Search NASA⌕ Search

SEARCH · Search NASA

Results for “Atmosphere/chemistry”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS2003

Termolecular ion-molecule reactions in Titan's atmosphere. IV. A search made at up to 1 micron in pure hydrocarbons

The results of a study of ion-molecule reactions occurring in pure methane, acetylene, ethylene, ethane, propyne, propene, propane, and diacetylene at pressures up to 40 microns of pressure are reported. A variety of experimental methods are used: The standard double resonance in an ICR, for determination of the precursor ions and the modulated double resonance ejection in an ICR, for the determination of the daughter ions. The FA-SIFT technique was used for validation and examination of termolecular reactions with rate coefficients that are less than 10(-26) cm(6) s(-1). An extensive database of reaction kinetics already exists for many of these reactions. The main point of this study was the determination of the accuracy of this database and to search for any missing reactions and reaction channels that may have been omitted from earlier investigations. A specific objective of this work was to extend the study to the highest pressures possible to find out if there were any important termolecular reaction channels occurring. A new approach was used here. In the pure hydrocarbon gases the mass spectra were followed as a function of the pressure changes of the gas. An initial guess was first made using the current literature as a source of the reaction kinetics that were expected. A model of the ion abundances was produced from the solution of the partial differential equations in terms of reaction rate coefficients and initial abundances. The experimental data was fitted to the model for all of the pressures by a least squares minimization to the reaction rate coefficients and initial abundances. The reaction rate coefficients obtained from the model were then compared to the literature values. Several new channels and reactions were discovered when the modeled fits were compared to the actual data. This is all explained in the text and the implications of these results are discussed for the Titan atmosphere.

Hydrocarbons, Acyclic/analysis↗
NASA NTRS2002

13CO2/12CO2 isotopic ratio measurements using a difference frequency-based sensor operating at 4.35 micrometers

A portable modular gas sensor for measuring the 13C/12C isotopic ratio in CO2 with a precision of 0.8%(+/-1 sigma) was developed for volcanic gas emission studies. This sensor employed a difference frequency generation (DFG)-based spectroscopic source operating at 4.35 micrometers (approximately 2300 cm-1) in combination with a dual-chamber gas absorption cell. Direct absorption spectroscopy using this specially designed cell permitted rapid comparisons of isotopic ratios of a gas sample and a reference standard for appropriately selected CO2 absorption lines. Special attention was given to minimizing undesirable precision degrading effects, in particular temperature and pressure fluctuations.

NASA Discipline Life Sciences Technologies↗
NASA NTRS2002

Chemical sensing with pulsed QC-DFB lasers operating at 15.6 micrometers

Pulsed thermoelectrically cooled QC-DFB lasers operating at 15.6 micrometers were characterized for spectroscopic gas sensing applications. A new method for wavelength scanning based on repetition rate modulation was developed. A non-wavelength-selective pyroelectric detector was incorporated in the sensor configuration giving the advantage of room-temperature operation and low cost. Absorption lines of CO2 and H2O were observed in ambient air, providing information about the concentration of these species.

NASA Discipline Life Sciences Technologies↗
NASA NTRS2001

Ambient formaldehyde detection with a laser spectrometer based on difference-frequency generation in PPLN

A laser spectrometer based on difference-frequency generation in periodically poled LiNbO3 (PPLN) has been used to quantify atmospheric formaldehyde with a detection limit of 0.32 parts per billion in a given volume (ppbV) using specifically developed data-processing techniques. With state-of-the-art fiber-coupled diode-laser pump sources at 1083 nm and 1561 nm, difference-frequency radiation has been generated in the 3.53-micrometers (2832-cm-1) spectral region. Formaldehyde in ambient air in the 1- to 10-ppb V range has been detected continuously for nine and five days at two separate field sites in the Greater Houston area operated by the Texas Natural Resource Conservation Commission (TNRCC) and the Houston Regional Monitoring Corporation (HRM). The acquired spectroscopic data are compared with results obtained by a well-established wet-chemical o-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine (PFBHA) technique.

NASA Discipline Life Sciences Technologies↗
NASA NTRS2000

Field intercomparison of a novel optical sensor for formaldehyde quantification

A one-week in situ intercomparison campaign was completed on the Rice University campus for measuring HCHO using three different techniques, including a novel optical sensor based on difference frequency generation (DFG) operating at room temperature. Two chemical derivatization methods, 2,4-dinitrophenylhydrazine (DNPH) and o-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine (PFBHA), were deployed during the daylight hours for three- to four-hour time-integrated samples. A real-time optical sensor based on laser absorption spectroscopy was operated simultaneously, including nighttime hours. This tunable spectroscopic source based on difference frequency mixing of two fiber-amplified diode lasers in periodically poled LiNb03 (PPLN) was operated at 3.5315 micrometers (2831.64 cm 1) to access a strong HCHO ro-vibrational transition free of interferences from other species. The results showed a bias of -1.7 and -1.2 ppbv and a gross error of 2.6 and 1.5 ppbv for DNPH and PFBHA measurements, respectively, compared with DFG measurements. These results validate the DFG sensor for time-resolved measurements of HCHO in urban areas.

NASA Discipline Life Sciences Technologies↗
NASA NTRS2000

Difference-frequency-based tunable absorption spectrometer for detection of atmospheric formaldehyde

High-sensitivity detection of formaldehyde (CH2O) at 3.5315 micrometers (2831.64 cm-1) is reported with a diode-laser-pumped, fiber-coupled, periodically poled LiNbO3 spectroscopic source. This source replaced the Pb-salt diode laser Dewar assembly of an existing tunable diode-laser absorption spectrometer designed for ultrasensitive detection of CH2O. Spectra are recorded with 2f-modulation spectroscopy and zero-air rapid background subtraction. Initial measurements reported here, determined from multiple measurements of a flowing 7.7 parts per billion by volume (ppbv, parts in 10(9)) CH2O in air mixture, indicate replicate precisions as low as 0.24 ppbv.

Non-NASA Center↗
NASA NTRS2000

On the origin of Titan's atmosphere

The present atmosphere of Titan exhibits evidence of extensive evolution, in the form of rapid photochemical destruction of methane and a large fractionation of the nitrogen and oxygen isotopes. Attempts to recover the initial inventory of volatiles lead toward a model in which nitrogen was originally supplied as NH3, essentially unmodified from its relative abundance in the outer solar nebula. Titan's atmospheric methane, in contrast, appears to have been formed from carbon and other carbon compounds, either by gas phase reactions in the subnebula or by accretional heating during the formation of Titan. These conclusions can be tested by further studies of abundances and isotope ratios in Titan's atmosphere, augmented by studies of comets. The possible similarity of carbon and nitrogen inventories on Titan to those on the inner planets makes this investigation particularly intriguing.

Non-NASA Center↗
NASA NTRS2000

The ultraviolet environment of Mars: biological implications past, present, and future

A radiative transfer model is used to quantitatively investigate aspects of the martian ultraviolet radiation environment, past and present. Biological action spectra for DNA inactivation and chloroplast (photosystem) inhibition are used to estimate biologically effective irradiances for the martian surface under cloudless skies. Over time Mars has probably experienced an increasingly inhospitable photobiological environment, with present instantaneous DNA weighted irradiances 3.5-fold higher than they may have been on early Mars. This is in contrast to the surface of Earth, which experienced an ozone amelioration of the photobiological environment during the Proterozoic and now has DNA weighted irradiances almost three orders of magnitude lower than early Earth. Although the present-day martian UV flux is similar to that of early Earth and thus may not be a critical limitation to life in the evolutionary context, it is a constraint to an unadapted biota and will rapidly kill spacecraft-borne microbes not covered by a martian dust layer. Microbial strategies for protection against UV radiation are considered in the light of martian photobiological calculations, past and present. Data are also presented for the effects of hypothetical planetary atmospheric manipulations on the martian UV radiation environment with estimates of the biological consequences of such manipulations.

NASA Center ARC↗
NASA NTRS2000

Life associated with a 2.76 Ga ephemeral pond?: evidence from Mount Roe #2 paleosol

Dark sericitic material at and near the top of the 2.765 +/- 0.01 Ga Mount Roe #2 paleosol in Western Australia contains 0.05-0.10 wt% organic carbon with delta 13C values between -33% and -51% PDB (Peedee belemnite). Such negative isotopic values strongly indicate that methanotrophs once inhabited this material. The textures and the chemical composition of the dark sericitic material indicate that the methanotrophs lived in or at the edges of ephemeral ponds, that these ponds became desiccated, and that heavy rains transported the material to its present sites. The discovery of methanotrophs associated with the Mount Roe #2 paleosol may extend their geologic record on land by at least 1.5 b.y. Methanotrophy in this setting is consistent with the notion that atmospheric methane levels were > or = 20 (mu)atm during the Late Archean. The radiative forcing due to such high atmospheric methane levels could have compensated for the faint younger sun and helped to prevent massive glaciation during the Late Archean.

Non-NASA Center↗
NASA NTRS2000

Geology and geochemistry of paleosols developed on the Hekpoort Basalt, Pretoria Group, South Africa

The Hekpoort paleosols comprise a regional paleoweathering horizon developed on 2.224 +/- 0.021 Ga basaltic andesite lavas at the top of the Hekpoort Formation of the Pretoria Group, Transvaal Supergroup, South Africa. In five separate profiles, from outcrops along road cuts near Waterval Onder and the Daspoort Tunnel and in three drill cores from the Bank Break Area (BB3, BB8, and BB14), the top of the paleosol is a sericite-rich zone. The sericite zone grades downward into a chlorite-rich zone. In core BB8 and in the road cut at the Daspoort Tunnel, we sampled the underlying or parent basaltic andesite into which the chlorite zone grades. We did not obtain samples of the parent material at Waterval Onder and in cores BB3 and BB14, but chemical analyses indicate that the chlorite and sericite zones in these profiles derive from underlying lavas similar to the ones we sampled in core BB8 and at the Daspoort Tunnel. The presence of apparent rip-up clasts of the paleosol in the overlying ironstones of the Strubenkop Formation in the cores from Bank Break makes it very unlikely that most of the alteration was a result of interactions with hydrothermal fluids. Desiccation cracks at the top of the paleosol that were filled with sand during the deposition of the overlying sediments at Waterval Onder point to a subaerial weathering origin. Very little, if any, Al, Ti, Zr, V, or Cr moved a discernible distance during weathering of any of the five profiles. The vertical distribution of Fe, Mg, Mn, Ni, and Co indicates that these elements were largely removed from the top of the soil during weathering. The overall abundance of these elements in each of the profiles indicates that a significant fraction of the complement lost from the top subsequently reprecipitated in the lower portion of the soil as constituents of an Fe2(+) -rich smectite. The loss of Fe from the top of the soil during weathering of the Hekpoort paleosols indicates that atmospheric PO2 was less than 8 x 10(-4) atm about 2.22 Ga. Fe2(+) -rich smectite should only precipitate during soil formation if atmospheric PCO2 is less than or equal to 2 x 10(-2) atm (Rye, Kuo, and Holland, 1995). Ca and Na were largely lost during weathering. Some Na was apparently added to the sericite zone in cores BB3, BB8, and BB14 after weathering. All five profiles are enriched in K and Rb, and most are enriched in Ba. The distribution of these elements indicates that they all were added during post-weathering hydrothermal metasomatism. Rb-Sr analysis of the paleosol at the Daspoort Tunnel indicates that metasomatism last affected that profile 1.925 +/- 0.032 Ga (Macfarlane and Holland, 1991).

Non-NASA Center↗
NASA NTRS1999

Methane concentration and isotopic composition measurements with a mid-infrared quantum-cascade laser

A quantum-cascade laser operating at a wavelength of 8.1 micrometers was used for high-sensitivity absorption spectroscopy of methane (CH4). The laser frequency was continuously scanned with current over more than 3 cm-1, and absorption spectra of the CH4 nu 4 P branch were recorded. The measured laser linewidth was 50 MHz. A CH4 concentration of 15.6 parts in 10(6) ( ppm) in 50 Torr of air was measured in a 43-cm path length with +/- 0.5-ppm accuracy when the signal was averaged over 400 scans. The minimum detectable absorption in such direct absorption measurements is estimated to be 1.1 x 10(-4). The content of 13CH4 and CH3D species in a CH4 sample was determined.

Non-NASA Center↗
NASA NTRS1987

Atmospheric H2O2 measurement: comparison of cold trap method with impinger bubbling method

Collection of atmospheric H2O2 was performed by a cold trap method using dry ice-acetone as the refrigerant. The air was drawn by a pump into a glass gas trap immersed in the dry ice-acetone slush in a dewar flask at a flow rate of 2.5 l min-1 for approximately 2 h. Collection efficiency was > 99% and negligible interferences by O3, SO2 or organic matter with the collected H2O2 in the trap were observed. This method was compared with the air impinger bubbling method which has been previously described (Kok et al., 1978a, b, Envir. Sci. Technol. 12, 1072-1080). The measured total peroxide (H2O2 + organic peroxide) values in a series of aim samples collected by the impinger bubbling method (0.06-3.7 ppb) were always higher than those obtained by the cold trap method (0.02-1.2 ppb). Laboratory experiments suggest that the difference in values between the two methods probably results from the aqueous phase generation of H2O2 and organic peroxide in the impinger solution by a reaction of atmospheric O3 with olefinic and aromatic compounds. If these O3-organic compound reactions which occur in the impinger also occur in aqueous droplets in the atmosphere, the process could be very important for aqueous phase generation of H2O2 in clouds and rainwater.

NASA Discipline Exobiology↗
NASA NTRS1987

Theoretical constraints on oxygen and carbon dioxide concentrations in the Precambrian atmosphere

Simple (one-dimensional) climate models suggest that carbon dioxide concentrations during the Archean must have been at least 100-1000 times the present level to keep the Earth's surface temperature above freezing in the face of decreased solar luminosity. Such models provide only lower bounds on CO2, so it is possible that CO2 levels were substantially higher than this and that the Archean climate was much warmer than today. Periods of extensive glaciation during the early and late Proterozoic, on the other hand, indicate that the climate at these times was relatively cool. To be consistent with climate models CO2 partial pressures must have declined from approximately 0.03 to 0.3 bar around 2.5 Ga ago to between 10(-3) and 10(-2) bar at 0.8 Ga ago. This steep decrease in carbon dioxide concentrations may be inconsistent with paleosol data, which implies that pCO2 did not change appreciably during that time. Oxygen was essentially absent from the Earth's atmosphere and oceans prior to the emergence of a photosynthetic source, probably during the late Archean. During the early Proterozoic the atmosphere and surface ocean were apparently oxidizing, while the deep ocean remained reducing. An upper limit of 6 x 10(-3) bar for pO2 at this time can be derived by balancing the burial rate of organic carbon with the rate of oxidation of ferrous iron in the deep ocean. The establishment of oxidizing conditions in the deep ocean, marked by the disappearance of banded iron formations approximately 1.7 Ga ago, permitted atmospheric oxygen to climb to its present level. O2 concentrations may have remained substantially lower than today, however, until well into the Phanerozoic.

Review, Tutorial↗
NASA NTRS1986

Amino acids derived from Titan tholins

An organic heteropolymer (Titan tholin) was produced by continuous dc discharge through a 0.9 N2/0.1 CH4 gas mixture at 0.2 mbar pressure, roughly simulating the cloudtop atmosphere of Titan. Treatment of this tholin with 6N HCl yielded 16 amino acids by gas chromatography after derivatization of N-trifluroacetyl isopropyl esters on two different capillary columns. Identifications were confirmed by GC/MS. Glycine, aspartic acid, and alpha- and beta-alanine were produced in greatest abundance; the total yield of amino acids was approximately 10(-2), approximately equal to the yield of urea. The presence of "nonbiological" amino acids, the absence of serine, and the fact that the amino acids are racemic within experimental error together indicate that these molecules are not due to microbial or other contamination, but are derived from the tholin. In addition to the HCN, HC2CN, and (CN)2 found by Voyager, nitriles and aminonitriles should be sought in the Titanian atmosphere and, eventually, amino acids on the surface. These results suggest that episodes of liquid water in the past or future of Titan might lead to major further steps in prebiological organic chemistry on that body.

Non-NASA Center↗
NASA NTRS1997

Temperature lapse rate and methane in Titan's troposphere

We have reanalyzed the Voyager radio occultation data for Titan, examining two alternative approaches to methane condensation. In one approach, methane condensation is facilitated by the presence of nitrogen because nitrogen lowers the condensation level of a methane/nitrogen mixture. The resulting enhancement in methane condensation lowers the upper limit on surface relative humidity of methane obtained from the Voyager occultation data from 0.7 to 0.6. We conclude that in this case the surface relative humidity of methane lies between 0.08 and 0.6, with values close to 0.6 indicated. In the other approach, methane is allowed to become supersaturated and reaches 1.4 times saturation in the troposphere. In this case, surface humidities up to 100% are allowed by the Voyager occultation data, and thus the upper limit must be set by other considerations. We conclude that if supersaturation is included, then the surface relative humidity of methane can be any value greater than 0.08--unless a deep ocean is present, in which case the surface relative humidity is limited to less than 0.85. Again, values close to 0.6 are indicated. Overall, the tropospheric lapse rate on Titan appears to be determined by radiative equilibrium. The lapse rate is everywhere stable against dry convection, but is unstable to moist convection. This finding is consistent with a supersaturated atmosphere in which condensation-and hence moist convection-is inhibited.

Methane/analysis↗
NASA NTRS1997

CO2 greenhouse in the early martian atmosphere: SO2 inhibits condensation

Many investigators of the early martian climate have suggested that a dense carbon dioxide atmosphere was present and warmed the surface above the melting point of water (J.B. Pollack, J.F. Kasting, S.M. Richardson, and K. Poliakoff 1987. Icarus 71, 203-224). However, J.F. Kasting (1991. Icarus 94, 1-13) pointed out that previous thermal models of the primitive martian atmosphere had not considered the condensation of CO2. When this effect was incorporated, Kasting found that CO2 by itself is inadequate to warm the surface. SO2 absorbs strongly in the near UV region of the solar spectrum. While a small amount of SO2 may have a negligible effect by itself on the surface temperature, it may have significantly warmed the middle atmosphere of early Mars, much as ozone warms the terrestrial stratosphere today. If this region is kept warm enough to inhibit the condensation of CO2, then CO2 remains a viable greenhouse gas. Our preliminary radiative modeling shows that the addition of 0.1 ppmv of SO2 in a 2 bar CO2 atmosphere raises the temperature of the middle atmosphere by approximately 10 degrees, so that the upper atmosphere in a 1 D model remains above the condensation temperature of CO2. In addition, this amount of SO2 in the atmosphere provides an effective UV shield for a hypothetical biosphere on the martian surface.

NASA Discipline Exobiology↗
NASA NTRS1997

Carbon dioxide warming of the early Earth

Svante Arrhenius' research in atmospheric physics extended beyond the recent past and the near future states of the Earth, which today are at the center of sociopolitical attention. His plan encompassed all of the physical phenomena known at the time to relate to the formation and evolution of stars and planets. His two-volume textbook on cosmic physics is a comprehensive synopsis of the field. The inquiry into the possible cause of the ice ages and the theory of selective wavelength filter control led Arrhenius to consider the surface states of the other terrestrial planets, and of the ancient Earth before it had been modified by the emergence of life. The rapid escape of hydrogen and the equilibration with igneous rocks required that carbon in the early atmosphere prevailed mainly in oxidized form as carbon dioxide, together with other photoactive gases exerting a greenhouse effect orders of magnitude larger than in our present atmosphere. This effect, together with the ensuing chemical processes, would have set the conditions for life to evolve on our planet, seeded from spores spreading through an infinite Universe, and propelled, as Arrhenius thought, by stellar radiation pressure.

NASA Discipline Exobiology↗
NASA NTRS1997

Habitable planets with high obliquities

Earth's obliquity would vary chaotically from 0 degrees to 85 degrees were it not for the presence of the Moon (J. Laskar, F. Joutel, and P. Robutel, 1993, Nature 361, 615-617). The Moon itself is thought to be an accident of accretion, formed by a glancing blow from a Mars-sized planetesimal. Hence, planets with similar moons and stable obliquities may be extremely rare. This has lead Laskar and colleagues to suggest that the number of Earth-like planets with high obliquities and temperate, life-supporting climates may be small. To test this proposition, we have used an energy-balance climate model to simulate Earth's climate at obliquities up to 90 degrees. We show that Earth's climate would become regionally severe in such circumstances, with large seasonal cycles and accompanying temperature extremes on middle- and high-latitude continents which might be damaging to many forms of life. The response of other, hypothetical, Earth-like planets to large obliquity fluctuations depends on their land-sea distribution and on their position within the habitable zone (HZ) around their star. Planets with several modest-sized continents or equatorial supercontinents are more climatically stable than those with polar supercontinents. Planets farther out in the HZ are less affected by high obliquities because their atmospheres should accumulate CO2 in response to the carbonate-silicate cycle. Dense, CO2-rich atmospheres transport heat very effectively and therefore limit the magnitude of both seasonal cycles and latitudinal temperature gradients. We conclude that a significant fraction of extrasolar Earth-like planets may still be habitable, even if they are subject to large obliquity fluctuations.

NASA Discipline Exobiology↗