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At least 703 records · Page 39

Direct Monitoring of Trace Atmospheric Species via Ion Trap Mass Spectrometry

There is an ever-increasing emphasis on the part of government agencies, academia, and industry on enhancing our understanding of atmospheric processes and assessing the impact of human activities on these processes. While issues such as the ozone hole and rising levels of greenhouse gases have received major attention. relatively little is known about the types, concentrations, sources, and sinks of hydrocarbons in the troposphere and stratosphere. Such information would be of tremendous utility in assessing the roles of various anthropogenic and biogenic processes on global carbon cycles. An ion trap mass spectrometer has been developed for monitoring trace levels of hydrocarbons in the atmosphere on NASA's DC-8 "flying laboratory". This aircraft is used to provide measurements in support of a number of "Mission to Planet Earth" activities and tropospheric chemistry experiments. In past missions, specific compounds have been monitored via highly specialized instrumentation, fast GO, or collection of whole air samples for subsequent ground-based analysis. The ion trap has several features. including small size. excellent sensitivity, and broad applicability, which make it highly atttrat:ive for atmospheric monitoring. The design of this instrument, its air sampling interface. and the various complications associated with aircraft-deployment will be described. Data showing the sensitivity of the instrument for detecting hydrocarbons at mixing ratios below one part-per-billion, and the use of MS/MS for direct, on-line, real-time monitoring will be presented.

Palmer, P. T.↗

Monitoring Trace Contaminants in Air Via Ion Trap Mass Spectrometry

Recent passage of the Clean Air Act with its stricter regulation of toxic gas emissions, and the ever-growing number of applications which require faster turnaround times between sampling and analysis are two major factors which are helping to drive the development of new instrument technologies for in-situ, on-line, real-time monitoring. The ion trap, with its small size, excellent sensitivity, and tandem mass spectrometry capability is a rapidly evolving technology which is well-suited for these applications. In this paper, we describe the use of a commercial ion trap instrument for monitoring trace levels of chlorofluorocarbons (CFCs) and volatile organic compounds (VOCs) in air. A number of sample introduction devices including a direct transfer line interface, short column GC, and a cryotrapping interface are employed to achieve increasing levels of sensitivity. MS, MS/MS, and MS/MS/MS methods are compared to illustrate trade-offs between sensitivity and selectivity. Filtered Noise Field (FNF) technology is found to be an excellent means for achieving lower detection limits through selective storage of the ion(s) of interest during ionization. Figures of merit including typical sample sizes, detection limits, and response times are provided. The results indicate the potential of these techniques for atmospheric assessments, the High Speed Research Program, and advanced life support monitoring applications for NASA.

Palmer, Peter T.↗

Calibration of a Vertical-Scan Long Trace Profiler at MSFC

The long trace profiler (LTP) is the instrument of a choice for the surface figure measurement of grazing incidence mirrors. The modification of conventional LTP, the vertical-scan LTP, capable of measuring the surface figure of replicated shell mirrors is now in operation at Marshall Space Flight Center. Sources of systematic error for vertical-scan LTP are discussed. Calibration method using a test flat mirror and results of measurements are presented.

Gubarev, Mikhail↗

Intra-Engine Trace Species Chemistry

Prompted by the needs of downstream plume-wake models, the Massachusetts Institute of Technology (MIT) and Aerodyne Research Incorporated (ART) initiated a collaborative effort, with funding from the NASA AEAP, to develop tools that would assist in understanding the fundamental drivers of chemical change within the intra-engine exhaust flow path. Efforts have been focused on the development of a modeling methodology that can adequately investigate the complex intra-engine environment. Over the history of this project, our research has increasingly pointed to the intra-engine environment as a possible site for important trace chemical activity. Modeling studies we initiated for the turbine and exhaust nozzle have contributed several important capabilities to the atmospheric effects of aviation assessment. These include a more complete understanding of aerosol precursor production, improved initial conditions for plume-wake modeling studies, and a more comprehensive analysis of ground-based test cell and in-flight exhaust measurement data. In addition, establishing a physical understanding of important flow and chemical processes through computational investigations may eventually assist in the design of engines to reduce undesirable species.

Waitz, Ian A.↗

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↗

Vertical Transport Processes for Inert and Scavenged Species: TRACE-A Measurements

The TRACE-A mission of the NASA DC-8 aircraft made a large-scale survey of the tropical and subtropical atmosphere in September and October of 1992. Both In-situ measurements of CO (G. Sachsen NASA Langley) and aerosol size (J. Browell group, NASA Langley) provide excellent data sets with which to constrain vertical transport by planetary boundary layer mixing and deep-cloud cumulus convection. Lidar profiles of aerosol-induced scattering and ozone (also by Bremen) are somewhat require more subtle interpretation as tracers, but the vertical information on layering largely compensates for these complexities. The reason this DC-8 dataset is so useful is that very large areas of biomass burning over Africa and South America provide surface sources of appropriate sizes with which to characterize vertical and horizontal motions; the major limitation of our source description is that biomass burning patterns move considerably every few days, and daily burning inventories are a matter of concurrent, intensive research. We use the Penn State / NCAR MM5 model in an assimilation mode on the synoptic and intercontinental scale, and assess the success it shows in vertical transport descriptions. We find that the general level of emissions suggested by the climatological approach (Will. Has, U. of Montana) appears to be approximately correct, possibly a bit low, for this October, 1992, time period. Vertical transport in planetary boundary layer mixing to 5.5 kin was observed and reproduced in our simulations. Furthermore we find evidence that Blackader "transilient" or matrix-transport scheme is needed, but may require some adaptation in our tracer model: CO seems to exhibit very high values at the top of the planetary boundary layer, a process that stretches the eddy-diffusion parameterization. We will report on progress in improving the deep convective transport of carbon monoxide: the Grail scheme as we used it at 100 kin resolution did not transport enough material to the upper troposphere. We expect to be able to attribute this to either parameterization reasons (inadequacy of this parameterization at the large 100km scale) or other reasons. Nevertheless, the qualitative nature of deep transport by clouds shows up well in the simulations. As for scavengable species, the simulations predict tens of micrograms per standard cubic meter of smoke aerosol in the boundary layer. In a straightforward illustration of our simple bulk-mass scavenging parameterization, to one or two micrograms per standard cubic meter of smoke aerosol in the free troposphere just above the source regions: very high concentrations for the free troposphere. We expect to report on comparisons of these predictions to a variety of observations.

Chatfield, Robert B.↗

Comparative Model Evaluation Studies of Biogenic Trace Gas Fluxes in Tropical Forests

Simulation modeling can play a number of important roles in large-scale ecosystem studies, including synthesis of patterns and changes in carbon and nutrient cycling dynamics, scaling up to regional estimates, and formulation of testable hypotheses for process studies. Recent comparative studies have shown that ecosystem models of soil trace gas exchange with the atmosphere are evolving into several distinct simulation approaches. Different levels of detail exist among process models in the treatment of physical controls on ecosystem nutrient fluxes and organic substrate transformations leading to gas emissions. These differences are is in part from distinct objectives of scaling and extrapolation. Parameter requirements for initialization scalings, boundary conditions, and time-series driven therefore vary among ecosystem simulation models, such that the design of field experiments for integration with modeling should consider a consolidated series of measurements that will satisfy most of the various model requirements. For example, variables that provide information on soil moisture holding capacity, moisture retention characteristics, potential evapotranspiration and drainage rates, and rooting depth appear to be of the first order in model evaluation trials for tropical moist forest ecosystems. The amount and nutrient content of labile organic matter in the soil, based on accurate plant production estimates, are also key parameters that determine emission model response. Based on comparative model results, it is possible to construct a preliminary evaluation matrix along categories of key diagnostic parameters and temporal domains. Nevertheless, as large-scale studied are planned, it is notable that few existing models age designed to simulate transient states of ecosystem change, a feature which will be essential for assessment of anthropogenic disturbance on regional gas budgets, and effects of long-term climate variability on biosphere-atmosphere exchange.

Potter, C. S.↗

Exploring a Black Body Source as an Absolute Radiometric Calibration Standard and Comparison with a NIST Traced Lamp Standard

Radiometric calibration of the Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) is required for the scientific research and application objectives pursued with the spectroscopic measurements. Specifically calibration is required for: inter-comparison of AVIRIS data measured at different locations and at different times; analysis of AVIRIS data with data measured by other instruments; and analysis of AVIRIS data in conjunction with computer models. The primary effect of radiometric calibration is conversion of AVIRIS instrument response values (digitized numbers, or DN) to units of absolute radiance. For example, a figure shows the instrument response spectrum measured by AVIRIS over a portion of Rogers Dry Lake, California, and another figure shows the same spectrum calibrated to radiance. Only the calibrated spectrum may be quantitatively analyzed for science research and application objectives. Since the initial development of the AVIRIS instrument-radiometric calibration has been based upon a 1000-W irradiance lamp with a calibration traced to the National Institute of Standards and Technology (NIST). There are several advantages to this irradiance-lamp calibration approach. First, the considerable effort of NIST backs up the calibration. Second, by changing the distance to the lamp, the output can closely span the radiance levels measured by AVIRIS. Third, this type of standard is widely used. Fourth, these calibrated lamps are comparatively inexpensive. Conversely, there are several disadvantages to this approach as well. First, the lamp is not a primary standard. Second, the lamp output characteristics may change in an unknown manner through time. Third, it is difficult to assess, constrain, or improve the calibration uncertainty delivered with the lamp. In an attempt to explore the effect and potentially address some of these disadvantages a set of analyses and measurements comparing an irradiance lamp with a black-body source have been completed. This research is ongoing, and the current set of measurements, analyses, and results are presented in this paper.

Green, Robert O.↗

Measurements of Long-Lived Trace Gases from Commercial Aircraft Platforms: Development of Instrumentation

The upper troposphere (6-12 km altitude) is a poorly understood and highly vulnerable region of the atmosphere. It is important because many trace species, including ozone, have their greatest impact as greenhouse (infrared-absorbing) gases in this region. The addition of relatively small amounts of anthropogenic chemicals, such as nitrogen oxides, can have a dramatic effect on the abundance of ozone. Some of these pollutants are deposited directly, e.g., by aircraft, while others are transported in. The primary goal of this project was to measure several chemical compounds in the upper troposphere that will help us to understand how air is to transported to that part of the atmosphere; that is, does it come down from the stratosphere, does it rise from the surface via convection, and so on. To obtain adequate sampling to accomplish this goal, we proposed to make measurements from revenue aircraft during normal flight operations.

Source record↗

Tropospheric Ozone during the TRACE-P Mission: Comparison between TOMS Satellite Retrievals and Aircraft Lidar Data, March 2001

Over the past several years, we have developed two new tropospheric ozone retrievals from the TOMS (Total Ozone Mapping Spectrometer) satellite instrument that are of sufficient resolution to follow pollution episodes. The modified-residual technique uses v. 7 TOMS total ozone and is applicable to tropical regimes in which the wave-one pattern in total ozone is observed. The TOMS-direct method ('TDOT' = TOMS Direct Ozone in the Troposphere) represents a new algorithm that uses TOMS radiances directly to extract tropospheric ozone in regions of constant stratospheric ozone. It is not geographically restricted, using meteorological regimes as the basis for classifying TOMS radiances and for selecting appropriate comparison data. TDOT is useful where tropospheric ozone displays high mixing ratios and variability characteristic of pollution. Some of these episodes were observed downwind of Asian biomass burning during the TRACE-P (Transport and Atmospheric Chemical Evolution-Pacific) field experiment in March 2001. This paper features comparisons among TDOT tropospheric ozone column depth, integrated uv-DIAL measurements made from NASA's DC-8, and ozonesonde data.

Frolov, A. D.↗

Calibration and Data Retrieval Algorithms for the NASA Langley/Ames Diode Laser Hygrometer for the NASA Trace-P Mission

This paper describes the procedures and algorithms for the laboratory calibration and the field data retrieval of the NASA Langley / Ames Diode Laser Hygrometer as implemented during the NASA Trace-P mission during February to April 2000. The calibration is based on a NIST traceable dewpoint hygrometer using relatively high humidity and short pathlength. Two water lines of widely different strengths are used to increase the dynamic range of the instrument in the course of a flight. The laboratory results are incorporated into a numerical model of the second harmonic spectrum for each of the two spectral window regions using spectroscopic parameters from the HITRAN database and other sources, allowing water vapor retrieval at upper tropospheric and lower stratospheric temperatures and humidity levels. The data retrieval algorithm is simple, numerically stable, and accurate. A comparison with other water vapor instruments on board the NASA DC-8 and ER-2 aircraft is presented.

Podolske, James R.↗

Global Reference Atmospheric Model and Trace Constituents

Global Reference Atmospheric Model (GRAM-99) is an engineering-level model of the Earth's atmosphere. It provides both mean values and perturbations for density, temperature, pressure, and winds, as well as monthly- and geographically-varying trace constituent concentrations. From 0-27 km, thermodynamics and winds are based on National Oceanic and Atmospheric Administration Global Upper Air Climatic Atlas (GUACA) climatology. Above 120 km, GRAM is based on the NASA Marshall Engineering Thermosphere (MET) model. In the intervening altitude region, GRAM is based on Middle Atmosphere Program (MAP) climatology that also forms the basis of the 1986 COSPAR Intemationa1 Reference Atmosphere (CIRA). MAP data in GRAM are augmented by a specially-derived longitude variation climatology. Atmospheric composition is represented in GRAM by concentrations of both major and minor species. Above 120 km, MET provides concentration values for N2, O2, Ar, O, He, and H. Below 120 km, species represented also include H2O, O3, N2O, CO, CH, and CO2. Water vapor in GRAM is based on a combination of GUACA, Air Force Geophysics Laboratory (AFGL), and NASA Langley Research Center climatologies. Other constituents below 120 km are based on a combination of AFGL and h4AP/CIRA climatologies. This report presents results of comparisons between GRAM Constituent concentrations and those provided by the Naval Research Laboratory (NRL) climatology of Summers (NRL,/MR/7641-93-7416, 1993). GRAM and NRL concentrations were compared for seven species (CH4, CO, CO2, H2O, N2O, O2, and O3) for months January, April, July, and October, over height range 0-115 km, and latitudes -90deg to + 90deg at 10deg increments. Average GRAM-NRL correlations range from 0.878 (for CO) to 0.975 (for O3), with an average over all seven species of 0.936 (standard deviation 0.049).

Justus, C.↗

Chemical Data Assimilation: A Case Study of Solar Occultation Data From the Atlas 1 Mission of the Atmospheric Trace Molecule Spectroscopy Experiment

A key advantage of using data assimilation is the propagation of information from data-rich regions to data-poor regions, which is particularly relevant to the use of solar occultation data such as from ATMOS. For the first time an in depth uncertainty analyses is included in a photochemical model-data intercomparison including observation, representativeness, and theoretical uncertainty. Chemical data assimilation of solar occultation measurements can be used to reconstruct full diurnal cycles and to evaluate their chemical self-consistency. This paper considers as an example the measurements made by the Atmospheric Trace Molecule Spectroscopy Experiment (ATMOS) instrument Atlas-1 during March 1992 for a vertical profile flow tracking coordinates at an equivalent PV latitude of 38 S. ATMOS was chosen because it simultaneously observes several species. This equivalent PV latitude was chosen as it was where ATMOS n observed the atmosphere's composition over the largest range of altitudes. A single vertical profile was used so that the detailed diurnal information that assimilation utilizes could be highlighted. There is generally good self-consistency between the ATMOS Atlas-1 observations and photochemical theory.

Lary, D. J.↗

Extraterrestrial Amino Acids in Orgueil and Ivuna: Tracing the Parent Body of CI Type Carbonaceous Chondrites

Amino acid analyses using HPLC of pristine interior pieces of the CI carbonaceous chondrites Orgueil and Ivuna have found that beta-alanine, glycine, and gamma-amino-n-butyric acid (ABA) are the most abundant amino acids in these two meteorites, with concentrations ranging from approx. 600 to 2,000 parts per billion (ppb). Other alpha-amino acids such as alanine, alpha-ABA, alpha-aminoisobutyric acid (AIB), and isovaline are present only in trace amounts (less than 200 ppb). Carbon isotopic measurements of beta-alanine and glycine and the presence of racemic (D/L 1) alanine and beta-ABA in Orgueil suggest that these amino acids are extraterrestrial in origin. In comparison to the CM carbonaceous chondrites Murchison and Murray, the amino acid composition of the CIs is strikingly distinct, suggesting that these meteorites came from a different type of parent body, possibly an extinct comet, than did the CM carbonaceous chondrites.

Meyer, Michael↗

Reassessing the Evidence for the Earliest Traces of Life

The isotopic composition of graphite is commonly used as a biomarker in the oldest (>3.5 Gyr ago) highly metamorphosed terrestrial rocks. Earlier studies on isotopic characteristics of graphite occurring in rocks of the approximately 3.8-Gyr-old Isua supracrustal belt (ISB) in southern West Greenland have suggested the presence of a vast microbial ecosystem in the early Archean. This interpretation, however, has to be approached with extreme care. Here we show that graphite occurs abundantly in secondary carbonate veins in the ISB that are formed at depth in the crust by injection of hot fluids reacting with older crustal rocks (metasomatism). During these reactions, graphite forms from the disproportionation of Fe(II)-bearing carbonates at high temperature. These metasomatic rocks, which clearly lack biological relevance, were earlier thought to be of sedimentary origin and their graphite association provided the basis for inferences about early life. The new observations thus call for a reassessment of previously presented evidence for ancient traces of life in the highly metamorphosed Early Archaean rock record.

vanZullen, Mark A.↗

An Intercomparison and Evaluation of Aircraft-Derived and Simulated CO from Seven Chemical Transport Models During the TRACE-P Experiment

Four global scale and three regional scale chemical transport models are intercompared and evaluated during NASA's TRACE-P experiment. Model simulated and measured CO are statistically analyzed along aircraft flight tracks. Results for the combination of eleven flights show an overall negative bias in simulated CO. Biases are most pronounced during large CO events. Statistical agreements vary greatly among the individual flights. Those flights with the greatest range of CO values tend to be the worst simulated. However, for each given flight, the models generally provide similar relative results. The models exhibit difficulties simulating intense CO plumes. CO error is found to be greatest in the lower troposphere. Convective mass flux is shown to be very important, particularly near emissions source regions. Occasionally meteorological lift associated with excessive model-calculated mass fluxes leads to an overestimation of mid- and upper- tropospheric mixing ratios. Planetary Boundary Layer (PBL) depth is found to play an important role in simulating intense CO plumes. PBL depth is shown to cap plumes, confining heavy pollution to the very lowest levels.

Kiley, C. M.↗

Trace Element Distribution Between Olivine and Kirschsteinite in Angra Dos Reis

The angrites are a small and enigmatic group of basaltic achondrites that possess unique mineralogical and chemical properties. The dominant mineralogy of the seven angrite members (Angra dos Reis, LEW 86010, LEW 87051, Asuka 881371, Sahara 99555, D Orbigny, and a new Moroccan member) is fassaite, olivine, and plagioclase. Angrites display a wide range of thermal histories, with Angra dos Reis (AdoR) exhibiting a cooling history different from that of the rapidly cooled members and from LEW86010, a more slowly cooled member. AdoR could represent either a cumulate or a porphyritic igneous rock that was later altered by metamorphism. We are re-examining the thermal history of AdoR in light of the more recently described angrite members. Our emphasis is a trace element study of low-Ca olivine, which we refer to as olivine, and high-Ca olivine, which we refer to as kirschsteinite, in AdoR.

Fittipaldo, M. M.↗