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All sourcesNASA NTRSDOE OSTI
NASA NTRS1987

Atmospheric infrared emission of ClONO2 observed by a balloon-borne Fourier spectrometer

ClONO2 was observed in high-resolution infrared emission spectra obtained on Nov. 6, 1984, by a balloon-borne Fourier spectrometer. The observations took place near 0300 LT at a latitude of 35 N. Spectral simulations are used to determine the mixing ratios of ClONO2. This analysis incorporates line by line calculations and new ClONO2 cross sections measured in the laboratory at 223 K. The inferred mixing ratios of ClONO2 are 1.3 + or - 0.45 ppb and 0.98 + or - 0.35 ppb at 14 and 34 mbar. One-dimensional photochemical model predictions are compared to the observations. The ClONO2 mixing ratio at 34 mbar appears to be larger than theory, while there is agreement at 14 mbar.

Massie, S. T.↗
NASA NTRS1988

Photochemistry of biogenic emissions over the Amazon forest

The boundary layer chemistry over the Amazon forest during the dry season is simulated with a photochemical model. Results are in good agreement with measurements of isoprene, NO, ozone, and organic acids. Photochemical reactions of biogenic isoprene and NOx can supply most of the ozone observed in the boundary layer. Production of ozone is very sensitive to the availability of NOx, but is insensitive to the isoprene source strength. High concentrations of total odd nitrogen (NOy) are predicted for the planetary boundary layer, about 1 ppb in the mixed layer and 0.75 ppb in the convective cloud layer. Most of the odd nitrogen is present as PAN-type species, which are removed by dry deposition to the forest. The observed daytime variations of isoprene are explained by a strong dependence of the isoprene emission flux on sun angle. Nighttime losses of isoprene exceed rates of reaction with NO3 and O3 and appear to reflect dry-deposition processes. The 24-hour averaged isoprene emission flux is calculated to be 38 mg/sq m per day. Photooxidation of isoprene could account for a large fraction of the CO enrichment observed in the boundary layer under unpolluted conditions and could constitute an important atmospheric source of formic acid, methacrylic acid, and pyruvic acid.

Jacob, Daniel J.↗
NASA NTRS1988

Iridium abundance maxima in the Upper Cenomanian extinction interval

Two iridium abundance peaks, both 0.11 ppb (whole-rock basis) over a local background of 0.017 ppb, have been found in Middle Cretaceous marine rocks near Pueblo, Colorado. They occur just below the 92-million-year-old Cenomanian-Turonian (C-T) stage boundary. No other peaks were found in 45 meters of strata (about 2.5 million years of deposition) above and below the boundary interval. The broad lower peak straddles the first in a series of extinctions of benthic and nektonic macrobiota which comprise the C-T extinction event. The sharp upper peak occurs stratigraphically about 1.2 meters above the lower peak. The excess Ir might be from meteoroid impacts.

Orth, C. J.↗
NASA NTRS1988

Sulfur dioxide at the Venus cloud tops, 1978-1986

Ultraviolet spectroscopy from the Pioneer Venus Orbiter shows a decline in the cloud top abundance of SO2 from about 100 ppb to about 10 ppb in the period 1978-1986. A consistent decline in polar haze has occurred over the same period, with the correlation coefficient between these two observables of r = 0.8. Star calibrations determine the instrument sensitivity to within 10 percent which rules out the possibility that this is an instrumental effect. Systematic errors could increase the SO2 abundance to twice the inferred values in later orbits. Tracking of SO2 features and power spectral analysis give rotation periods for the longer-lived features of 3.6-5.2 days, consistent with cloud-tracked winds observed at other wavelengths. The behavior of SO2 and polar haze can be plausibly explained by episodic injection of SO2 into the cloud top regions, for example, by active volcanism.

Esposito, Larry W.↗
NASA NTRS1988

Volatile/mobile trace elements in meteoritic, non-lunar basalts: Guides to Martian sample contents

A variety of genetic processes on or in extraterrestrial objects can be examined by study of volatile/mobile trace elements. Doubtless, considerable efforts will be expended on determining these elements in returned Martian samples. The purpose is to estimate levels of such elements expected to be present in returned Martian samples. Some ideas about Martian genesis were already advanced from the volatile/mobile element contents in SNC meteorites, assuming that Mars was their parent body. Even is Mars and the SNC meteorite parent body are identical, compositional ranges for returned Martian samples should exceed those of SNC meteorites. It is expected, therefore, that Martian samples returned from locations other than Polar regions will have indigenous volatile/mobile element contents within howardite-diogenite ranges. Elements with strong lithophile tendences may be more abundant, as they are in many lunar samples. Most of these elements should be at ppb levels except for Co, Ga, Zn, and Rb, which should lie at ppm levels. If Martian volcanism was accompanied by fumarolic emanations, it should be reflected in occasional huge enrichments of mobile trance elements, as in lunar meteorite Y 791197. During collection and transport Earthward, samples must be contained under conditions appropriate to ppb concentrations. Materials must be used that will not cause contamination which occurred during the Apollo program, where indium from seals contaminated many samples.

Lipschutz, M. E.↗
NASA NTRS1989

Measurements of peroxyacetyl nitrate (PAN) and peroxypropionyl nitrate (PPN) at selected urban, rural and remote sites

PAN and PPN were measured in a series of eight field studies performed at urban, rural and remote locations in the contiguous U.S. during 1983-1985. Seven of the eight studies were performed in the winter/spring period, a period of sparsely available data. Nearly 2000 air samples were analyzed during these studies. Mean PAN and PPN levels in the range of 45-1600 ppt (max. 7.9 ppb) and 5-230 ppt (max. 0.9 ppb), respectively, were measured. Despite a great deal of observed variability, PAN and PPN showed virtually identical behavior at all sites and in all seasons, supporting the view that these nitrogenous compounds are produced and destroyed by very similar mechanisms. On the average PPN concentrations were about 8 percent (range 3-14 percent) of PAN values. It is inferred that PPN/PAN ratio is highest in urban areas and declines as polluted air masses are transported over long distances.

Singh, Hanwant B.↗
NASA NTRS1990

Low level vapor verification of monomethyl hydrazine

The vapor scrubbing system and the coulometric test procedure for the low level vapor verification of monomethyl hydrazine (MMH) are evaluated. Experimental data on precision, efficiency of the scrubbing liquid, instrument response, detection and reliable quantitation limits, stability of the vapor scrubbed solution, and interference were obtained to assess the applicability of the method for the low ppb level detection of the analyte vapor in air. The results indicated that the analyte vapor scrubbing system and the coulometric test procedure can be utilized for the quantitative detection of low ppb level vapor of MMH in air.

Mehta, Narinder↗
NASA NTRS1992

Hydrazine monitoring in spacecraft

Hydrazine (HZ) and monomethyl hydrazine (MMH) are highly toxic compounds used as fuels in the Space Shuttle Orbiter Main Engines and in its maneuvering and reaction control system. Satellite refueling during a mission may also result in release of hydrazines. During extravehicular activities, the potential exists for hydrazines to contaminate the suit and to be brought into the internal atmosphere inadvertantly. Because of the high toxicity of hydrazines, a very sensitive, reliable, interference-free, and real-time method of measurement is required. A portable ion mobility spectrometer (IMS) has exhibited a low ppb detection limit for hydrazines suggesting a promising technology for the detection of hydrazines in spacecraft air. The Hydrazine Monitor is a modified airborne vapor monitor (AVM) with a custom-built datalogger. This off-the-shelf IMS was developed for the detection of chemical warfare agents on the battlefield. After early evaluations of the AVM for hydrazine measurements showed a serious interference from ammonia, the AVM was modified to measure HZ and MMH in the ppb concentration range without interference from ammonia in the low ppm range. A description of the Hydrazine Monitor and how it functions is presented.

Cross, J. H.↗
NASA NTRS1990

Sulfur dioxide and its variations

UV spectroscopy from the Pioneer Venus Orbiter shows a decline in the cloud top abundance of SO2 from about 100 ppb to about 10 ppb in the period 1978-1986. A consistent decline in polar haze has occurred over the same period with the correlation coefficient between these two observables of 0.8. Star calibrations determine the instrument sensitivity to within 10 percent, which rules out the possibility that this is an instrumental effect. Systematic errors could increase the SO2 abundance to twice the inferred values in later orbits. Tracking of SO2 features and power spectral analysis give rotation periods for the longer lived features of 3.6-5.2 d, consistent with cloud tracked winds observed at other wavelengths. The behavior of SO2 and polar haze can be plausibly explained by episodic injection of SO2 into the cloud top regions, for example, by active volcanism.

Esposito, Larry W.↗
NASA NTRS1992

Rhenium-osmium isotope systematics in meteorites. I - Magmatic iron meteorite groups IIAB and IIIAB

Resonance ionization mass spectrometry is used to determine the Re and Os abundances by isotope dilution (ID) and to measure Os-187/Os-186 ratios from 19 iron meteorites. Abundances range from 1.4 to 4800 ppb Re, and from 13 to 65,000 ppb Os, and generally agree well with previous ID and neutron activation results. The Re and Os data suggest that abundance trends in these iron groups may be entirely explained by fractional crystallization. Whole-rock isochrons for the IIAB and IIIAB groups are statistically indistinguishable. Pooled data yield an initial Os-187/Os-186 of 0.794 +/- 0.010 Ga. Given the errors in the slope and half life, this age does not differ significantly from the canonical chondrite age of 4.56 Ga, but could be as young as 4.46 Ga.

Morgan, John W.↗
NASA NTRS1992

Catastrophic loss of stratospheric ozone in dense volcanic clouds

Rapid, localized loss of ozone is predicted to occur in the midlatitude and tropical stratosphere in the presence of very large concentrations of sulfate aerosols. Volcanic eruptions can increase the effective surface area of sulfuric acid so that heterogeneous reactions involving ClONO2, and secondarily N2O5, are able to suppress NO(x) abundances by more than a factor of 10 relative to gas phase chemistry. When NO(x) levels fall below a threshold, e.g., 0.6 ppb at 24 km in mid-latitudes, the chlorine-catalyzed loss of O3 proceeds at rates comparable to those during the formation of the Antarctic ozone hole, more than 50 ppb per day. If such losses occurred following the eruption of Mount Pinatubo in the most volcanically perturbed regions over the tropics and mid-latitudes, this model predicts that they are driven primarily by the suppression of NO(x) below these critical levels. The increase in stratospheric chlorine since El Chichon has made Mount Pinatubo more than twice as effective in causing rapid O3 loss.

Prather, Michael↗
NASA NTRS1993

Active Hydrazine Vapor Sampler (AHVS)

The Active Hydrazine Vapor Sampler (AHVS) was developed to detect vapors of hydrazine (HZ) and monomethylhydrazine (MMH) in air at parts-per-billion (ppb) concentration levels. The sampler consists of a commercial personal pump that draws ambient air through paper tape treated with vanillin (4-hydroxy-3-methoxybenzaldehyde). The paper tape is sandwiched in a thin cardboard housing inserted in one of the two specially designed holders to facilitate sampling. Contaminated air reacts with vanillin to develop a yellow color. The density of the color is proportional to the concentration of HZ or MMH. The AHVS can detect 10 ppb in less than 5 minutes. The sampler is easy to use, low cost, and intrinsically safe and contains no toxic material. It is most beneficial for use in locations with no laboratory capabilities for instrumentation calibration. This paper reviews the development, laboratory test, and field test of the device.

Young, Rebecca C.↗
NASA NTRS1993

Simulation of summertime ozone over North America

The concentrations of O3 and its precursors over North America are simulated for three summer months with a 3D, continental-scale photochemical model using meteorological input from the Goddard Institute for Space Studies (GISS) GCM. The model has 4 x 5 deg grid resolution and represents nonlinear chemistry in urban and industrial plumes with a subgrid nested scheme. Simulated median afternoon O3 concentrations at rural U.S. sites are within 5 ppb of observations in most cases, except in the south central U.S., where concentrations are overpredicted by 15-20 ppb. The model captures successfully the development of regional high-O3 episodes over the northeastern United States on the back side of weak, warm, stagnant anticyclones. Simulated concentrations of CO and nonmethane hydrocarbons are generally in good agreement with observations, concentrations of NO(x) are underpredicted by 10-30 percent, and concentrations of PANs are overpredicted by a factor of 2 to 3. The overprediction of PANs is attributed to flaws in the photochemical mechanism, including excessive production from oxidation of isoprene, and may also reflect an underestimate of PANs deposition. Subgrid nonlinear chemistry as captured by the nested plumes scheme decreases the net O3 production computed in the U.S. boundary layer by 8 percent on average.

Jacob, Daniel J.↗
NASA NTRS1993

Geochemical evidences for two chondritic-like cometary or asteroidal impacts before and at the K/T boundary

A number of geological and palaeontological evidences support multiple impacts of cometary showers within a short time (approximately 1-3 Ma) and their connection with mass extinctions. Observations include clustered crater ages, stratigraphic horizons of impact ejecta closely spaced in time, and evidence for stepwise mass extinctions spanning intervals of 1-3 Ma. For the K/T boundary, three candidates, Popigai, Manson, and Yucatan, have been proposed as impact craters. Two distinct strata at the K/T boundary in western North America have been interpreted as evidence for two sequential impacts. If multiple impacts occurred within a time span of about 1 Ma then multiple Ir enrichments should be observed. DSDP Hole 577B on the Shatsky Plateau in the northern Pacific at K/T time is the first site. Samples contain approximately greater than 97 percent CaCO3, which exhibit clear chemical signals associated with asteroidal/cometary impact. Ir, Fe, and Cr data are presented. From the Th-normalized data, two satellite peaks below the major peak at 78 cm and 81 cm of 577B-1-4 are clearly shown. The major Ir peak (K/T boundary) is at 72 cm. Fe and Cr, from C1-like impactor ejecta fallout, also show two peaks at the same positions. For hole 738C on the southern Kerguelen Plateau, Ir values reach a peak concentration of 18 ppb in the clay layer at 96.0-96.2 cm in section 20R-5, and gradually tail off. In the sample 115 cm above the boundary, Ir concentrations have still not reached background levels. From the Ir peak downward to the lowermost sample analyzed at 102 cm, the Ir concentration is still as high as 1.7 ppb. From the Th-normalized data, we observe a small Ir/Th peak at 100-101 cm. Though this peak is within the error margin, the trend is clear. Fe and Cr exhibit the same pattern. The third case is Hole 690C on the Queen Maud Ridge. Again, the Ir/Th plot indicates the strong possibility of satellite peaks at approximately 52 cm. The main peak is at 39-40 cm. For the Stevns Klint K/T boundary layers, the stratification of trace elements appears threefold with peak concentrations in sublayers A1, A3, and B2 for different element groups, including Ir. C1 ratios for many siderophile elements found in combined layers III and IV, corresponding to layers A, B, C, and D, strongly support the impact hypothesis. Also, multiple Ir anomalies in the K/T section at Lattengebirge, Bavarian Alps are reported. Recent works on Ni-rich spinels and Ir at the K/T boundaries clearly establish cometary/asteroidal impacts at the K/T boundary. Lastly, cometary showers can explain the enhanced Ir contents over approximately a 1 Ma interval in Gubbio shales.

Liu, Y.-G.↗
NASA NTRS1994

A new material for removing heavy metals from water

The NASA Lewis Research Center developed and is patenting a new high capacity ion exchange material (IEM) that removes toxic metals from contaminated water in laboratory tests. The IEM can be made into many forms, such as thin films, coatings, pellets, and fibers. As a result, it can be adapted to many applications to purify contaminated water wherever it is found, be it in waste water treatment systems, lakes, ponds, industrial plants, or in homes. Laboratory tests have been conducted on aqueous solutions containing only one of the following metal cations: lead, copper, mercury, cadmium, silver, chromium (III), nickel, zinc, and yttrium. Tests were also conducted with: (1) calcium present to determine its effects on the uptake of cadmium and copper, and (2) uranium and lanthanides which are stand-ins for other radioactive elements, (3) drinking water for the removal of copper and lead, and (3) others compositions. The results revealed that the IEM removes all these cations, even in the presence of the calcium. Of particular interest are the results of the tests with the drinking water: the lead concentration was reduced from 142 ppb down to 2.8 ppb (well below the accepted EPA standard).

Philipp, Warren H., Jr.↗
NASA NTRS1994

Measurements of the vertical profile, diurnal variation, and secular change of ClO in the stratosphere over Thule, Greenland, February-March, 1992

We report observations of stratospheric chlorine monoxide over the altitude range approx. 16 to 50 km at Thule, Greenland from Feb. 8 to Mar. 24, 1992. A new, more sensitive ground-based mm-wave spectrometer was employed for these measurements, similar in principle to that used earlier for the discovery of low altitude ClO in the Antarctic springtime. In this report, we discuss different aspects of vertical distribution, secular trends, and diurnal variation of ClO in the Arctic stratosphere, based on a preliminary analysis of our Thule data. We see no evidence for large (approx. 1.2-1.5 ppb) amounts of ClO in the lower stratosphere at any time during February or March, in agreement with UARS-MLS findings for this period, and in marked contrast to findings reported for the Arctic in January. We have some evidence for small enhancements (approx. 0.2-0.5 ppb) in the 18-30 km range in late February-early March, which might be associated with volcanic aerosol, rather than PSC, processing.

Dezafra, Robert L.↗
NASA NTRS1994

Reevaluation of the NOAA/CMDL carbon monoxide reference scale and comparisons with CO reference gases at NASA-Langley and the Fraunhofer Institut

The carbon monoxide (CO) reference scale created by the National Oceanic and Atmospheric Administration/Climate Monitoring and Diagnostics Laboratory (NOAA/CMDL) is used to quantify measurements of CO in the atmosphere, calibrate standards of other laboratories and to otherwise provide reference gases to the community measuring atmospheric CO. This reference scale was created based upon a set of primary standards prepared by gravimetric methods at CMDL and has been propagated to a set of working standards. In this paper we compare CO mixing ratios assigned to the working standards by three approaches: (1) calibration against the original gravimetric standards, (2) calibration using only working standards as the reference gas, and (3) calibration against three new gravimetric standards prepared to CMDL. The agreement between these values was typically better than 1%. The calibration histories of CMDL working standards are reviewed with respect to expected rates of CO change in the atmosphere. Using a Monte Carlo approach to simulate the effect of drifting standards on calculated mixing ratios, we conclude that the error solely associated with the maintenance of standards will limit the ability to detect small CO changes in the atmosphere. We also report results of intercalibration experiments conducted between CMDL and the Diode Laser Sensor Group (DACOM) at the NASA Langley Research Center (Hampton, Virginia), and CMDL and the Fraunhofer-Institut (Garmisch-Partenkirchen, Germany). Each laboratory calibrated several working standards for CO using their reference gases, and these results were compared to calibrations conducted by CMDL. The intercomparison of eight standards (CO concentrations between approximately 100 and approximately 165 ppb) by CMDL and NASA agreed to better than +/- 2%. The calibration of six standards (CO concentrations between approximately 50 and approximately 210 ppb) by CMDL and the Fraunhofer-Institut agreed to within +/- 2% for four standards, and to within +/- 5% for all six standards.

Novelli, P. C.↗
NASA NTRS1995

Sensing strategies for toxic vapor detection

This work was motivated by the recommendations of the American Conference of Governmental Industrial Hygienists (ACGIH) that threshold limits for hydrazine, H2N-NH2 in air be lowered from 100 to 10 parts-per-billion (ppb) concentration levels. Hydrazine is one of the high-energy propellants used in large volumes in Space Shuttle, Titan, payloads, and other aerospace operations. Since analytical methods presently available for hydrazine detection and/or determination do not satisfy such low levels of detection, the ultimate goal of this research is the development and characterization of a portable and compact chemical sensor ideally capable to detect (in real time) 1 ppb of hydrazine, continuously and reversibly. The laboratory prototype developed as part of this project is comprised of: (1) a reactor part in which H2N-NH2 reacts, generating chemiluminescence emission, with tris(2,2'-bipyridine)ruthenium(III), which is immobilized on an ion-exchange polymeric materials of a perfluorinated hydrocarbon containing sulfonate groups as exchange centers (Nafion); (2) an electrochemical three-electrode cell posed at a potential at which the immobilized ruthenium complex could be reoxidized to the 3-oxidation state (as to provide reversible and continuous detection); and (3) a low power consumption photomultiplier tube to collect and quantitatively integrate the emitted photons with the help of auxiliary electronics and readout device.

Mottola, Horacio A.↗