sensitivity of Tropospheric Ozone Over the Southeast USA to Dry Deposition

Dry deposition (DD) is a major loss process for tropospheric ozone and some reactive nitrogen and carbon precursors. We investigate the response of summertime ozone and its production chemistry over the Southeast United States (USA) to variability in this sink. Turning off DD of oxidized nitrogen, ozone, or all species over the United States in the Geophysical Fluid Dynamics Laboratory AM3 model increases regional mean surface ozone by 5, 18, or 25 ppb, respectively. Additional sensitivity simulations demonstrate that, assuming linearity, surface ozone has a similar sensitivity to ozone DD as to NOx emissions. Trends in ozone production efficiency derived from observed relationships between ozone and precursor oxidation products may not solely reflect precursor emission changes if ozone DD varies (e.g., with meteorology). We conclude that DD variability merits consideration when interpreting observed ozone trends. Quantifying the impact of changes in sinks versus sources will require long‐term DD measurements across the region of interest.

dry deposition↗

Ammonia electrosynthesis on single-atom catalysts: Mechanistic understanding and recent progress

Ammonia has been regarded as an irreplaceable chemical for human life as its essential role in fertilizers, pharmaceuticals, and renewable energy. At present, ammonia is industrially derived from fossil fuels with the well-known Haber–Bosch process, which is energy-consuming as well as environmentally unfriendly. The electrosynthesis approach is currently under intensive research as a future basis for producing ammonia from renewable sources. This review presents in-depth mechanistic studies and recent progress in single-atom electrocatalysts as an emerging platform for ammonia synthesis from the electroreduction of molecular dinitrogen and nitrogen oxides, particularly nitrate anion. In the conclusions and outlook, our discussion explores some key perspectives of future developments in the field. It is believed that ammonia electrosynthesis from a variety of nitrogen species via renewable electricity is of a great prospect to offer environmental, energy, and sustainability benefits.

Li, Panpan↗

Spatial and Temporal Variability of Ground and Satellite Column Measurements of NO2 and O3 over the Atlantic Ocean During the Deposition of Atmospheric Nitrogen to Coastal Ecosystems Experiment

In situ measurements of O3 and nitrogen oxides (NO + NO2=NOx) and remote sensing measurements of total column NO2 and O3 were collected on a ship in the North Atlantic Ocean as part of the Deposition of Atmospheric Nitrogen to Coastal Ecosystems (DANCE) campaign in July August 2014,100 km east of the mid-Atlantic United States. Relatively clean conditions for both surface in situ mixing ratio and total column O3 and NO2 measurements were observed throughout the campaign. Increased surface and column NO2 and O3 amounts were observed when a terrestrial air mass was advected over the study region. Relative to ship-based total column measurements using a Pandora over the entire study, satellite measurements overestimated total column NO2 under these relatively clean atmospheric conditions over offshore waters by an average of 16. Differences are most likely due to proximity, or lack thereof, to surface emissions; spatial averaging due to the field of view of the satellite instrument; and the lack of sensitivity of satellite measurements to the surface concentrations of pollutants. Total column O3 measurements from the shipboard Pandora showed good correlation with the satellite measurements(r 0.96), but satellite measurements were 3 systematically higher than the ship measurements, in agreement with previous studies. Derived values of boundary layer height using the surface in situ and total column measurements of NO2 are much lower than modeled and satellite-retrieved boundary layer heights, which highlight the differences in the vertical distribution between terrestrial and marine environments.

Martins, Douglas K.↗

Evaluating the Impact of Agricultural Soil NOx Emissions on Air Quality Using Advanced Satellite, Ground-based, and Model Data

Soil moisture can also influence the concentration of atmospheric trace gases by moderating the emission of nitrogen oxides (NOx = NO + NO2) from agricultural fields. Human activities can play an important role in controlling the available soil moisture depending on irrigation demand and agricultural management. To further complicate matters, nitrogen fertilizer use has also been found to be a significant source of NOx emissions in agricultural areas. In fact, some of the highest emissions have been reported from fertilized soils in high-temperature agricultural regions, such as the Imperial Valley of California. Since NO2 is an important precursor to ozone formation in the troposphere, which is a leading cause of premature death in humans, it is critical to understand how natural and anthropogenic factors contribute to NOx emissions in these areas. O3 pollution is also a growing threat to global food security due to its detrimental impacts on crop production. This work uses a suite of satellite, ground-based, and model data to investigate how agricultural soil NOx emissions from natural (rainfall) and anthropogenic factors (irrigation, nitrogen fertilizer) govern air quality over California. We evaluate the capabilities of using SMAP retrievals and SMAP Land Information System (LIS) output for monitoring irrigation activities over the major agricultural areas of California by conducting intensive analyses of soil moisture and precipitation data. High-resolution trace gas observations from the new generation TROPOspheric Monitoring Instrument (TROPOMI) sensor are used to characterize and monitor the variability of trace gases and air quality conditions associated with soil NOx emissions. We also synthesize satellite, ground-based, and agriculture data to estimate the separate contributions from rainfall, irrigation, and nitrogen fertilizer practices on soil NOx emissions and associated air quality conditions. Finally, unprecedented hourly trace gas retrievals from the NASA Tropospheric Emissions: Monitoring of Pollution (TEMPO) geostationary satellite sensor are used to monitor the diurnal evolution of NO2 and O3 concentrations from soil NOx emissions.

Aaron R Naeger↗

Detection and Quantification of Nitrogen Compounds in the First Drilled Martian Solid Samples by the Sample Analysis at Mars (SAM) Instrument Suite on the Mars Science Laboratory (MSL)

The Sampl;e Analysis at Mars (sam) instrument suite on the Mars Science Laboratory (MSL) Curiosity Rover detected both reduced and oxidized nitrogen bearing compounds during the pyrolysis of surface materials from the three sites at Gale Crater. Preliminary detections of nitrogen species include No, HCN, ClCN, and TFMA ((trifluoro-N-methyl-acetamide), Confirmation of indigenous Martian nitrogen-bearing compounds requires quantifying N contribution from the terrestrial derivatization reagents carried for SAM's wet chemistry experiment that contribute to the SAM background. Nitrogen species detected in the SAM solid sample analyses can also be produced during laboratory pyrolysis experiments where these reagents are heated in the presence of perchlorate a compound that has also been identified by SAM in Mars solid samples.

Stern, Jennifer C.↗

A Space-based, High-resolution View of Notable Changes in Urban Nox Pollution Around the World (2005 - 2014)

Nitrogen oxides (NOxNO+NO2) are produced during combustion processes and, thus may serve as a proxy for fossil fuel-based energy usage and committed greenhouse gases and other pollutants. We use high-resolution nitrogen dioxide (NO2) data from the Ozone Monitoring Instrument (OMI) to analyze changes in urban NO2 levels around the world from 2005 to 2014, finding complex heterogeneity in the changes. We discuss several potential factors that seem to determine these NOx changes. First, environmental regulations resulted in large decreases. The only large increases in the United States may be associated with three areas of intensive energy activity. Second, elevated NO2 levels were observed over many Asian, tropical, and subtropical cities that experienced rapid economic growth. Two of the largest increases occurred over recently expanded petrochemical complexes in Jamnagar (India) and Daesan (Korea). Third, pollution transport from China possibly influenced the Republic of Korea and Japan, diminishing the impact of local pollution controls. However, in China, there were large decreases over Beijing, Shanghai, and the Pearl River Delta, which were likely associated with local emission control efforts. Fourth, civil unrest and its effect on energy usage may have resulted in lower NO2 levels in Libya, Iraq, and Syria. Fifth, spatial heterogeneity within several megacities may reflect mixed efforts to cope with air quality degradation. We also show the potential of high-resolution data for identifying NOx emission sources in regions with a complex mix of sources. Intensive monitoring of the world's tropical subtropical megacities will remain a priority, as their populations and emissions of pollutants and greenhouse gases are expected to increase significantly.

spatial heterogeneity↗

Determination of Carbon, Hydrogen, Nitrogen, and Oxygen in Bio-Oils: Laboratory Analytical Procedure (LAP)

The determination of total carbon, hydrogen, and nitrogen in bio-oils is important as these values can be used to track the carbon balance of production processes as well as calculate total oxygen content by difference. Oxygen content of bio-oils is a key metric for production and upgrading strategies as these are typically aimed at reducing oxygen. Oxygenates in bio-oils contribute to poor hydrocarbon miscibility, high acidity, high viscosity, and poor stability. Upgrading of bio-oils via deoxygenation produces hydrocarbons which can be used to generate feedstocks for renewable fuels and chemicals. In this Laboratory Analytical Procedure (LAP), combustion-based ultimate analysis is used to determine the weight percent (wt%) of C, H, and N in bio-oils and upgraded products. Ultimate analysis uses high temperatures and a pure oxygen environment to completely combust organic samples to carbon dioxide (CO 2 ), water (H 2 O), and nitrogen oxides (NO x ). In this procedure the amount of C and H in the sample are quantified by measuring resultant CO 2 and H 2 O with Fourier-transform infrared spectroscopy (FTIR). For N, NO x is reduced to nitrogen (N 2 ) which is measured with a thermal conductivity detector (TCD), providing total N content.

09 BIOMASS FUELS↗

Iodine Capture Studies of Silver Mordenite and Novel Alternative Metal Sorbents

Radioiodine is one of the radionuclides of concern when considering reprocessing of used nuclear fuel (UNF). It is expected to be released primarily in the dissolver off-gas (DOG) stream. Sorbents that target I 2 removal from a UNF processing off gas must perform efficiently under elevated temperatures in the presence of water vapor and nitrogen oxide gasses (NOx). Many studies have been conducted that examine the adsorption of iodine species in the presence of NOx gases through reduced silver-exchanged mordenite (Ag 0 Z), a zeolite mineral. This study characterizes the effects of iodine, water vapor, and nitrogen dioxide on the adsorption of I 2 by Ag 0 Z at lower temperatures suitable for comparison with novel Cu- and Bi- bearing sorbents which offer a non-RCRA alternative. When exposed to ‘harsh’ conditions such as I 2 , H 2 O, and NO 2 vapors carried by air, Cu 2 S-polyacrylonitrile (PAN) is more efficient than Ag 0 Z and all other novel sorbents, providing with 11% I capture efficiency. However, under ‘ideal’ conditions in which I 2 is carried by dry air), Ag 0 Z is more efficient than Cu 2 S-PAN and other novel sorbents, providing 74% I capture efficiency. To investigate this result and the overall performance of all sorbents tested, several characterization techniques were employed, including thermal gravimetric analysis, scanning electron microscopy – electron dispersion X-Ray spectroscopy, powder X-ray diffraction, and X-ray photoelectron spectroscopy. These techniques are discussed within this report. This document also includes a design and test plan update from Idaho National Laboratory as the next step in testing the high performing sorbents from thin-bed tests carried out by Oak Ridge National Laboratory.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗