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At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
NASA NTRS1992

Ground-based infrared measurements of carbonyl sulfide total column abundances - Long-term trends and variability

Attention is given to total vertical column abundances of carbonyl sulfide (OCS) derived from time series of high-resolution IR solar absorption spectra recorded near Tucson, Arizona, and in the Swiss Alps. The analysis of both data sets is based on nonlinear least squares spectral fittings of narrow intervals centered on lines of the intense nu3 band of OCS, the P(37) transition at 2045.5788/cm, and the P(15) transition at 2055.8609/cm, with a consistent set of spectroscopic line parameters. The Arizona measurements, recorded on 20 different days between May 1977 and March 1991, show a 10-percent peak-to-peak seasonal cycle with a summer maximum and a winter minimum and a trend in the total column abundance equal to (0.1 +/-0.2) percent/yr, 2sigma. The Alpine total columns exhibit a more complex seasonal variation than noted in the Arizona data. The results from the two sites indicate that there has been no significant change in the OCS total column abundance at northern midlatitudes over the last decade.

Rinsland, C. P.↗
NASA NTRS1992

Line intensities and collisional-broadening parameters for the nu4 and nu6 bands of carbonyl fluoride

Line intensities, air- and self-broadening parameters have been measured for selected lines in the nu4 (1243/cm) and nu6 (774/cm) bands of carbonyl fluoride at 296 and 215 K using a tunable diode-laser spectrometer. Measured line intensities are in good agreement +/- 6 percent with recently reported values derived from rotational analyses of the nu4 and nu6 bands. The measured average air-broadening coefficient at 296 K also agrees well (+/- 5 percent) with N2-broadening coefficients determined from microwave studies, while the average self-broadening coefficient reported here is smaller than a previously reported value by 45 percent.

May, Randy D.↗
NASA NTRS1994

Application of static and dynamic enclosures for determining dimethyl sulfide and carbonyl sulfide exchange in Sphagnum peatlands: Implications for the magnitude and direction of flux

A static enclosure method was applied to determine the exchange of dimethyl sulfide (DMS) and carbonyl sulfide (OCS) between the surface of Sphagnum peatlands and the atmosphere. Measurements were performed concurrently with dynamic (flow through) enclosure measurements with sulfur-free air used as sweep gas. This latter technique has been used to acquire the majority of available data on the exchange of S gases between the atmosphere and the continental surfaces and has been criticized because it is thought to overestimate the true flux of gases by disrupting natural S gas gradients. DMS emission rates determined by both methods were not statistically different between 4 and greater than 400 nmol/sq m/h, indicating that previous data on emissions of at least DMS are probably valid. However, the increase in DMS in static enclosures was not linear, indicating the potential for a negative feedback of enlosure DMS concentrations on efflux. The dynamic enclosure method measured positive OCS flux rates (emission) at all sites, while data using static enclosures indicated that OCS was consumed from the atmosphere at these same sites at rates of 3.7 to 55 nmol/sq m/h. Measurements using both enclosure techniques at a site devoid of vegetation showed that peat was a source of both DMS and OCS. However, the rate of OCS efflux from decomposing peat was more than counterbalanced by OCS consumption by vegetation, including Sphagnum mosses, and net OCS uptake occurred at all sites. We propose that all wetlands are net sinks for OCS.

De Mello, William Z.↗
NASA NTRS1993

Operational overview of the NASA GTE/CITE 3 airborne instrument intercomparisons for sulfur dioxide, hydrogen sulfide, carbonyl sulfide, dimethyl sulfide, and carbon disulfide

This paper reports the overall experimental design and gives a brief overview of results from the third airborne Chemical Instrumentation Test and Evaluation (CITE 3) mission conducted as part of the National Aeronautics and Space Administration's Global Tropospheric Experiment. The primary objective of CITE 3 was to evaluate the capability of instrumentation for airborne measurements of ambient concentrations of SO2, H2S, CS, dimethyl sulfide, and carbonyl sulfide. Ancillary measurements augmented the intercomparison data in order to address the secondary objective of CITE 3 which was to address specific issues related to the budget and photochemistry of tropospheric sulfur species. The CITE 3 mission was conducted on NASA's Wallops Flight Center Electra aircraft and included a ground-based intercomparison of sulfur standards and intercomparison/sulfur science flights conducted from the NASA Wallops Flight Facility, Wallops Island, Virginia, followed by flights from Natal, Brazil. Including the transit flights, CITE 3 included 16 flights encompassing approximately 96 flight hours.

Hoell, James M., Jr.↗
NASA NTRS1993

Atmospheric measurements of carbonyl sulfide, dimethyl sulfide, and carbon disulfide using the electron capture sulfur detector

Measurements of atmospheric dimethyl sulfide (DMS), carbonyl sulfide (COS), and carbon disulfide (CS2) were conducted over the Atlantic Ocean on board the NASA Electra aircraft during the Chemical Instrumentation Test and Evaluation (CITE 3) project using the electron capture sulfur detector (ECD-S). The system employed cryogenic preconcentration of air samples, gas chromatographic separation, catalytic fluorination, and electron capture detection. Samples collected for DMS analysis were scrubbed of oxidants with NaOH impregnated glass fiber filters to preconcentration. The detection limits (DL) of the system for COS, DMS, and CS2 were 5, 5, and 2 ppt, respectively. COS concentrations ranged from 404 to 603 ppt with a mean of 489 ppt for measurements over the North Atlantic Ocean (31 deg N to 41 deg N), and from 395 to 437 ppt with a mean of 419 ppt for measurements over the Tropical Atlantic Ocean (11 deg S to 2 deg N). DMS concentrations in the lower marine boundary layer, below 600-m altitude, ranged from below DL to 150 ppt from flights over the North Atlantic, and from 9 to 104 ppt over the Tropical Atlantic. CS2 concentrations ranged from below DL to 29 ppt over the North Atlantic. Almost all CS2 measurements over the Tropical Atlantic were below DL.

Johnson, James E.↗
NASA NTRS1993

Measurements of atmospheric carbonyl sulfide during the NASA Chemical Instrumentation Test and Evaluation Project: Implications for the global COS budget

Atmospheric carbonyl sulfide COS concentrations were measured by three analytical systems during the Chemical Instrumentation Test and Evaluation (CITE 3) project. The three systems all used cryogenic sample preconcentration and gas chromatographic (GC) separation but differed in the method of detection. The FPD system used a flame photometric detector, the MS system used a mass selective detector, and the ECD-S system used a fluorinating catalyst followed by an electron capture detector. With the FPD system, we found a mean COS concentration of 510 ppt over the North Atlantic and 442 ppt over the Tropical Atlantic. With the ECD-S system, we found a mean COS concentration of 489 ppt over the North Atlantic and 419 ppt over the Tropical Atlantic. All three systems registered a latitudinal gradient in atmospheric COS of between 1.6 and 2.0 ppt per degree of latitude, with increasing COS concentrations northward which was similar to the gradient measured by Bingemer et al. (1990). It is difficult to reconcile the measured latitudinal concentration gradient with present theories of the global COS budget since the largest sink of COS is thought to be a flux to land plants, most of which are in the northern hemisphere.

Johnson, James E.↗
NASA NTRS1994

Structure-property relationships in addition polyimides. 1: Resins from four-ring aromatic diamines containing carbonyl and methylene groups

In an effort to improve the processing characteristics of addition-type polyimide resins the use of flexibilized four-ring aromatic diamine moieties was investigated. A series of 12 diamines containing carbonyl and methylene, as well as oxo and thio bridging groups, was synthesized. The diamines were polymerized with the dimethyl ester of 3.3', 4.4' - benzophenonetetracarboxylic acid (BTDE), using the monomethyl ester of nadic acid (NE) as an end-cap. The effect of diamine structure on the solubility and rheological properties during cure was determined. This paper also describes the effect of diamine structure and formulated molecular weight on the glass transition temperature and thermo-oxidative stability at elevated temperatures after various post-cure regimes. The results indicate that polyimides from some of the diamines containing methylene connecting groups have potential as matrix resins for long-term applications at temperatures up to 300 C.

Delvigs, Peter↗
NASA NTRS1995

Quantum yield for carbon monoxide production in the 248 nm photodissociation of carbonyl sulfide (OCS)

Tunable diode laser absorption spectroscopy has been coupled with excimer laser flash photolysis to measure the quantum yield for CO production from 248 nm photodissociation of carbonyl sulfide (OCS) relative to the well-known quantum yield for CO production from 248 nm photolysis of phosgene (Cl2CO2). The temporal resolution of the experiments was sufficient to distinguish CO formed directly by photodissociation from that formed by subsequent S((sup 3)P(sub J)) reaction with OCS. Under the experimental conditions employed, CO formation via the fast S((sup 1)D(sub 2)) + OCS reaction was minimal. Measurements at 297K and total pressures from 4 to 100 Torr N2 + N2O show the CO yield to be greater than 0.95 and most likely unity. This result suggests that the contribution of OCS as a precursor to the lower stratospheric sulfate aerosol layer is somewhat larger than previously thought.

Zhao, Z.↗
NASA NTRS1995

Solid Carbonyl Sulphide (OCS) in W33A

We present ground-based observations of the 2041/cm (4.9 micrometer) absorption feature toward the deeply embedded protostar W33A. We attribute this interstellar feature to solid carbonyl sulphide (OCS) embedded in icy grain mantles along the line of sight. We have made an extensive laboratory study of the infrared characteristics of OCS in various ice mixtures. Studies of the 2041/cm band of solid OCS and solid mixtures containing OCS show that its shape and peak position are sensitive to the molecular environment of the OCS molecule. Mie scattering calculations show that the peak position and profile of the OCS band depend on the shape and size of the absorbing grain when the OCS concentration is larger than 0.05. For lower OCS concentrations, laboratory-measured bulk spectra agree very well with the absorption spectra of small grains. We have compared the observed feature with laboratory and theoretical spectra of astrophysically relevant mixtures. The best agreement is obtained for mixtures with traces of OCS in a methanol-rich matrix. This would suggest the presence of independent grain components and in particular of a minor fraction of methanol-rich icy grain mantles in which OCS is embedded. From the strength of the absorption feature we deduce a OCS/H 20 ratio, along the line of sight, of 4 x 10(exp -4).

Palumbo, M. E.↗
NASA NTRS1995

Solid Carbonyl Sulphide (OCS) in W33A

We present ground-based observations of the 2041 cm(exp -1) (4.9 mm) absorption feature toward the deeply embedded protostar W33A. We attribute this interstellar feature to solid carbonyl sulphide (OCS) embedded in icy grain mantles along the line of sight. We have made an extensive laboratory study of the infrared characteristics of OCS in various ice mixtures. Studies of the 2041 cm(exp -1) band of solid OCS and solid mixtures containing OCS show that its shape and peak position are sensitive to the molecular environment of the OCS molecule. Mie scattering calculations show that the peak position and profile of the OCS band depend on the shape and size of the absorbing grain when the OCS concentration is larger than 0.05. For lower OCS concentrations, laboratory-measured bulk spectra agree very well with the absorption spectra of small grains. We have compared the observed feature with laboratory and theoretical spectra of astrophysically relevant mixtures. The best agreement is obtained for mixtures with traces of OCS in a methanol-rich matrix. This would suggest the presence of independent grain components and in particular of a minor fraction of methanol-rich icy grain mantles in which OCS is embedded. From the strength of the absorption feature we deduce a OCS/H2O ratio, along the line of sight, of 4 x 10(exp -4).

Palumbo, M. E.↗
NASA NTRS1996

Atmospheric Sulfur Cycle Effects of Carbonyl Sulfide (OCS)

Carbonyl Sulfide(OCS) is considered to be one of the major sources of sulfur appearing in the stratosphere due to its relative inertness, about I to 10 yearsl. However, the roles of OCS as well as other reduced sulfur compounds such as carbon disulfide (CS2), hydrogen sulfide (H2S), and dimethyl disulfide(CH3)2S2, are not completely understood in the atmosphenc sulfur cycle. Consequently vely little information is available about the effect of sulfur compounds in the stratosphere. The ability of OCS to penetrate into the stratosphere makes it an excellent tracer for study of the role of the sulfi r cycle in stratospheric chemistry. Previously techniques such as gas chromatography and whole air sampling have been used to measure OCS analytically. Each technique had its drawbacks however, with both being quite slow, and whole air sampling being somewhat unreliable. With molecular spectroscopy, however, it has been found in recent years that the tunable diode laser absorption spectrometer (TDL) provides a very rapid and accurate method of measuring OCS and other trace gases

McBee, Joshua↗
NASA NTRS2004

Deployment of a Fast-GCMS System to Measure C2 to C5 Carbonyls, Methanol and Ethanol Aboard Aircraft

Through funding of this proposal, a fast response gas chromatograph/mass spectrometer (FGCMS) instrument to measure less than or equal to C4 carbonyl compounds and methanol was developed for the NASA GTE TRACE-P (Global Tropospheric Experiment, Transport And Chemical Evolution Over The Pacific) mission. The system consists of four major components: sample inlet, preconcentration system, gas chromatograph (GC), and detector. The preconcentration system is a custom-built cryogen-conservative system. The GC is a compact, custom-built unit that can be temperature programmed and rapidly cooled. Detection is accomplished with an Agilent Technologies 5973 mass spectrometer. The FGCMS instrument provides positive identification because the compounds are chromatographically separated and mass selected. During TRACE-P, a sample was analyzed every 5 minutes. The FGCMS limit of detection was between 5 and 75 pptv, depending on the compound. The entire instrument package is contained in a standard NASA instrument rack (106 cm x 61 cm x 135 cm), consumes less than 1200 watts and is fully automated with LabViEW 6i. Methods were developed or producing highly accurate gas phase standards for the target compounds and for testing the system in the presence of potential interferents. This report presents data on these tests and on the general overall performance of the system in the laboratory and aboard the DC-8 aircraft during the mission. Vertical profiles for acetaldehyde, methanol, acetone, propanal, methyl ethyl ketone, and butanal from FGCMS data collected over the entire mission are also presented.

Apel, Eric C.↗
NASA NTRS2008

Photosynthetic Control of Atmospheric Carbonyl Sulfide during the Growing Season

Climate models incorporate photosynthesis-climate feedbacks, yet we lack robust tools for large-scale assessments of these processes. Recent work suggests that carbonyl sulfide (COS), a trace gas consumed by plants, could provide a valuable constraint on photosynthesis. Here we analyze airborne observations of COS and carbon dioxide concentrations during the growing season over North America with a three-dimensional atmospheric transport model. We successfully modeled the persistent vertical drawdown of atmospheric COS using the quantitative relation between COS and photosynthesis that has been measured in plant chamber experiments. Furthermore, this drawdown is driven by plant uptake rather than other continental and oceanic fluxes in the model. These results provide quantitative evidence that COS gradients in the continental growing season may have broad use as a measurement-based photosynthesis tracer.

Campbell, J. Elliott↗
NASA NTRS2020

Carbonyl Sulfide (OCS): Detections in Comets C/2002 T7 (LINEAR), C/2015 ER61 (PanSTARRS), and 21P/Giacobini-Zinner and Stringent Upper Limits in 46P/Wirtanen

Carbonyl sulfide (OCS) is one of the sulfur-bearing molecules detected in different astronomical environments, including comets. The present-day sulfur chemistry in comets may reveal much about the origin of these ices and their subsequent processing history. Cometary sulfur molecules such as H2S, H2CS, SO2, SO, CS, CS2, S2, and NS have been detected in many comets. However, OCS, the only sulfur-bearing species with fluorescence emission lines at infrared wavelengths, is under-represented in comet volatile studies, having been reported in only six comets so far. We targeted OCS with the NASA Infrared Telescope Facility in comets 46P/Wirtanen, 21P/Giacobini–Zinner, and C/2015 ER61 (PanSTARRS) in 2017–2018 using the high-resolution iSHELL spectrograph, and in C/2002 T7 (LINEAR) in 2004 using the heritage CSHELL spectrograph. In comet C/2015 ER61, the OCS abundance was similar to those measured in bright comets such as comets C/2012 S1 (ISON) and C/1996 B2 (Hyakutake), whereas in C/2002 T7 it was relatively depleted. Our OCS measurement in 21P/Giacobini–Zinner is the first definitive detection of this molecule in a Jupiter-family comet from a ground-based facility and is close to the average OCS abundance determined in comet 67P/Churyumov–Gerasimenko by the Rosetta mission. Our 3σ upper limit for comet 46P/Wirtanen is the lowest reported OCS abundance in any comet. We present production rates and mixing ratios (with respect to H2O) for these comets and place our results in the context of comets measured to date.

Mohammad Saki↗
NASA NTRS2020

Carbonyl Sulfide (OCS): Detections in Comets C/2002 T7 (LINEAR), C/2015 ER61 (PanSTARRS), and 21P/Giacobini-Zinner and Stringent Upper Limits in 46P/Wirtanen

Carbonyl sulfide(OCS)is one of the sulfur-bearing molecules detected in different astronomical environments, including comets. The present-day sulfur chemistry in comets may reveal much about the origin of these ices and their subsequent processing history. Cometary sulfur molecules such as H2S, H2CS, SO2, SO, CS, CS2,S2, and NShave been detected in many comets. However, OCS, the only sulfur-bearing species with fluorescence emission lines at infrared wavelengths, is under-represented in comet volatile studies, having been reported in only six comets so far. We targeted OCS with the NASA Infrared Telescope Facility in comets 46P/Wirtanen, 21P/Giacobini–Zinner, and C/2015 ER61(Pan STARRS)in 2017–2018 using the high-resolution iSHELL spectrograph, and in C/2002 T7(LINEAR)in 2004 using the heritage CSHELL spectrograph. In comet C/2015 ER61, the OCS abundance was similar to those measured in bright comets such as comets C/2012 S1(ISON)and C/1996 B2(Hyakutake), whereas in C/2002 T7 it was relatively depleted. Our OCS measurement in21P/Giacobini–Zinner is the first definitive detection of this molecule in a Jupiter-family comet from a ground-based facility and is close to the average OCS abundance determined in comet 67P/ Churyumov–Gerasimenko by the Rosetta mission. Our 3σupper limit for comet 46P/Wirtanen is the lowest reported OCS abundance in any comet. We present production rates and mixing ratios(with respect to H2O)for these comets and place our results in the context of comets measured to date

Mohammad Saki↗