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At least 73 records · Page 4

Implications of stratospheric aerosol measurements for models of aerosol formation and evolution

Calculations of the distribution of stratospheric sulfur gases and of stratospheric aerosols are compared with measurements obtained in Alaska during July 1979. Generally, the measurements are reasonably consistent with the model results. COS is the major sulfur-bearing gas in the stratosphere while CS2 plays a lesser role in the formation of sulfate aerosols. Ammonia, which earlier measurements suggested was a major aerosol constituent, is found to be a contaminant, so models without ammonia chemistry may be justified. The model and the measurements suggest that stratospheric sulfuric acid aerosols nucleate just above the tropopause, but they are older and have grown to larger sizes at higher altitudes.

Toon, O. B.↗

Measurement of stratospheric sulfur constituents

New measurements of mixing ratios of OCS in the lower stratosphere at midlatitude (Northern California) and high-latitude (Alaska) locations are reported which are in essential agreement with previous results. Weak signals due to stratospheric SO2 have been detected, and the estimated mixing ratios ranged from 36 to 51 pptv at altitudes 15.2 to 20.3 km. A very weak signal observed in the analysis is thought to be due to CS2 and, if this identification is correct, an upper limit concentration is estimated to be 1 pptv.

Inn, E. C. Y.↗

Reduction of thionucleosides - A prebiotic pathway to deoxyribonucleosides

A mechanism is proposed for the prebiotic synthesis of deoxyribonucleotides and possible nucleic acid analogs from ribonucleotides by a pathway involving 2'-thio-2'-deoxyribonucleosides. The mechanism is supported by laboratory experiments in which 2'-thio-2'-deoxycytidine was synthesized from anhydro arabinosyl cytosine in dithiophosphate and CS2. The subsequent reduction of the thio-analogs has been achieved with ferrous ion, and photochemically. It is noted that the proposed pathway for prebiotic deoxyribonucleotide synthesis is in harmony with the Principle of Continuity, as both the proposed and present pathways rely on the reduction of a 2' functional group.

Patel, A. D.↗

Production of CS and S in Comet Bradfield /1979 X/

High and low resolution ultraviolet spectra of carbon monosulfide (CS) in Comet Bradfield (1979 X) were obtained with the IUE satellite. The high resolution rotational profile of the (0, 0) band at 257.5 nm can be fitted with a theoretical profile derived assuming a Boltzmann temperature of 70 K. Spatial plots of the low resolution data for both S and CS show that these emissions are concentrated toward the cometary nucleus. The results that have been obtained are consistent with a Haser model for CS and S where the parent molecule is CS2. A very rapid variation of CS brightness with heliocentric distance is found.

Jackson, W. M.↗

Collisional narrowing in the optically pumped CH3OH and CH3F lasers

The gain linewidth of the optically pumped CH3F laser is observed to narrow and rebroaden with the addition of He. In addition, the same effect is observed in the CH3OH laser with the addition of the polyatomic buffer gases SF6 and CS2. These results offer conclusive evidence of the Dicke narrowing phenomena in these inverted pure rotational transitions. The effect is observed using a high harmonic mixing technique in a Schottky barrier diode.

Lawandy, N. M.↗

The discovery of S2 in comet IRAS-Araki-Alcock 1983d

Ultraviolet spectra of comet IRAS-Araki-Alcock 1983d, obtained with the International Ultraviolet Explorer spacecraft when the comet was only 0.032 AU from earth, show strong emission bands due to S2, the first detection of this species in an astronomical object. The spatial profiles imply that the S2 is released directly from the nucleus and has a lifetime of the order of 450 s. The derived production rate of S2 was 2 x 10 to the 25th per s. It is suggested that the S2 can be formed by cosmic-ray irradiation of other sulfurous compounds in the ices and that it need not be primordial. It has been also determined that the scale length of the parent of CS (presumably CS2) is 300 km and that the CS production is approximately equal to that of S2, both near 5 x 10 to the -4th that of OH and comparable to that of other trace species observed in comets.

Ahearn, M. F.↗

Photodissociation rates of molecules by the interstellar radiation field

The photodissociation rates of CO, NO, H2O, HCN, NO2, SO2, CS2, OCS, NH3, CH4, H2O2, and C2H2 dissociated by the interstellar ultraviolet background in the solar neighborhood are calculated for the 106-200 nm wavelength region. The processes for photodissociation of various interstellar molecules into fragments are discussed.

Lee, L. C.↗

Some thoughts on GAIA and the sulfur cycle

The data hypothesis states that the composition, oxidation reduction state, and temperature of the troposphere are actively regulated by the biota for the biota. One of the early predictions of the Gaia hypothesis was that there should be a sulfur compound made by the biota in the oceans. It would need to be stable enough against oxidation in water to allow its transfer to the air. Either the sulfur compound itself or its atmospheric oxidation product would have to return sulfur from the sea to the land surfaces. The most likely candidate for this role was dimethyl sulfide. Another sulfur compound of interest from a Gaian viewpoint CS2 (carbon disulfide) is discussed. Theories on the production of dimethyl sulfide and carbon disulfide related to the Gaian hypothesis are examined.

Lovelock, J. E.↗

Sulfur Cycle

Among the general categories of tropospheric sulfur sources, anthropogenic sources have been quantified the most accurately. Research on fluxes of sulfur compounds from volcanic sources is now in progress. Natural sources of reduced sulfur compounds are highly variable in both space and time. Variables, such as soil temperature, hydrology (tidal and water table), and organic flux into the soil, all interact to determine microbial production and subsequent emissions of reduced sulfur compounds from anaerobic soils and sediments. Available information on sources of COS, CS2, DMS, and H2S to the troposphere in the following paragraphs are summarized; these are the major biogenic sulfur species with a clearly identified role in tropospheric chemistry. The oxidation of SO2 to H2SO4 can often have a significant impact on the acidity of precipitation. A schematic representation of some important transformations and sinks for selected sulfur species is illustrated.

Hariss, R.↗

OH measurement by laser light absorption

Since the first attempt to measure atmospheric hydroxyl radicals by optical absorption in 1975 (Perner et al., 1976) this method has been continuously developed further and its major obstacles and limitations are known today. The laser beam needs to be expanded in order to reduce the beam divergence. At the same time the energy density of the laser beam which produces OH via ozone photolysis is reduced to such an extent that the self-produced OH concentration ranges well below the atmospheric value. Atmospheric absorptions should be observed over a wide spectral range so that not only the OH radicals are properly identified by several rotational lines but their absorption can be corrected for interfering absorptions from other air constituents as SO2, CH2O, CS2, etc., which can be identified in a wide spectral range with more confidence. Air turbulence demands fast spectral scanning or probing on and off the absorption line. Energy requirements should be kept small in field operations. In the experiment frequency doubled dye laser pulses at 308 nm are produced. The picosecond light pulses are expected to show a smooth profile (light intensity against wavelength) which will be broadened to the required spectral width according to the uncertainty principle. The pump laser will be an optoacoustically modulated Nd:YAG laser.

Perner, D.↗

Trace gas measurements from tethered balloon platforms

Instrumentation and chemical sampling and analysis procedures are described for making measurements of atmospheric carbon disulfide in the concentration range 1-1000 pptv from tethered balloon platforms. Results of a study on the CS2 composition of air downward of a saltwater marsh are reported. A method for obtaining the necessary data for solving the budget equations for surface fluxes, chemical formation rates and chemical destruction rates using data acquired from tethered balloon platforms is presented.

Bandy, Alan R.↗

A rotational-state population analysis of the high-resolution IUE observation of CS emission in comet P/Halley

The high resolution spectrum of comet P/Halley has been measured in the region of the CS emission. CS in comet Halley is produced by photodissociation of CS2 and subsequently reexcited by broad band solar radiation. An inversion procedure is introduced to extract the rotational population distribution from the dispersed fluorescence spectrum. Intensity anomalies in the wavelength region corresponding to P and Q branch emission are considered.

Prisant, M. G.↗

IUE observations of comets P/Brorsen-Metcalf and Okazaki-Levy-Rudenko

Comet P/Brorsen-Metcalf (1989c) was observed with the International Ultraviolet Explorer (IUE) on several dates from 27 July 1989 through 5 August 1989; comet Okazaki-Levy-Rudenko (1989r) was observed in low dispersion with IUE on 2 and 22 December 1989. The water production rates for P/Brorsen-Metcalf were derived from OH measurements using the vectorial model of Festou (1981). Included also are the water production rates for Okazaki-Levy-Rudenko. Two estimates of the water production rate from the O I emission around 1304 A(octogons) are included. The ultraviolet continuum was not reliably measurable in comet P/Brorsen-Metcalf in most of the spectra, but Afp is approximately 30 cm for 2 August. For the comet Okazaki-Levy-Rudenko, an Afp = 50 cm was derived for 22 December. Both comets have very little dust compared to other recently observed comets. The ratio of CS to water production rates are presented. Relative to water, both comets had less CS than P/Halley in the same range of heliocentric distances. The CS production rates were obtained from a Haser model, assuming a short-lived parent (CS2). Because the dynamic range of the IUE spectrographs are limited, not all species can be measured in each spectrum. The P/Brorsen-Metcalf spectra from 31 July and 3 August were obtained from the NSSDC Archives. Due to the observing technique used for these spectra, the exposure time and hence, the brightnesses and derived quantities have a small uncertainty associated with them.

Roettger, E. E.↗

Airborne sulfur trace species intercomparison campaign: Sulfur dioxide, dimethylsulfide, hydrogen sulfide, carbon disulfide, and carbonyl sulfide

Results from an airborne intercomparison of techniques to measure tropospheric levels of sulfur trace gases are presented. The intercomparison was part of the NASA Global Tropospheric Experiment (GTE) and was conducted during the summer of 1989. The intercomparisons were conducted on the Wallops Electra aircraft during flights from Wallops Island, Virginia, and Natal, Brazil. Sulfur measurements intercompared included sulfur dioxide (SO2), dimethylsulfide (DMS), hydrogen sulfide (H2S), carbon disulfide (CS2), and carbonyl sulfide (OCS). Measurement techniques ranged from filter collection systems with post-flight analyses to mass spectrometer and gas chromatograph systems employing various methods for measuring and identifying the sulfur gases during flight. Sampling schedules for the techniques ranged from integrated collections over periods as long as 50 minutes to one- to three-minute samples every ten or fifteen minutes. Several of the techniques provided measurements of more than one sulfur gas. Instruments employing different detection principles were involved in each of the sulfur intercomparisons. Also included in the intercomparison measurement scenario were a host of supporting measurements (i.e., ozone, nitrogen oxides, carbon monoxide, total sulfur, aerosols, etc.) for purposes of: (1) interpreting results (i.e., correlation of any noted instrument disagreement with the chemical composition of the measurement environment); and (2) providing supporting chemical data to meet CITE-3 science objectives of studying ozone/sulfur photochemistry, diurnal cycles, etc. The results of the intercomparison study are briefly discussed.

Gregory, Gerald L.↗

Thermodynamic models of the chemistry of lunar volcanic gases

Thermodynamic models and mass-balance arguments are used to constrain the chemistry of lunar volcanic gases. The results predict that lunar gases were dominated by reduced C and S gases such as CO, COS, CS2, S2. The more oxidized gases CO2 and SO2 were also important, but only in limited temperature ranges. Gases such as Cl2, CCl4, and CF4 were more abundant than HF and HCl, which were the two major H compounds in the lunar gases. Chlorides and fluorides were important species for transporting many volatile and ore-forming metals, and the implications for fractionating and concentrating metals into lunar ore-deposits merit further study.

Fegley, Bruce, Jr.↗

Synthesis, vapor growth, polymerization, and characterization of thin films of novel diacetylene derivatives of pyrrole. The use of computer modeling to predict chemical and optical properties of these diacetylenes and poly(diacetylenes)

In the present work two diacetylene derivatives of pyrrole which are predicted by semiempirical AM1 calculations to have very different properties, are synthesized; the polymerizability of these diacetylenes in the solid state is determined, and the results are compared to the computer predictions. Diacetylene 1 is novel in that the monomer is a liquid at room temperature; this may allow for the possibility of polymerization in the liquid state as well as the solid state. Thin poly(diacetylene) films are obtained from compound 1 by growing films of the monomer using vapor deposition and polymerizing with UV light; these films are then characterized. Interestingly, while the poly(diacetylene) from 1 does not possess good nonlinear optical properties, the monomer exhibits very good third-order effects (phase conjugation) in solution. Dilute acetone solutions of the monomer 1 give intensity-dependent refractive indices on the order of 10 exp -6 esu; these are 10 exp 6 times better than for CS2.

Paley, M. S.↗

Nonlinear optical parameters of 7-prime,7-prime-dicyano-7-prime-apo-beta-carotene in hexane by self-action techniques

Quantitative measurements of the nonlinear refractive index coefficient n(2) and the third-order nonlinear susceptibility chi(3) for a solution of 7-prime,7-prime-dicyano-7-prime-apo-beta-carotene (DCAC) in hexane have been measured at different concentrations. The measurements have been performed by both the self-trapping and self-phase modulation techniques using a CW Ar(+) laser. The results show that DCAC has a relatively large nonlinearity, attributed to a thermal mechanism, with n(2) of the order of 10 exp 9 times that of CS2.

Abdeldayem, Hossin A.↗

Emissions of sulfur gases from marine and freshwater wetlands of the Florida Everglades - Rates and extrapolation using remote sensing

Rates of emissions of the biogenic sulfur (S) gases carbonyl sulfide (COS), methyl mercaptan (MSH), dimethyl sulfide (DMS), and carbon disulfide (CS2) were measured in a variety of marine and freshwater wetland habitats in the Florida Everglades during a short duration period in October using dynamic chambers, cryotrapping techniques, and gas chromatography. The most rapid emissions of over 500 nmol/sq m/h occurred in red mangrove-dominated sites that were adjacent to open seawater and contained numerous crab burrows. Poorly drained red mangrove sites exhibited lower fluxes of about 60 nmol/sq m/h, which were similar to fluxes from the black mangrove areas which dominated the marine-influenced wetland sites in the Everglades. DMS was the dominant organo-S gas emitted especially in the freshwater areas. Spectral data from a scene from the Landsat TM were used to map habitats in the Everglades. Six vegetation categories were delineated using geographical information system software and S gas emissions were extrapolated for the entire Everglades National Park. The black mangrove-dominated areas accounted for the largest portion of S gas emissions to the area. The large area extent of the saw grass communities accounted for about 24 percent of the total S emissions.

Hines, Mark E.↗