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Fracture mechanics and surface chemistry investigations of environment-assisted crack growth

It is pointed out that environment-assisted subcritical crack growth in high-strength steels and other high-strength alloys (particularly in hydrogen and in hydrogenous environments) is an important technological problem of long standing. This problem is directly related to issues of structural integrity, durability, and reliability. The terms 'hydrogen embrittlement' and 'stress corrosion cracking' have been employed to describe the considered phenomenon. This paper provides a summary of contributions made during the past ten years toward the understanding of environmentally assisted crack growth. The processes involved in crack growth are examined, and details regarding crack growth and chemical reactions are discussed, taking into account crack growth in steels exposed to water/water vapor, the effect of hydrogen, reactions involving hydrogen sulfide, and aspects of fracture surface morphology and composition. Attention is also given to the modeling of crack growth response, crack growth in gas mixtures, and the interaction of solute atoms with the crack-tip stress field.

Wei, R. P.↗

The production of trace gases by photochemistry and lightning in the early atmosphere

Recent atmospheric calculation suggest that the prebiological atmosphere was most probably composed of nitrogen, carbon dioxide, and water vapor, resulting from volatile outgassing, as opposed to the older view of a strongly reducing early atmosphere composed of methane, ammonia, and hydrogen. Photochemical calculations indicate that methane would have been readily destroyed via reaction with the hydroxyl radical produced from water vapor and that ammonia would have been readily lost via photolysis and rainout. The rapid loss of methane and ammonia, coupled with the absence of a significant source of these gases, suggest that atmospheric methane and ammonia were very short lived, if they were present at all. An early atmosphere of N2, CO2, and H2O is stable and leads to the chemical production of a number of atmospheric species of biological significance, including oxygen, ozone, carbon monoxide, formaldehyde, and hydrogen cyanide. Using a photochemical model of the early atmosphere, the chemical productionof these species over a wide range of atmospheric parameters were investigated. These calculations indicate that early atmospheric levels of O3 were significantly below the levels needed to provide UV shielding. The fate of volcanically emitted sulfur species, e.g., sulfur dioxide and hydrogen sulfide, was investigated in the early atmosphere to assess their UV shielding properties. The photochemical calculations show that these species were of insufficient levels, due in part to their short photochemical lifetimes, to provide UV shielding.

Levine, J. S.↗

Occurrence of low molecular weight thiols in biological systems

Bromobimane labeling and high performance chromatography analysis were applied to various species of bacteria, plant tissues, and animal tissues. The reaction between thiols and monobromobimane is studied. Chromatograms revealing peaks produced by nonthiols and thiols are analyzed and compared. It is observed that all the bacteria species contain hydrogen sulfide, and glutathione is contained in facultative and aerobic gram-negative bacteria. For the plant tissues, the data reveal that mung bean sprouts contain homoglutathione and no glutathione; alfalfa sprouts contain homoglutathione and glutathione; the pea seed, nonlegumes, and fungi contain glutathione and no homoglutathione. It is detected that the main thiol in the animal tissues is glutathione. Based on the data, it is suggested that glutathione has an essential function in higher organisms.

Fahey, Robert C.↗

Voyager 2 at Neptune - Imaging science results

Neptune's atmosphere is revealed by Voyager 2 images to contain clouds of methane ice above a lower deck of hydrogen sulfide or ammonia ices, and to be dominated by an anticyclonic storm system designated the 'Great Dark Spot'; this bears both similarities and differences to the Great Red Spot of Jupiter. Like the rings of Uranus, those of Neptune are composed of very dark, but in addition very dusty, material. Six new regular satellites have been discovered whose radii range from 25 to 200 km. Triton is noted to be a differentiated body showing evidence of early surface-melting episodes. At least two active plumes are found on Triton, which may be driven by solar heating.

Smith, B. A.↗

Millimetre observations of comets P/Brorsen-Metcalf (1989o) and Austin (1989c1) with the IRAM 30-m radio telescope

Millimeter observations with the IRAM 30 m telescope were conducted in comet P/Brorsen-Metcalf (1989o) on September 1989 and Austin (1989c1) on April and May 1990. The HCN J(1-0) and J(3-2) lines were detected in both comets. The HCN production rate relative to water in P/Brorsen-Metcalf is comparable to that previously measured in comet P/Halley, while that inferred in comet Austin might be smaller by a factor of two. The H2CO(3 sub 12 - 2 sub 11) transition, marginally observed in comet P/Brorsen-Metcalf, was firmly detected in May 1990 in comet Austin. Observations performed at offset positions suggest that the source of H2CO might be distributed. The H2CO abundance is on the order of 0.5 percent that of water for both comets, assuming a scalelength of 10(exp 4) km at 1 AU from the Sun for the distributed source. During the May observing period of comet Austin, two new species were detected for the first time in a comet: hydrogen sulfide (H2S) through its 1(sub 10) - 1(sub 01) ortho line at 169 GHz, and methanol (CH3OH) through J(3-2) delta K = 0 transitions at 145 GHz. Preliminary estimates of their abundances are 1.5 x 10(exp -3) for H2S and 8 x 10(exp -3) for CH3OH.

Colom, P.↗

Laboratory evaluation and application of microwave absorption properties under simulated conditions for planetary atmospheres

Laboratory measurements of microwave and millimeter wave properties of the simulated atmosphere of the outer planets and their satellites has continued. One of the focuses is on the development of a radiative transfer model of the Jovian atmosphere at wavelengths from 1 mm to 10 cm. This modeling effort led to laboratory measurements of the millimeter wave opacity of hydrogen sulfide (H2S) under simulated Jovian conditions. Descriptions of the modeling effort, the Laboratory experiment, and the observations are presented. Correlative studies of measurements with Pioneer-Venus radio occultation measurements with longer wavelength emission measurements have provided new ways for characterizing temporal and spatial variations in the abundance of both gases H2SO4 and SO2, and for modeling their roles in the subcloud atmosphere. Laboratory measurements were conducted on 1.35 cm (and 13 cm) opacity of gaseous SO2 and absorptivity of gaseous SO2 at the 3.2 mm wavelength under simulated Venus conditions. Laboratory measurements were completed on millimeter wave dielectric properties of liquid H2SO4, in order to model the effects of the opacity of the clouds of Venus onto millimeter wave emission spectrum.

Steffes, Paul G.↗

Low temperature measurement of the vapor pressures of planetary molecules

Interpretation of planetary observations and proper modeling of planetary atmospheres are critically upon accurate laboratory data for the chemical and physical properties of the constitutes of the atmospheres. It is important that these data are taken over the appropriate range of parameters such as temperature, pressure, and composition. Availability of accurate, laboratory data for vapor pressures and equilibrium constants of condensed species at low temperatures is essential for photochemical and cloud models of the atmospheres of the outer planets. In the absence of such data, modelers have no choice but to assume values based on an educated guess. In those cases where higher temperature data are available, a standard procedure is to extrapolate these points to the lower temperatures using the Clausius-Clapeyron equation. Last summer the vapor pressures of acetylene (C2H2) hydrogen cyanide (HCN), and cyanoacetylene (HC3N) was measured using two different methods. At the higher temperatures 1 torr and 10 torr capacitance manometers were used. To measure very low pressures, a technique was used which is based on the infrared absorption of thin film (TFIR). This summer the vapor pressure of acetylene was measured the TFIR method. The vapor pressure of hydrogen sulfide (H2S) was measured using capacitance manometers. Results for H2O agree with literature data over the common range of temperature. At the lower temperatures the data lie slightly below the values predicted by extrapolation of the Clausius-Clapeyron equation. Thin film infrared (TFIR) data for acetylene lie significantly below the values predicted by extrapolation. It is hoped to bridge the gap between the low end of the CM data and the upper end of the TFIR data in the future using a new spinning rotor gauge.

Kraus, George F.↗

Millimeter-wave spectra of the Jovian planets

The millimeter wave portion of the electromagnetic spectrum is critical for understanding the subcloud atmospheric structure of the Jovian planets (Jupiter, Saturn, Uranus, and Neptune). This research utilizes a combination of laboratory measurements, computer modeling, and radio astronomical observation in order to obtain a better understanding of the millimeter-wave spectra of the Jovian planets. The pressure broadened absorption from gaseous ammonia (NH3) and hydrogen sulfide (H2S) was measured in the laboratory under simulated conditions for the Jovian atmospheres. Researchers developed new formalisms for computing the absorptivity of gaseous NH3 and H2S based on their laboratory measurements. They developed a radiative transfer and thermochemical model to predict the abundance and distribution of absorbing constituents in the Jovian atmospheres. They used the model to compute the millimeter wave emission from the Jovian planets.

Joiner, Joanna↗

Properties of scatterers in the troposphere and lower stratosphere of Uranus based on Voyager imaging data

Scalar and vector radiative transfer and microphysical models are presently constructed from photometrically and geometrically corrected Voyager images of Uranus defining spatially-resolved intensities over a range of phase angles for two latitude bands. The methane ice cloud occupying 1.2-1.3 bar is of 0.7 optical depth at 22.5 deg S, rising to 2.4 at 65 deg S; the volume absorption coefficient of the cloud particles is 50 percent greater at the low latitude than at the high, assuming constant mean cloud particle size. The scattering model also includes photochemically-produced stratospheric hydrocarbon ices in the upper troposphere and stratosphere, as well as an optically thick hydrogen sulfide cloud.

Rages, Kathy↗

Development of a cryogenic mixed fluid J-T cooling computer code, 'JTMIX'

An initial study was performed for analyzing and predicting the temperatures and cooling capacities when mixtures of fluids are used in Joule-Thomson coolers and in heat pipes. A computer code, JTMIX, was developed for mixed gas J-T analysis for any fluid combination of neon, nitrogen, various hydrocarbons, argon, oxygen, carbon monoxide, carbon dioxide, and hydrogen sulfide. When used in conjunction with the NIST computer code, DDMIX, it has accurately predicted order-of-magnitude increases in J-T cooling capacities when various hydrocarbons are added to nitrogen, and it predicts nitrogen normal boiling point depressions to as low as 60 K when neon is added.

Jones, Jack A.↗

Search for sulfur (H2S) on Jupiter at millimeter wavelengths

Jupiter was observed at two wavelengths near 1.4 mm in an attempt to detect gaseous hydrogen sulfide (H2S) or place new upper limits on its abundance on Jupiter's atmosphere. Although no H2S was detected, the first brightness temperature observations of Jupiter at 1.4 mm are reported with a spectral resolution of approximately 1 GHz using Mars as a calibration standard. The methodology and results of a laboratory experiment in which H2S absorption at 1.4 mm was measured in a simulated Jovian atmosphere. The results of laboratory measurements are applied to a radiative transfer model which is used to interpret the observations of Jupiter.

Joiner, Joanna↗

Low level measurements of atmospheric DMS, H2S, and SO2 for GTE/CITE-3

This project involved the measurement of atmospheric dimethylsulfide (DMS) and hydrogen sulfide (H2S) as part of the GTE/CITE-3 instrument intercomparison program. The two instruments were adapted for use on the NASA Electra aircraft and participated in all phases of the mission. This included ground-based measurements of NIST-provided standard gases and a series of airborne missions over the Western Atlantic Ocean. Analytical techniques used are described and the results are summarized.

Saltzman, Eric↗

New laboratory measurements on ammonia's inversion spectrum, with implications for planetary atmospheres

Microwave spectral measurements have been performed on pure room-temperature gaseous ammonia at frequencies from 1.75 to 18 GHz (1.7-17 cm), at 50-, 100-, and 300-torr pressures. These measurements are part of a laboratory program to measure the microwave absorption spectrum of ammonia, under conditions applicable to giant planet atmospheres, now in progress at the Jet Propulsion Laboratory. The pure ammonia data reported here agree well with previous data by Bleaney and Loubser (1950) at 100 and 300 torrs, and with predictions of the absorptivity formalism published by Berge and Gulkis. Success with pure ammonia but failure with mixtures of ammonia in hydrogen and helium (Spilker, 1990) indicates that the Berge and Gulkis formalism does not correctly handle foreign-gas effects on ammonia inversion lines. This may require modifying conclusions of radio astronomical and radio occultation studies that used this formalism. Notably, a suggested depletion of ammonia and superabundance of hydrogen sulfide may have been exaggerated as a result of inaccuracies in the Berge and Gulkis formalism.

Spilker, Thomas R.↗

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.↗

Study of secondary-flow patterns in an annular cascade of turbine nozzle blades with vortex design

In order to increase understanding of the origin of losses in a turbine, the secondary-flow components in the boundary layers and the blade wakes of an annular cascade of turbine nozzle blades (vortex design) was investigated. A detailed study was made of the total-pressure contours and, particularly, of the inner-wall loss cores downstream of the blades. The inner-wall loss core associated with a blade of the turbine-nozzle cascade is largely the accumulation of low-momentum fluids originating elsewhere in the cascade. This accumulation is effected by a secondary-flow mechanism which acts to transport the low-momentum fluids across the channels on the walls and radially in the blade wakes and boundary layers. The patterns of secondary flow were determined by use of hydrogen sulfide traces, paint, flow fences, and total pressure surveys. At one flow condition investigated, the radial transport of low-momentum fluid in the blade wake and on the suction surface near the trailing edge accounted for 65 percent of the loss core; 30 percent resulted from flow in the thickened boundary layer on the suction surface and 35 percent from flow in the blade wake.

FLOW, SUBSONIC↗

Program For Joule-Thomson Analysis Of Mixed Cryogens

JTMIX computer program predicts ideal and realistic properties of mixed gases at temperatures between 65 and 80 K. Performs Joule-Thomson analysis of any gaseous mixture of neon, nitrogen, various hydrocarbons, argon, oxygen, carbon monoxide, carbon dioxide, and hydrogen sulfide. When used in conjunction with DDMIX computer program of National Institute of Standards and Technology (NIST), JTMIX accurately predicts order-of-magnitude increases in Joule-Thomson cooling capacities occuring when various hydrocarbons added to nitrogen. Also predicts boiling temperature of nitrogen depressed from normal value to as low as 60 K upon addition of neon. Written in Turbo C.

Jones, Jack A.↗

A preliminary study of the variability and magnitude of the flux of biogenic sulfur gases from a New Hampshire salt marsh

Salt marshes have highly variable spatial and temporal fluxes of hydrogen sulfide, carbonyl sulfide, methane thiol, dimethyl sulfide, and carbon disulfide (H2S, COS, MeSH, DMS, and CS2, respectively). This variability was tested at nine emission sites in a New Hampshire, USA salt marsh: three replicates in each of three vegetation zones, Spartina alterniflora, S. patens, and a transition zone. Three sites were sampled simultaneously, either within or across vegetation zones, using a dynamic flux chamber technique. Difficulties with calibration and field equipment resulted in fluxes with maximum absolute uncertainties of greater than plus or minus 200 percent. However, the relative uncertainty between subsequent samples was closer to plus or minus 20 percent. Chambers are expected to affect the natural flux of gases by altering the humidity, temperature, and composition of the gas inside the chamber. Summertime fluxes are highest for all gases except COS which demonstrated evidence of a springtime peak. A summertime background flux of 5 to 100 x 10(exp -9) g S/m(sup -2) min was observed for all gases, while S alternifora fluxes of MeSH and DMS were approximately 8 fold and approximately 100 fold higher than S. patens, respectively. DMS and MeSH fluxes were higher during the day than at night. Evidence of COS uptake by plants was observed. CS2 appeared to be the quantitatively least important sulfur gas emitted. Improved laboratory and sample collection techniques and further data collection in the field will yield information on the details of salt marsh variability, will improve estimates of the error associated with single flux measurements, and will allow a more accurate estimation of sulfur fluxes from salt marshes based on vegetation and area coverage data. Inability to control the temperature and humidity inside of the chamber remain significant problems with the chamber design.

Morrison, Michael Cope↗

The effects of acid deposition on sulfate reduction and methane production in peatlands

Peatlands, as fens and bods, make up a large percentage of northern latitude terrestrial environments. They are organic rich and support an active community of anaerobic bacteria, such as methanogenic and sulfate-reducing bacteria. The end products of these microbial activities, methane and hydrogen sulfide, are important components in the global biogeochemical cycles of carbon and sulfur. Since these two bacterial groups compete for nutritional substrates, increases in sulfate deposition due to acid rain potentially can disrupt the balance between these processes leading to a decrease in methane production and emission. This is significant because methane is a potent greenhouse gas that effects the global heat balance. A section of Mire 239 in the Experimental Lakes Area, in Northwestern Ontario, was artificially acidified and rates of sulfate reduction and methane production were measured with depth. Preliminary results suggested that methane production was not affected immediately after acidification. However, concentrations of dissolved methane decreased and dissolved sulfide increased greatly after acidification and both took several days to recover. The exact mechanism for the decrease in methane was not determined. Analyses are under way which will be used to determine rates of sulfate reduction. These results will be available by Spring and will be discussed.

Murray, Georgia L.↗