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NASA NTRS1991

Titan aerosol and gas experiment for the Huygens Probe

The Cassini Mission is a joint undertaking of NASA and the European Space Agency (ESA) to explore the Saturnian System with a Saturn Orbiter and a Titan Probe. The launch vehicle and the Saturn Orbiter are the responsibility of NASA while the Huygens Probe (detachable Titan Probe) is the responsibility of ESA. The spacecraft will be launched in 1996 and the Huygens Probe will arrive at Titan in 2003. The Cassini Mission-Huygens Probe provides a unique opportunity to obtain detailed information about the atmosphere and, possibly, the surface of Titan. Titan possesses a substantial nitrogen atmosphere containing methane and many other organic compounds. Aerosols play an important role in the atmospheric processes on Titan. The Huygens Probe offers an opportunity to determine how organic particles are formed and grow which will clarify their role on Earth. A powerful analytical instrument, capable of addressing the above technology and other science questions, was recently proposed for the Huygens Probe. It is comprised of an aerosol and gas sampler and processor, and a gas chromatograph-ion mobility spectrometer. The instrument will be able to measure complex organics that make up the collected aerosols to the approximate 1 ppm level. Gases will be measured to approximately 10 ppb. Because the Titan atmosphere is expected to be quite complex, a gas chromatograph-ion mobility spectrometer is used to provide unequivocal identification of the components of the analytes. Further details of the science question to be investigated and the proposed instrument are described. The expected results and their implications are also addressed.

Carle, G. C.↗

NASA NTRS1990

Toxicology of atmospheric degradation products of selected hydrochlorofluorocarbons

Trifluoroacetic acid (TFA) is a liquid with a sharp biting odor. It has been proposed as the product of environmental degradation of the hydrochlorofluorocarbons HCFC-123, HCFC-124, HFC-134a, and HFC-125. Compounds HCFC-141b and HCFC-142b could yield mixed fluorochloroacetic acids, for which there is no available toxicologic data. The release of hydrochlorofluorocarbons into the environment could also give rise to HF, but the additional fluoride burden (1 to 3 ppb) in rainwater is trivial compared to levels in fluoridated drinking water (1 ppm), and would provide an insignificant risk to humans. Thus, in this paper only the toxocologic data on TFA is reviewed to assess the potential risks of environmental exposure.

Kaminsky, Laurence S.↗

NASA NTRS1991

Total Organic Carbon Analyzer

The development and testing of a breadboard version of a highly sensitive total-organic-carbon (TOC) analyzer are reported. Attention is given to the system components including the CO2 sensor, oxidation reactor, acidification module, and the sample-inlet system. Research is reported for an experimental reagentless oxidation reactor, and good results are reported for linearity, sensitivity, and selectivity in the CO2 sensor. The TOC analyzer is developed with gravity-independent components and is designed for minimal additions of chemical reagents. The reagentless oxidation reactor is based on electrolysis and UV photolysis and is shown to be potentially useful. The stability of the breadboard instrument is shown to be good on a day-to-day basis, and the analyzer is capable of 5 sample analyses per day for a period of about 80 days. The instrument can provide accurate TOC and TIC measurements over a concentration range of 20 ppb to 50 ppm C.

Godec, Richard G.↗

NASA NTRS1991

Development of a proton-exchange membrane electrochemical reclaimed water post-treatment system

A single-cell electrochemical reactor that utilizes a proton exchange membrane (PEM) as a solid electrolyte is being investigated for posttreatment of reclaimed waste waters with low or negligible electrolyte content. Posttreatment is a final 'polishing' of reclaimed waste waters prior to reuse, and involves removing organic impurities at levels as high as 100 ppm to below 500 ppb total organic carbon (TOC) content to provide disinfection. The system does not utilize or produce either expendable hardware components or chemicals and has no moving parts. Test data and kinetic analysis are presented. The feasibility and application for water reclamation processes in controlled ecological environments (e.g., lunar/Mars habitats) are also presented. Test results show that the electrochemical single cell reactor provides effective posttreatment.

Kaba, Lamine↗

NASA NTRS1992

Daily estimates of the earth's pole position with the Global Positioning System

Daily estimates of the earth's pole position have been obtained with measurements from a worldwide network of GPS receivers, obtained during the three week GIG '91 experiment in January-February 1991. For this short-term study, the GPS based polar motion series agrees with the other space based geodetic techniques (Very Long Baseline Interferometry and Satellite Laser Ranging) to about 0.4 mas rms, after the removal of mean biases of order 1-3 mas. The small error in day-to-day variability is not sensitive to the fiducial strategy used, nor are fiducial sites even necessary for monitoring high frequency pole position variability. The small biases indicate that the applied reference frames of the three geodetic techniques are nearly aligned, that the GPS fiducial errors are small, and that systematic errors in GPS are also small (of order 5 ppb). A well determined reference frame is necessary for monitoring the long-term stability of polar motion and for separating it from other long-term signals such as tectonic motion and internal systematic errors.

Lindqwister, Ulf J.↗

NASA NTRS1992

FAGE measurements of tropospheric HO with measurements and model of interferences

Ambient HO measurements by low-pressure laser-excited fluorescence with chemical modulation, and supporting ozone and water-vapor data, are presented for periods in May and August 1987. The observed peak daytime ambient HO concentrations are in the range (2.5 to 8) x 10 exp 6 molecules/cu cm and show small negative offsets due to photochemical interference. Direct measurements of the interference at fixed (O3) give the dependence on ambient (H2O) and on the modulating reagent (isobutane). At ambient (O3) = 30 ppb and 10 torr H2O, with excitation and detection at a total pressure of 4 torr, the net interference is equal to (HO) = -1.3 x 10 exp 6 molecules/cu cm. Production of HO by the reaction of isobutane with O(1D) accounts for the negative interference. Quenching of HO fluorescence by the modulating reagent contributes a smaller positive term to the interference; kinetic measurements of the quenching rate coefficient are reported. The experimental interference results are compared with a detailed kinetic model of HO production, excitation, relaxation, and detection; reasonable agreement is found.

Hard, T. M.↗

NASA NTRS1991

Aerodyne Research mobile infrared methane monitor

An improved real-time methane monitor based on infrared absorption of the 3.39 micron line of a HeNe laser is described. Real time in situ measurement of methane has important applications in stratospheric and tropospheric chemistry, especially when high accuracy measurements can be made rapidly, providing fine spatial-scale information. The methane instrument provides 5 ppb resolution in a 1 sec averaging time. A key feature in this instrument is the use of magnetic (Zeeman) broadening to achieve continuous tunability with constant output power over a range of 0.017/cm. The instruments optical absorption path length is 47 m through sampled air held at 50 torr in a multipass cell of the Herriott (off-axis resonator) type. A microprocessor controls laser frequency and amplitude and collects data with minimal operator attention. The instrument recently has been used to measure methane emissions from a variety of natural and artificial terrestrial sources.

Mcmanus, J. B.↗

NASA NTRS1992

Search for a meteoritic component at the Beaverhead impact structure, Montana

The Beaverhead impact structure, in southwestern Montana, was identified recently by the presence of shatter cones and impactites in outcrops of Proterozoic sandstones of the Belt Supergroup. The cones occur over an area greater than 100 sq km. Because the geologic and tectonic history of this region is long and complex, the outline of the original impact crater is no longer identifiable. The extent of the area over which shatter cones occur suggests, however, that the feature may have been at least 60 km in diameter. The absence of shatter cones in younger sedimentary units suggests that the impact event occurred in late Precambrian or early Paleozoic time. We have collected samples of shocked sandstone from the so-called 'Main Site' of dark-matrix breccias, and of impact breccias and melts from the south end of Island Butte. The melts, occurring often as veins through brecciated sandstone, exhibit a distinctive fluidal texture, a greenish color, and a cryptocrystalline matrix, with small inclusions of deformed sandstone. Samples of the same type, along with country rock, were analyzed previously for major- and trace-element abundances. It was found that, although the major-element composition as relatively uniform, trace-element composition showed variations between the melt material and the adjacent sandstone. These variations were attributed to extensive weathering and hydrothermal alteration. In a more specific search for a possible meteoritic signature in the breccia and the melt material we have conducted a new series of trace-element analyses on powders of our own samples by thermal neutron activation analysis. Our results indicate that Ir abundances in the breccia, the melts, and the adjacent sandstone clasts are no greater than about 0.1 ppb, suggesting no Ir enrichment of the breccia or the melts relative to the country rock. However, both the breccia and the melt material exhibit notable enrichments in Cr (8- and 10-fold), in U (9- and 5-fold), and in the heavy REE's (1.5- and 3-fold), respectively.

Lee, Pascal↗

NASA NTRS1992

Measuring the earth to within an inch using GPS satellites

In 1991, NASA-JPL coordinated the GPS for International Earth Rotation Service and Geodynamics '91, or GIG'91, three-week experiment; this had as its fundamental purpose the demonstration of GPS monitoring of earth rotation. Distance precisions of 3-20 ppb, or several cm across the diameter of the earth, were demonstrated by several analysis groups by means of their software systems; these results are approximately 100 times more precise than commercial GPS software. While satellite laser ranging and VLBI have been capable of such precision for several years, GPS is more cost-effective in many cases.

Blewitt, Geoffrey↗

NASA NTRS1993

A search for C60 in carbonaceous chondrites

Analysis of interior samples of the Murchison meteorite by two routes yielded an upper limit of 2 ppb for its C60 content, as compared to parts per million levels for individual polycyclic aromatic hydrocarbons (PAHs ). Provided the samples contain an interstellar component, which is probable since Murchison hydrocarbons contain excess deuterium, this result argues against the ubiquitous presence of C60 in the interstellar medium. A possible explanation for the absence of C60 was found in experiments showing how PAHs replace fullerenes as stable end products when hydrogen is present during carbon condensation. As a secondary result we found high molecular weight PAHs in the Murchison and Allende meteorites. Coronene and its methyl derivatives are especially interesting since features in the coronene spectrum have been shown to match some of the unidentified interstellar infrared emission bands.

De Vries, M. S.↗

NASA NTRS1993

Rates of oxidative weathering on the surface of Mars

A model of acid weathering is proposed for the iron-rich basalts on Mars. Aqueous oxidation of iron sulfides released SO4(2-) and H(+) ions that initiated the dissolution of basaltic ferromagnesian silicates and released Fe(2+) ions. The Fe(2+) ions eventually underwent ferrolysis reactions and produced insoluble hydrous ferric oxide phases. Measurements of the time-dependence of acid weathering reactions show that pyrrhotite is rapidly converted to pyrite plus dissolved ferrous iron, the rate of pyrite formation decreasing with rising pH and lower temperatures. On Mars, oxidation rates of dissolved Fe(2+) ions in equatorial melt-waters in contact with the atmosphere are estimated to lie in the range 0.3-3.0 ppb Fe/yr over the pH range 2 to 6. Oxidation of Fe(2+) ions is estimated to be extremely slow in brine eutectic solutions that might be present on Mars and to be negligible in the frozen regolith.

Burns, Roger G.↗

NASA NTRS1993

Measurement of the temperature coefficient of ratio transformers

We have measured the temperature coefficient of the output of several ratio transformers at ratios near 0.500,000 using an ac bridge and a dual-phase, lock-in amplifier. The two orthogonal output components were each resolved to +/- ppb of the bridge drive signal. The results for three commercial ratio transformers between 20 and 50 C range from 0.5 to 100 ppb/K for the signal component in phase with the bridge drive, and from 4 to 300 ppb/K for the quadrature component.

Briggs, Matthew E.↗

NASA NTRS1991

Iridium and trace element measurements from the Cretaceous-Tertiary boundary, site 752, Broken Ridge, Indian Ocean

Fourteen samples spanning a 2.5 m interval that includes the Cretaceous-Tertiary (K/T) boundary from Hole 752B near the crest of Broken Ridge in the eastern Indian Ocean were studied in order to search for anomalous enrichments of iridium (Ir) and shock-metamorphosed quartz grains. No allogenic quartz grains larger than 10 microns were observed, hence the presence of quartz containing diagnostic evidence of shock-metamorphism could not be confirmed. Two Ir anomalies of 2.2 +/- 0.6 and 2.0 +/- 0.4 parts per billion (ppb) were measured in samples of dark green ash-bearing chalk at depths of 357.93 and 358.80 m below seafloor, respectively. These samples containing anomalous enrichments of Ir were taken from approximately 82 cm above and 5 cm below the extinction level of Globotruncanids. Our results are consistent with those of Michel et al., who observe elevated concentrations of Ir at these depths in addition to a larger Ir anomaly associated with the extinction level of Globotruncanids.

Schuraytz, B. C.↗

NASA NTRS1992

Measurement of volatile organic chemicals at selected sites in California

Urban air concentrations of 24 selected volatile organic chemicals that may be potentially hazardous to human health and environment were measured during field experiments conducted at two California locations, at Houston, and at Denver. Chemicals measured included chlorofluorocarbons, halomethanes, haloethanes, halopropanes, chloroethylenes, and aromatic hydrocarbons. With emphasis on California sites, data from these studies are analyzed and interpreted with respect to variabilities in ambient air concentrations, diurnal changes, relation to prevailing meteorology, sources and trends. Except in a few instances, mean concentrations are typically between 0 and 5 ppb. Significant variabilities in atmospheric concentrations associated with intense sources and adverse meteorological conditions are shown to exist. In addition to short-term variability, there is evidence of systematic diurnal and seasonal trends. In some instances it is possible to detect declining trends resulting from the effectiveness of control strategies.

Singh, Hanwant B.↗

NASA NTRS1992

Catalytic oxidation for treatment of ECLSS and PMMS waste streams

Catalytic oxidation was added to the baseline multifiltration technology for use on the Space Station Freedom in order to convert low-molecular weight organic waste components such as alcohols, aldehydes, ketones, amides, and thiocarbamides to CO2 at low temperature (121 C), thereby reducing the total organic carbon (TOC) to below 500 ppb. The rate of reaction for the catalytic oxidation of aqueous organics to CO2 and water depends primarily upon the catalyst, temperature, and concentration of reactants. This paper describes a kinetic study conducted to determine the impact of each of these parameters upon the reaction rate. The results indicate that a classic kinetic model, the Langmuir-Hinshelwood rate equation for heterogeneous catalysis, can accurately represent the functional dependencies of this rate.

Akse, James R.↗

NASA NTRS1985

A field gas chromatograph using technology developed for solar system exploration

Trace gas analysis is an integral part of biospheric studies. Analytical instruments, primarily gas chromatographs (GC), are capable of measuring gases and volatiles to the ppb-level in real time. Trace gases significant in the study of biocycles include nitrous oxide, hydrogen sulfide, other nitrogen and sulfur species, as well as methane and ethylene. The concept of a field gas chromatograph is derived from technology being pursued in the design of ultra-compact instruments for solar system exploration. The instrument breadboard incorporates the specialized porous column packings and the highly sensitive metastable ionization detector developed by the Solar System Exploration Office. These parts ensure a broad capability for which the analysis of ambient N2O is one example. A commercial, portable gas chromatograph is currently being extensively modified to incorporate analytical concepts and components derived from flight GC technology. Data storage devices suitable for field use are presently being studied.

Woeller, F. H.↗

NASA NTRS1994

Hydrazine-Vapor Samplers

Active sampling unit capable of detecting hydrazine and monomethyl hydrazine vapors at levels as low as 10 ppb in air developed. Includes detachable badge holder and pump which draws air through badge holder at selectable rate of 1 or 2 L/min. Coated strip in each badge designed to align with air passage in badge holder. Two types of badge holders constructed: one has open-face design for general monitoring of air in open spaces, while other has closed-face design with viewing window and intended for sampling through small openings to detect leaks.

Young, Rebecca↗

NASA NTRS1993

The solubility of gold in silicate melts: First results

The effects of oxygen fugacity and temperature on the solubility of Au in silicate melts were determined. Pd-Au alloys were equilibrated with silicate of anorthite-diopside eutectic composition at different T-fO2 conditions. The behavior of Au was found to be similar to that of Pd reported recently. Au solubilities for alloys with 30 to 40 at. percent Au decrease at 1400 C from 12 ppm in air to 160 ppb at a log fO2 = -8.7. The slope of the log(Me-solubility) vs. log(fO2) curve is close to 1/4 for Au and the simultaneously determined Pd suggesting a formal valence of Au and Pd of 1+. Near the IW buffer Pd and Au solubilities become even less dependent on fO2 perhaps reflecting the presence of some metallic Au and Pd.

Borisov, A.↗