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At least 217 records · Page 12

Trace gas emissions to the atmosphere by biomass burning in the west African savannas

Savanna fires and atmospheric carbon dioxide (CO2) detection and estimating burned area using Advanced Very High Resolution Radiometer_(AVHRR) reflectance data are investigated in this two part research project. The first part involves carbon dioxide flux estimates and a three-dimensional transport model to quantify the effect of north African savanna fires on atmospheric CO2 concentration, including CO2 spatial and temporal variability patterns and their significance to global emissions. The second article describes two methods used to determine burned area from AVHRR data. The article discusses the relationship between the percentage of burned area and AVHRR channel 2 reflectance (the linear method) and Normalized Difference Vegetation Index (NDVI) (the nonlinear method). A comparative performance analysis of each method is described.

Frouin, Robert J.↗

Impact of August 2017 British Columbia Pyrocumulonimbus Injection Events on Lower Stratospheric Composition

On August 12-13, 2017 large wildfires in the Cariboo region of British Columbia, Canada sparked a series of pyrocumulonimbus events lifting carbonaceous aerosol and other trace gases to the tropopause region (~10-11 km). Over the subsequent days, this plume of trace gas and aerosol species was observed from numerous NASA satellite instruments to rise to over 22 km due to the strong shortwave heating of the carbonaceous aerosol. We will show observations of CO and H2O from the Microwave Limb Sounder (MLS) instrument on Aura satellite demonstrating the clear rise and spread of the plume which can be coherently tracked for at least 2 months. Enhancements in HCN, CH3CN, and methanol (CH3OH) are also evident in MLS measurements with the former two having low vertical resolution. We have also detected a significantly lower concentration of O3 and HNO3 in the plume compared to the surrounding environment, which is consistent with a dynamical perturbation from the rapid diabatic rise of the heated plume from the tropopause through the lower stratosphere. In the weeks and months that followed this plume spread over much of the Northern Hemisphere and the aerosol was observed to be slowly removed by transport back into the troposphere. We will compare and contrast the Aug. 2017 event with the other large event in the MLS record, the Feb. 2009 Australian "Black Saturday" event, and use the Goddard Earth Observing System Chemistry-Climate Model (GEOSCCM) replayed to observed meteorology to understand the effect of the British Columbia event on trace gas species. GEOSCCM helps us to separate the relative roles of dynamics and chemistry on lower stratospheric trace gas composition changes, not only in the rising plume but also the impact of its eventual spread over the Northern Hemisphere during fall and winter of 2017-2018.

Oman, Luke D.↗

Composition, Emissions, and Air Quality Impacts of Hazardous Air Pollutants in Unburned Natural Gas from Residential Stoves in California

The presence of hazardous air pollutants (HAPs) entrained in end-use natural gas (NG) is an understudied source of human health risks. We performed trace gas analyses on 185 unburned NG samples collected from 159 unique residential NG stoves across seven geographic regions in California. Our analyses commonly detected 12 HAPs with significant variability across region and gas utility. Mean regional benzene, toluene, ethylbenzene, and total xylenes (BTEX) concentrations in end-use NG ranged from 1.6–25 ppmv–benzene alone was detected in 99% of samples, and mean concentrations ranged from 0.7–12 ppmv (max: 66 ppmv). By applying previously reported NG and methane emission rates throughout California’s transmission, storage, and distribution systems, we estimated statewide benzene emissions of 4,200 (95% CI: 1,800–9,700) kg yr –1 that are currently not included in any statewide inventories–equal to the annual benzene emissions from nearly 60,000 light-duty gasoline vehicles. Additionally, we found that NG leakage from stoves and ovens while not in use can result in indoor benzene concentrations that can exceed the California Office of Environmental Health Hazard Assessment 8-h Reference Exposure Level of 0.94 ppbv–benzene concentrations comparable to environmental tobacco smoke. This study supports the need to further improve our understanding of leaked downstream NG as a source of health risk.

42 ENGINEERING↗

Elemental characteristics of aerosols emitted from a coal-fired heating plant

Size differentiated aerosols were collected downstream from a heating plant fueled with eastern coal and analyzed using particle induced X-ray emission technique. Based on aerosol masses collected in various size ranges, the aerosol size distribution is determined to be trimodal, with the three peaks centered at 0.54 microns, 4.0 microns, and 11.0 microns, respectively. Of the various trace elements present in the aerosols, sulphur is the only element that shows very strong concentration in the smallest size group. Iron is strongly concentrated in the 4.0 micron group. Potassium, calcium, and titanium also exhibit stronger concentration in the 4.0 micron group than any other group. Other trace elements - vanadium, chromium, manganese, nickel, copper, and barium - are equally divided between the 0.54 microns and the 4.0 microns groups. Apparently, all of the trace elements - except S - enter aerosols during the initial formation and subsequent condensation phases in the combustion process. Excess concentration of sulphur in the 0.54 microns group can only be accounted for by recondensation of sulphur vapors on the combustion aerosols and gas-to-particle phase conversion of sulfate vapors at the stack top.

Singh, J. J.↗

A Modeling and Simulation Study for the GeoXO Atmospheric Composition Instrument (ACX): System Level SO2 and O3 Retrieval Performance as a Function of SNR

NOAA’s Geostationary Extended Observations (GeoXO) program is planning to include a hyperspectral UV/visible atmospheric composition instrument in geostationary orbit slated for operations by the early 2030s. Trace gas retrievals provide critical information about our Earth’s system as it relates to both natural and anthropogenic activity. This work focused on the impacts of the signal-to-noise ratio (SNR) on the retrieval uncertainty of SO2 and O3. An end-to-end physics-based imaging system and scene modeling and simulation framework was developed to assess instrument performance considerations in support of the planned GeoXO atmospheric composition instrument (ACX). The framework is composed of three primary components: 1) simulated at-sensor radiance via radiative transfer models of a known atmospheric composition, 2) a noise model driven by previous and planned sensor specifications, and 3) a physical retrieval algorithm. In this analysis, the tropospheric concentrations of SO2 and O3 in the atmospheric column were varied in the boundary layer (0-3 km) and at an elevation of 5 km with a thickness of 1-2 km; the uncertainty in retrieval was studied for various SNR levels for multiple viewing geometries and solar zenith angles. This effort supports the development of the GeoXO ACX instrument by providing a simulated ACX performance assessment of the system-level retrieval performance as a function of SNR, particularly with respect to the wavelength range of interest (approximately 305 – 340 nm) for SO2 and O3 trace gas retrievals.

Monica Cook↗

Laser absorption spectroscopy - Method for monitoring complex trace gas mixtures

A frequency stabilized CO2 laser was used for accurate determinations of the absorption coefficients of various gases in the wavelength region from 9 to 11 microns. The gases investigated were representative of the types of contaminants expected to build up in recycled atmospheres. These absorption coefficients were then used in determining the presence and amount of the gases in prepared mixtures. The effect of interferences on the minimum detectable concentration of the gases was measured. The accuracies of various methods of solution were also evaluated.

Green, B. D.↗

Determination of methane in ambient air by multiplex gas chromatography

A multiplex gas chromatographic technique for the determination of methane in ambient air over extended periods is reported. A modest gas chromatograph which uses air as the carrier gas was modified by adding a silver oxide sample modulator for multiplex operation. The modulator selectively catalyzes the decomposition of methane in air. The resulting analytical system requires no consumables beyond power. A profile of the methane concentration in this laboratory was obtained for an 8-day period. During this period, methane concentration varied with an approximately daily period from a low of 1.53 + or - 0.60 ppm to a high of 4.63 + or - 0.59 ppm over the entire 8 days. Some of the measured concentrations are higher than those reported elsewhere indicating the presence of some local source or sources for methane. This work has demonstrated the utility of a relatively simple multiplex gas chromatograph for the analysis of environmental samples. The technique should be applicable to other trace components in air through use of other selective modulators.

Valentin, J. R.↗

Implementation of the Glycolate Destruction Process with Sodium Permanganate in the Defense Waste Processing Facility (DWPF) - 20141

The Savannah River Site (SRS) seeks to replace formic acid with glycolic acid as a chemical reductant in the Defense Waste Processing Facility (DWPF), where borosilicate glass is mixed with high-level radioactive waste, melted at high temperatures, then poured into stainless steel canisters for safe storage. Prior research and development have demonstrated the feasibility and advantages of the new nitric-glycolic acid flowsheet over the current nitric-formic acid flowsheet to chemically adjust the radioactive sludge slurry waste in the Sludge Receipt and Adjustment Tank (SRAT) prior to vitrification. Use of glycolic acid reduces hydrogen and ammonia generation during the reduction process, thus reducing flammability hazards and purge requirements in the DWPF processing vessels. In addition, glycolic acid will support the new Salt Waste Processing Facility (SWPF) by allowing for receipt of higher volumes of waste due to reduction of flammable gases, increased boil-up rates in the vessels, and easing the processing of future sludge batches containing high levels of mercury. However, during DWPF operations, trace amounts of glycolate are anticipated to be entrained in the recycle stream and sent to the Concentration, Storage, and Transfer Facilities (CSTF) via the Recycle Collection Tank (RCT). The RCT receives condensate from the Slurry Mix Evaporator Condensate Tank (SMECT) and Off-gas Condensate Tank (OGCT) that may contain unreacted glycolate. A literature review found the potential for hydrogen generation due to thermolysis of glycolate in caustic CSTF conditions. Savannah River National Laboratory (SRNL) conducted several tests on simulant and radioactive waste from various tanks at SRS and confirmed that glycolate added to waste at concentrations of approximately 1000 mg/L and higher generates hydrogen through thermolysis. There are potential operating scenarios in the future where glycolate concentration could exceed 1000 mg/L in the 2H Evaporator Drop Tank, the highest accumulation point for DWPF organics received via recycle. These findings presented a need to develop another process to mitigate the impact of glycolic acid to the CSTF. Several DWPF compatible options were evaluated for their ability to destroy glycolate in the DWPF recycle stream under various processing conditions, thereby mitigating its introduction to the CSTF. Downselection testing identified sodium permanganate as the most promising and simplest option to oxidize glycolate. It has been demonstrated to be effective in various RCT simulant compositions, operating temperatures, oxidant addition rates, solution pH, and initial glycolate concentrations. A feasibility study identified existing tanks within the facility that could be used for receiving and storing the commercially available sodium permanganate, as well as feeding it to the RCT for processing. The use of existing equipment as well as the ability to purchase the pre-mixed chemical reduces implementation and operational complexity. The downstream impacts of the sodium permanganate reaction were also evaluated and demonstrated to have minimal impact on other chemical species present in the RCT and CSTF, as well as on the materials of construction of the RCT and CSTF vessels and associated piping and instrumentation. Future work is in progress to validate the glycolate destruction process with testing in actual radioactive RCT waste before implementation in DWPF. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Cloud draft structure and trace gas transport

During the second Amazon Boundary Layer Experiment (ABLE 2B), meteorological observations, chemical measurements, and model simulations are utilized in order to interpret convective cloud draft structure and to analyze its role in transport and vertical distribution of trace gases. One-dimensional photochemical model results suggest that the observed poststorm changes in ozone concentration can be attributed to convective transports rather than photochemical production and the results of a two-dimensional time-dependent cloud model simulation are presented for the May 6, 1987 squall system. The mesoscale convective system exhibited evidence of significant midlevel detrainment in addition to transports to anvil heights. Chemical measurements of O3 and CO obtained in the convective environment are used to predict photochemical production within the troposphere and to corroborate the cloud model results.

Scala, John R.↗

Noble gases in E-chondrites

The combination of noble gas data for 12 E-chondrites with literature data shows K-Ar ages greater than 4 AE for 14 out of 18 meteorites, while U, Th-He ages are often shorter. Cosmic ray exposure ages are found to differ systematically between types E4 and E6, with the respective, below-16 Myr and above-30 Myr values implying that the E-chondrite parent body predominantly contains a single petrologic type on the 1 km scale of individual impacts in contrast to the mixed parent bodies of the ordinary chondrites. Amounts of planetary gas in E4-E6 chondrites fall in the range for ordinary chondrites of types 4-6, but fail to correlate with petrologic type or volatile trace element contents, in contrast to the ordinary chondrites. Analyses of mineral separates show that the planetary gases are concentrated in an HFand HCl-insoluble mineral, similar to phase Q. The subsolar gases are located in an HCl- and HNO3-resistant phase.

Crabb, J.↗

Development of data processing, interpretation and analysis system for the remote sensing of trace atmospheric gas species

The major emphasis is on the advancement of remote sensing technology. In particular, the gas filter correlation radiometer (GFCR) technique was applied to the measurement of trace gas species, such as carbon monoxide (CO), from airborne and Earth orbiting platforms. Through a series of low altitude aircraft flights, high altitude aircraft flights, and orbiting space platform flights, data were collected and analyzed, culminating in the first global map of carbon monoxide concentration in the middle troposphere and stratosphere. The four major areas of this remote sensing program, known as the Measurement of Air Pollution from Satellites (MAPS) experiment, are: (1) data acquisition, (2) data processing, analysis, and interpretation algorithms, (3) data display techniques, and (4) information processing.

Casas, Joseph C.↗

Transport into the south polar vortex in early spring

The effect of transport on the springtime decline in ozone in the southern polar vortex was investiated using data on long-lived gas tracers (N2O, CH4, CCl4, CH3CCl3, CO, CFC-11, CFC-12, and CFC-113) obtained by the ER-2 aircraft in the period between August 23 and September 22 during the Airborne Antarctic Ozone Experiment. It was found that, while the concentrations of long-lived trace gases remained relatively constant for fixed potential temperature and latitude, the ozone mixing ratio over the same period declined by more than 50 percent inside the polar vortex near 18-km altitude. These data indicate a substantial photochemical sink of ozone. The evidence of the zero or negative time tendencies for long-lived trace gases and the meridional and vertical gradients of ozone imply that transport is supplying ozone to the polar region during springtime.

Hartmann, D. L.↗

Measurements of CCl3F, CCl2F2, CCl4, N2O and SF6 in the Northern Hemisphere stratosphere

An overview of the Department of Energy's High Altitude Sampling Program and some recent trace gas measurement results are presented. Analysis of whole air samples, collected in pressurized bottles, provides information on stratospheric inventories and distributions for CCl3F, CCl2F2, CCl4, N2O and SF6 in the Northern Hemisphere. Based on a linear regression analysis of the data the estimated mean Northern Hemisphere stratospheric concentration of each gas increased as follows: CCl3F changed from 54 to 142 p1/1 (4/74-11/83); CCl2F2 changed from 133 to 268 p1/1 (4/76-11/83); SF6 changed from 160 to 480 f1/1 (4/74-11/83); CC1, changed from 58 to 91 p1/1 (4/75-11/83); N2O changed from 246 to 261 n1/1 (4/76-11/83). The calculated mean Northern Hemisphere stratospheric concentrations of N2O, CCl3F, CCl2F2, and CCl4 after 1980 show larger than expected fluctuations with time. Recent volcanic activity may be a partial cause for these fluctuations through induced changes in stratospheric dynamical processes.

Leifer, R.↗

Advanced Global Atmospheric Gases Experiment (AGAGE): MIT Contribution

We describe in detail the instrumentation and calibrations used in the ALE, GAGE and AGAGE experiments and present a history of the majority of the anthropogenic ozone- depleting and climate-forcing gases in air based on these experiments. Beginning in 1978, these three successive automated high frequency in-situ experiments have documented the long-term behavior of the measured concentrations of these gases over the past twenty years, and show both the evolution of latitudinal gradients and the high frequency variability due to sources and circulation. We provide estimates of the long-term trends in total chlorine contained in long- lived halocarbons involved in ozone depletion. We summarize interpretations of these measurements using inverse methods to determine trace gas lifetimes and emissions. Finally, we provide a combined observational and modeled reconstruction of the evolution of chlorocarbons by latitude in the atmosphere over the past sixty years which can be used as boundary conditions for interpreting trapped air in glaciers and oceanic measurements of chlorocarbon tracers of the deep oceanic circulation. Some specific conclusions are: (a) International compliance with the Montreal Protocol is so far resulting in chlorofluorocarbon and chlorocarbon mole fractions comparable to target levels, (b) Mole fractions of total chlorine contained in long-lived halocarbons (CCl2F2, CCl3F, CH3CCl3, CCl4, CHClF2, CCl2FCClF2, CH3Cl, CH2Cl2, CHCl3, CCl2=CCl2) in the lower troposphere reached maximum values of about 3.6 ppb in 1993 and are beginning to slowly decrease in the global lower atmosphere, (c) The chlorofluorocarbons have atmospheric lifetimes consistent with destruction in the stratosphere being their principal removal mechanism, (d) Multi-annual variations in chlorofluorocarbon and chlorocarbon emissions deduced from ALUGAGWAGAGE data are consistent approximately with variations estimated independently from industrial production and sales data where available (CCl2F2 (CFC-12) and CCl2FCClF2 (CFC-113) show the greatest discrepancies), (e) The mole fractions of the hydrochlorofluorocarbons and hydrofluorocarbons, which are replacing the regulated halocarbons, are rising very rapidly in the atmosphere but, with the exception of the much longer manufactured CHClF2 (HCFC-22), they are not yet at levels sufficient to contribute significantly to atmospheric chlorine loading. These replacement species could in the future provide independent estimates of the global weighted-average OH concentration provided their industrial emissions are accurately documented, (f) In the future, analysis of pollution events measured using high frequency in-situ measurements of chlorofluorocarbons and their replacements may enable emission estimates at the regional level which, together with industrial end-use data, are of sufficient accuracy to be capable of identifying regional non-compliance with the Montreal Protocol.

Kurylo, Michael↗

Miniaturized system of a gas chromatograph coupled with a Paul ion trap mass spectrometer

Miniature gas chromatography (GC) and miniature mass spectrometry (MS) instrumentation has been developed to identify and quantify the chemical compounds present in complex mixtures of gases. The design approach utilizes micro-GC components coupled with a Paul quadrupole ion trap (QIT) mass spectrometer. Inherent to the system are high sensitivity, good dynamic range, good QIT resolution, low GC flow-rates to minimize vacuum requirements and the need for consumables; and the use of a modular approach to adapt to volatile organic compounds dissolved in water or present in sediment. Measurements are reported on system response to gaseous species at concentrations varying over four orders of magnitude. The ability of the system to deal with complicated mixtures is demonstrated, and future improvements are discussed. The GC/QIT system described herein has a mass, volume and power that are, conservatively, one-twentieth of those of commercial off-the-shelf systems. Potential applications are to spacecraft cabin-air monitoring, robotic planetary exploration and trace-species detection for residual gas analysis and environmental monitoring.

Miniaturization/instrumentation/methods↗

The fall, recovery, classification, and initial characterization of the Hamburg, Michigan H4 chondrite

Abstract The Hamburg meteorite fell on January 16, 2018, near Hamburg, Michigan, after a fireball event widely observed in the U.S. Midwest and in Ontario, Canada. Several fragments fell onto frozen surfaces of lakes and, thanks to weather radar data, were recovered days after the fall. The studied rock fragments show no or little signs of terrestrial weathering. Here, we present the initial results from an international consortium study to describe the fall, characterize the meteorite, and probe the collision history of Hamburg. About 1 kg of recovered meteorites was initially reported. Petrology, mineral chemistry, trace element and organic chemistry, and O and Cr isotopic compositions are characteristic of H4 chondrites. Cosmic ray exposure ages based on cosmogenic 3 He, 21 Ne, and 38 Ar are ~12 Ma, and roughly agree with each other. Noble gas data as well as the cosmogenic 10 Be concentration point to a small 40–60 cm diameter meteoroid. An 40 Ar‐ 39 Ar age of 4532 ± 24 Ma indicates no major impact event occurring later in its evolutionary history, consistent with data of other H4 chondrites. Microanalyses of phosphates with LA‐ICPMS give an average Pb‐Pb age of 4549 ± 36 Ma. This is in good agreement with the average SIMS Pb‐Pb phosphate age of 4535.3 ± 9.5 Ma and U‐Pb Concordia age of 4535 ± 10 Ma. The weighted average age of 4541.6 ± 9.5 Ma reflects the metamorphic phosphate crystallization age after parent body formation in the early solar system.

79 ASTRONOMY AND ASTROPHYSICS↗

Detection of trace quantities of dimethylacetamide during the curing process of a polyimide film

An experimental study of positive ion clustering of dimethylacetamide (DMAC) with water molecules using high pressure mass spectrometry techniques is reported. The possibilities of using these techniques to determine the concentration levels of DMAC evolved from a polyimide film during the curing process, are examined. The test sample of gas contained DMAC of the order of a few micrograms, water, nitrogen, oxygen, and other compounds that might evolve during the curing cycle of a polyimide film. It is found that PPM concentrations such as DMAC lost from polyimide during curing stages can be detected with this technique. Improvement of the detection of lower concentrations (50 picograms) can be made by using electron multipliers with a gain in the 10 to the 8th power range and pulse counting techniques.

Smith, A. C.↗

In situ aircraft measurements of enhanced levels of N2O associated with thunderstorm lightning

A series of measurements of enhanced levels of atmospheric N2O associated with thunderstorm lightning are reported. The data were gathered by instrumentation on-board an aircraft operated as part of the NASA Storm Hazards Project. Air samples were taken both during storms and in clear conditions to have a basis for comparisons; sample bottles were filled at altitudes from 11,000-40,000 ft. Gas chromatography was employed for sample composition analyses, revealing clear air N2O concentrations of about 310 ppbv, while storm concentrations reached, for example, 490, 729, and 393 ppbv. Although the measurements did not precisely characterize the actual lightning contributions, the enhancements being present during electrically active storms did confirm that trace gases are produced by lightning. Calculations are presented to demonstrate that the 3 to greater than 12 keV X rays detected in storm clouds are of sufficient energy to drive the production of N2O from the reaction of metastable nitrogen with molecular oxygen.

Levine, J. S.↗