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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
NASA NTRS1999

Permeation Resistance of Chlorinated Polyethylene Against Hydrazine Fuels

The permeation resistance of chlorinated polyethylene (CPE) used in chemical protective clothing against the aerospace fuels hydrazine, monomethylhydrazine (MMH), and uns-dimethylhydrazine (UDMH) was determined by measuring breakthrough times and time-averaged vapor transmission rates using an ASTM F 739 permeation cell. Two exposure scenarios were simulated: a 2 hour (h) fuel vapor exposure, and a liquid fuel "splash" followed by a 2 h vapor exposure. To simulate internal suit pressure during operation, a positive differential pressure of 0.3 in. water (75 Pa) on the collection side of the permeation apparatus was used. Breakthrough was observed after exposure to liquid MMH, and to vapor and liquid UDMH. No breakthrough was observed after exposure to vapor and liquid hydrazine, or vapor MMH. A model was then used to calculate propellant concentrations inside a totally encapsulating chemical protective suit based on the ASTM permeation data obtained in the present study. Concentrations were calculated under conditions of fixed vapor transmission rate, variable breathing air flow rate, and variable splash exposure area. Calculations showed that the maximum allowable permeation rates of hydrazine fuels through CPE were of the order of 0.05 to 0.08 ng sq cm/min for encapsulating suits with low breathing air flow rates (of the order of 5 scfm or 140 L/min). Above these permeation rates, the 10 parts per billion (ppb) threshold limit value time - weighted average could be exceeded for chemical protective suits having a CPE torso. To evaluate suit performance at ppb level concentrations, use of a sensitive analytical method such as cation exchange high performance liquid chromatography with amperometric detection was found to be essential.

Waller, J. M.↗
NASA NTRS1971

Phenol Analysis -- Some Analytical Considerations

Contamination of potable water supplies with halogenated phenols in concentrations of 2-10 parts per billion (ppb) produces objectionable tastes and odors capable of influencing consumer acceptability. Routine analysis by the distillation/ 4-aminoantipyrine method is limited by lack of sensitivity and subject to interference by aryl amines. This has been overcome by developing a continuous liquid-liquid extraction system to selectively isolate phenols and eliminate major interfering substances. Stable reagents have been formulated to reduce blank color and extend sensitivity. Equipment suitable for analysis of phenols at the 1 ppb level or less in 20 minutes is described.

Starkey, R. J., Jr.↗
NASA NTRS1999

Sensitive Procedures for Determining the Permeation Resistance of Chlorinated Polyethylene Against Liquid Propellants

The permeation resistance of chlorinated polyethylene (CPE) used in totally encapsulating chemical protective suits against the aerospace fuels hydrazine, monomethylhydrazine, and uns-dimethylhydrazine was determined by measuring the breakthrough time (BT) and time-averaged vapor transmission rate (VTR) using procedures consistent with ASTM F 739 and ASTM F 1383. Two exposure scenarios were simulated: a 2 hour (h) fuel vapor exposure, and a liquid fuel "splash" followed by a 2 h vapor exposure. To simulate internal suit pressure during operation, a positive differential pressure of 0.3 in. water (75 Pa) on the collection side of the permeation apparatus was used. Using the available data, a model was developed to estimate propellant concentrations inside an air-line fed, totally encapsulating chemical protective suit. Concentrations were calculated under simulated conditions of fixed vapor transmission rate, variable breathing air flow rate, and variable splash exposure area. Calculations showed that the maximum allowable permeation rates of hydrazine fuels through CPE were of the order of 0.05 to 0.08 ng/sq cm min for encapsulating suits with low breathing air flow rates (of the order of 5 scfm or 140 L min-1). Above these permeation rates, the 10 parts-per-billion (ppb) threshold limit value time-weighted average could be exceeded. To evaluate suit performance at 10 ppb threshold-limiting value/time-weighted average level concentrations, use of a sensitive analytical method such as cation exchange high performance liquid chromatography with amperometric detection was found to be essential. The analytical detection limit determines the lowest measurable VTR, which in turn governed the lowest per meant concentration that could be calculated inside the totally encapsulating chemical protective suit.

Waller, Jess M.↗
NASA NTRS2000

On the Relationship of Multiple Solutions in Tropospheric Photochemistry to Observable Phenomena

Multiple steady-state solutions are a fairly robust feature of simplified models of tropospheric photochemistry and have been reported for a range of different modeling assumptions. Multiple solutions occur through a bifurcation as changes in a control parameter induce a transition from low to high NO(x) conditions. The usual control parameters are the sources of NO and of CO, CH4 or non-methane hydrocarbons. Typically, with increasing NO source, bifurcations occur at NO(x). concentrations that are higher than would be expected of even heavily polluted conditions. However, there are other ways of inducing a low NO(x) - high NO(x) transition. In this paper the primary control parameter is solar zenith angle. This is varied throughout the year by computing noontime steady states on successive days. Background NO(x), varied by assuming different NO(x) sources values, is used as a secondary control parameter. It is found that bifurcations can occur from high to low NO(x) conditions, for reasonable background NO(x) levels, as the model progresses through spring and then from low to high NO,, during the progression through fall. A time dependent version of this model has been run for the same parameter values as in the steady state runs. This shows rapid spring and fall transitions between high and low NO(x) states. H2O2, for example, rises from sub-ppb levels to about 2 ppb over a five day period in spring and declines quickly, but less precipitously, in fall. This study supports the suggestions that the rapid change in peroxide concentrations between summer and winter conditions may be understood as a manifestation of different underlying steady-state behavior.

Stewart, Richard W.↗
NASA NTRS2001

Measurements of an Anomalous Global Methane Increase During 1998

Measurements of atmospheric methane from a globally distributed network of air sampling sites indicate that the globally averaged CH4 growth rate increased from an average of 3.9 ppb/yr during 1995-1997 to 12.7 +/- 0.6 ppb in 1998. The global growth rate then decreased to 2.6 +/- 0.6 ppb during 1999, indicating that the large increase in 1998 was an anomaly and not a return to the larger growth rates observed during the late 1970s and early 1980s. The increased growth rate represents an anomalous increase in the imbalance between CH4 sources and sinks equal to approximately 24 Tg CH4 during 1998. Wetlands and boreal biomass burning are sources that may have contributed to the anomaly. During 1998, the globally averaged temperature anomaly was +0.67 C, the largest temperature anomaly in the modern record. A regression model based on temperature and precipitation anomalies was used to calculate emission anomalies of 11.6 Tg CH4 from wetlands north of 30 N and 13 Tg CH4 for tropical wetlands during 1998 compared to average emissions calculated for 1982-1993. In 1999, calculated wetland emission anomalies were negative for high northern latitudes and the tropics, contributing to the low growth rate observed in 1999. Also 1998 was a severe fire year in boreal regions where approximately 1.3x10(exp 5) sq km of forest and peat land burned releasing an estimated 5.7 Tg CH4

Dlugokencky, E. J.↗
NASA NTRS1997

Upper Tropospheric/Lower Stratospheric Distribution of Reactive Nitrogen and Ozone

In-situ measurements of a large number of trace chemicals from upper troposphere/lower stratosphere (UT/LS) were performed with the NASA DC-8 aircraft during February/March 1994 over the Pacific Ocean (10 S to 60 N). Mixing ratios in the UT were relatively low in the warm tropical and subtropical air south of the polar jetstream (approx. =28 N) but increased sharply with latitude in the cold polar air north of the jetstream. At about 45 N, high concentrations of PAN (300 ppt) coexisted with extremely low (approx. = 20 ppt) concentrations of NOx. Elevated NOx levels in the UT did not always correspond to continental outflow conditions. Deepest penetrations into the stratosphere (550 ppb O3, 279 ppb NOx, and 350 K potential temperature) corresponded to a region that has been defined as the 'lowermost stratosphere' (LS) by Holton et al. Analysis of data shows that the mixing ratios of long-lived tracer species (e.g., CH4, HNO3, NOy, CFCs, HCFCs) are linearly correlated with those of O3 and N2O. A delta-NOY/delta-O3 of 0.0054 ppb/ppb and delta-NOy/delta-N2O of -0.081 ppb/ppb is in good agreement with other reported measurements from the DC-8. These slopes are however, somewhat steeper than those reported from the ER-2 studies. We find that the reactive nitrogen budget in the UT/LS is largely balanced with shortfalls that are no greater than 15%. A number of oxygenated species (e.g., acetone, H2O2) are present and may provide an important in-situ source of HOx in the UT/LS region.

Singh, H. S.↗
NASA NTRS2001

Electronic Nose: Evaluation of Kamina Prototype Unit

The Kamina, Sam and Cyranose electronic nose systems were evaluated and partially trained. Much work was performed on the Kamina as it has the ability to respond to low (less than 10 ppb) concentrations of hydrazine compounds. We were able to tell the difference between Hydrazine (Hz) and Monomethylhydrazine (MMH) in standard clean humid air. We were able to detect MMH in reduced pressure (1/3 atm) at about 250 ppb, however the training set was to far from the real situation to be useful now. Various engineering and usability aspects of both the noses was noted, especially the software. One serious physical engineering flaw was remedied in the Kamina system. A gas flow manifold was created for the Sam system. Different chips were evaluated for the Kamina system. It is still unclear if they can be exchanged without retraining the software.The Sam Detect commercial unit was evaluated for solvent detection and evaluation. It was able to successfully identify some solvents. The Cyranose, was observed and evaluated for two days. It has the ability to detect gasses in the 100 parts per million level but not the 10 parts per billion level. It is very sensitive to humidity changes; there is software to partially handle this.

Schattke, Nathan↗
NASA NTRS2002

Geodetic Results from Mark 4 VLBI

We present geodetic results of a series of 30 VLBI experiments recorded in Mark 4 mode at rates of 128 and 256 Mbps. The formal uncertainties of UT1, polar motion, and nutation offsets derived from these experiments are better than the corresponding uncertainties from NEOS-A experiments by a factor of 1.3-2. Baseline length repeatability for the series of 32 experiments over a period of one year is about 0.9 ppb. For comparison, NEOS-A length repeatability is about 1.4 ppb. We will discuss optimal use of Mark 4 in the design of future observing networks.

MacMillan, Daniel↗
NASA NTRS2003

Tropospheric Ozone Over the North Pacific from Ozonesdonde Observations

As part of the TRACE-P mission, ozone vertical profile measurements were made at a number of locations in the North Pacific. At most of the sites there is also a multi-year record of ozonesonde observations. From seven locations in the western Pacific (Hong Kong; Taipei; Jeju Island, Korea; and Naha, Kagoshima, Tsukuba, and Sapporo, Japan), a site in the central Pacific (Hilo, HI), and a site on the west coast of the U.S. (Trinidad Head, CA) both a seasonal and event specific picture of tropospheric ozone over the North Pacific emerges. At all of the sites there is a pronounced spring maximum through the troposphere. There are, however, differences in the timing and strength of this feature. Over Japan the northward movement of the jet during the spring and summer influences the timing of the seasonal maximum. The ozone profiles suggest that transport of ozone rich air from the stratosphere plays a strong role in the development of this maximum. During March and April at Hong Kong ozone is enhanced in a layer that extends from the lower free troposphere into the upper troposphere that likely has its origin in biomass burning in northern Southeast Asia and equatorial Africa. During the winter the Pacific subtropical sites (latitude -25N) are dominated by air with a low-latitude, marine source that gives low ozone amounts particularly in the upper troposphere. In the summer in the boundary layer at all of the sites marine air dominates and ozone amounts are generally quite low (less than 25 ppb). The exception is near large population centers (Tokyo and Taipei but not Hong Kong) where pollution events can give amounts in excess of 80 ppb. During the TRACE-P intensive campaign period (February-April 2001) tropospheric ozone amounts were rather typical of those seen in the long-term records of the stations with multi-year soundings.

Oltmans, S. J.↗
NASA NTRS2001

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↗
NASA NTRS2002

Relative Amino Acid Concentrations as a Signature for Parent Body Processes of Carbonaceous Chondrites

Most meteorites are thought to have originated from objects in the asteroid belt. Carbonaceous chondrites, which contain significant amounts of organic carbon including complex organic compounds, have also been suggested to be derived from comets. The current model for the synthesis of organic compounds found in carbonaceous chondrites includes the survival of interstellar organic compounds and the processing of some of these compounds on the meteoritic parent body. The amino acid composition of five CM carbonaceous chondrites, two CIs, one CR, and one CV3 have been measured using hot water extraction-vapor hydrolysis, OPA/NAC derivatization and high-performance liquid chromatography (HPLC). Total amino acid abundances in the bulk meteorites as well as the amino acid concentrations relative to glycine = 1.0 for beta-alanine, alpha-aminoisobutyric acid and D-alanine were determined. Additional data for three Antarctic CM meteorites were obtained from the literature. All CM meteorites analyzed in this study show a complex distribution of amino acids and a high variability in total concentration ranging from approx. 15,300 to approx. 5800 parts per billion (ppb), while the CIs show a total amino acid abundance of approx. 4300 ppb. The relatively (compared to glycine) high AIB content found in all the CMs is a strong indicator that Strecker-cyanohydrin synthesis is the dominant pathway for the formation of amino acids found in these meteorites. The data from the Antarctic CM carbonaceous chondrites are inconsistent with the results from the other CMs, perhaps due to influences from the Antarctic ice that were effective during their residence time. In contrast to CMs, the data from the CI carbonaceous chondrites indicate that the Strecker synthesis was not active on their parent bodies.

Botta, Oliver↗
NASA NTRS2004

Tropospheric Methane Over the Pacific Basin During TRACE-P

We received funding for the acquisition, statistical analysis, interpretation, and publication of atmospheric methane data collected during the Transport and Chemical Evolution over the Pacific (TRACE-P) mission, flown February through April of 2001. These high precision measurements were made aboard the NASA DC-8 and P-3B aircraft using a fast response, tunable diode laser system, the DACOM instrument. Our analysis focused on the vertical and geographical distribution of this key trace gas, particularly in the context of other data available from the region such as those from the Pacific NOAA CMDL surface sites, and earlier NASA aircraft missions (such as PEM-West A and B). The paper reporting these results, "Large-Scale Distribution of CH4 in the Western Pacific: Sources and Transport from the Asian Continent" by authors K.B. Bartlett, G.W. Sachse, T. Slate, C. Harward, and D.R. Blake, is attached. The dataset of roughly 13,800 CH4 measurements ranged between 1602 ppb in stratospherically impacted air and 2149 ppb in highly polluted air. Overall, we found that CH4 concentrations were highly correlated with trace gases characteristic of a mix of anthropogenic industrial and combustion sources. They were strikingly correlated with ethane (C2H6) in particular, whose major sources are natural gas leakage and biomass burning. Correlation between the two hydrocarbons indicated that these sources may dominate for CH4 as well at this time.

Bartlett, Karen B.↗
NASA NTRS2000

Effective utilization of quantum-cascade distributed-feedback lasers in absorption spectroscopy

A variable duty cycle quasi-cw frequency scanning technique was applied to reduce thermal effects resulting from the high heat dissipation of type I quantum-cascade lasers. This technique was combined with a 100-m path-length multipass cell and a zero-air background-subtraction technique to enhance detection sensitivity to a parts-in-10(9) (ppb) concentration level for spectroscopic trace-gas detection of CH4, N2O, H2O, and C2H5OH in ambient air at 7.9 micrometers. A new technique for analysis of dense high resolution absorption spectra was applied to detection of ethanol in ambient air, yielding a 125-ppb detection limit.

NASA Discipline Environmental Health↗
NASA NTRS1999

High-power continuous-wave mid-infrared radiation generated by difference frequency mixing of diode-laser-seeded fiber amplifiers and its application to dual-beam spectroscopy

We report the generation of up to 0.7 mW of narrow-linewidth (<60-MHz) radiation at 3.3 micrometers by difference frequency mixing of a Nd:YAG-seeded 1.6-W Yb fiber amplifier and a 1.5-micrometers diode-laser-seeded 0.6-W Er/Yb fiber amplifier in periodically poled LiNbO3. A conversion efficiency of 0.09%/W (0.47 mWW-2 cm-1) was achieved. A room-air CH4 spectrum acquired with a compact 80-m multipass cell and a dual-beam spectroscopic configuration indicates an absorption sensitivity of +/-2.8 x 10(-5) (+/-1 sigma), corresponding to a sub-parts-in-10(9) (ppb) CH4 sensitivity (0.8 ppb).

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 NTRS1997

Fullerenes, fulleranes and polycyclic aromatic hydrocarbons in the Allende meteorite

In this paper, we confirm our earlier observations of fullerenes (C60 and C70) in the Allende meteorite (Becker et al., 1994a, 1995). Fullerene C60 was also detected in two separate C-rich (approximately 0.5-1.0%) dark inclusions (Heymann et al., 1987) that were hand picked from the Allende sample. The amounts of C60 detected were approximately 5 and approximately 10 ppb, respectively, which is considerably less than what was detected in the Allende 15/21 sample (approximately 100 ppb; Becker et al., 1994a, 1995). This suggests that fullerenes are heterogeneously distributed in the meteorite. In addition, we present evidence for fulleranes, (C60Hx), detected in separate samples by laser desorption (reflectron) time-of-flight (TOF) mass spectrometry (LDMS). The LDMS spectra for the Allende extracts were remarkably similar to the spectra generated for the synthetic fullerane mixtures. Several fullerane products were synthesized using a Rh catalyst (Becker et al., 1993a) and separated using high-performance liquid chromatography (HPLC). Polycyclic aromatic hydrocarbons (PAHs) were also observed ppm levels) that included benzofluoranthene and corannulene, a cup-shaped molecule that has been proposed as a precursor molecule to the formation of fullerenes in the gas phase (Pope et al., 1993).

NASA Center ARC↗
NASA NTRS1993

Ion mobility spectrometry of hydrazine, monomethylhydrazine, and ammonia in air with 5-nonanone reagent gas

Hydrazine (HZ) and monomethylhydrazine (MMH) in air were monitored continuously using a hand-held ion mobility spectrometer equipped with membrane inlet, 63Ni ion source, acetone reagent gas, and ambient temperature drift tube. Response characteristics included detection limit, 6 ppb; linear range, 10-600 ppb; saturated response, >2 ppm; and stable response after 15-30 min. Ammonia interfered in hydrazines detection through a product ion with the same drift time as that for MMH and HZ. Acetone reagent gas was replaced with 5-nonanone to alter drift times of product ions and separate ammonia from MMH and HZ. Patterns in mobility spectra, ion identifications from mass spectra, and fragmentation cross-sections from collisional-induced dissociations suggest that drift times are governed by ion-cluster equilibria in the drift region of the mobility spectrometer. Practical aspects including calibration, stability, and reproducibility are reported from the use of a hand-held mobility spectrometer on the space shuttle Atlantis during mission STS-37.

Flight Experiment↗
NASA NTRS2001

Global Modeling of Tropospheric Chemistry with Assimilated Meteorology: Model Description and Evaluation

We present a first description and evaluation of GEOS-CHEM, a global three-dimensional (3-D) model of tropospheric chemistry driven by assimilated meteorological observations from the Goddard Earth Observing System (GEOS) of the NASA Data Assimilation Office (DAO). The model is applied to a 1-year simulation of tropospheric ozone-NOx-hydrocarbon chemistry for 1994, and is evaluated with observations both for 1994 and for other years. It reproduces usually to within 10 ppb the concentrations of ozone observed from the worldwide ozonesonde data network. It simulates correctly the seasonal phases and amplitudes of ozone concentrations for different regions and altitudes, but tends to underestimate the seasonal amplitude at northern midlatitudes. Observed concentrations of NO and peroxyacetylnitrate (PAN) observed in aircraft campaigns are generally reproduced to within a factor of 2 and often much better. Concentrations of HNO3 in the remote troposphere are overestimated typically by a factor of 2-3, a common problem in global models that may reflect a combination of insufficient precipitation scavenging and gas-aerosol partitioning not resolved by the model. The model yields an atmospheric lifetime of methylchloroform (proxy for global OH) of 5.1 years, as compared to a best estimate from observations of 5.5 plus or minus 0.8 years, and simulates H2O2 concentrations observed from aircraft with significant regional disagreements but no global bias. The OH concentrations are approximately 20% higher than in our previous global 3-D model which included an UV-absorbing aerosol. Concentrations of CO tend to be underestimated by the model, often by 10-30 ppb, which could reflect a combination of excessive OH (a 20% decrease in model OH could be accommodated by the methylchloroform constraint) and an underestimate of CO sources (particularly biogenic). The model underestimates observed acetone concentrations over the South Pacific in fall by a factor of 3; a missing source from the ocean may be implicated.

Bey, Isabelle↗