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At least 55 records · Page 3

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↗

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.↗

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↗

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↗

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↗

Fast metastable fragments produced by dissociative excitation of carbonyl sulfide

Dissociative excitation of OCS by electron impact has been studied using the method of translational spectroscopy. Time-of-flight distributions and excitation functions of the fast metastable fragments have been measured. The results are compared with similar measurements on CO2 and show that a variety of metastable fragments including CO(a 3Pi), S(5S), O(5S) as well as long-lived high-lying atomic and molecular Rydberg fragments can contribute to dissociation.

Van Brunt, R. J.↗

Ab initio projected-unrestricted Hartree-Fock calculation of some potential energy curves for carbonyl fluoride

Some potential energy curves for CF2O were calculated using projected-unrestricted Hartree-Fock (PUHF) theory. The calculations employed a contracted (4s 3p) Gaussian-type atomic orbital basis set. Bound states were found for the X-tilde 1A1 and 1,3A2 states while the 1,3B1 and 1,3B2 states were repulsive in the valence representation. The merits of the PUHF treatment for excited states are discussed. The results are discussed in terms of available experimental information and previous calculations with particular emphasis on the question of the photolysis channels open in the solar spectral region.

Brewer, D. A.↗

Long wavelength carbonyl sulfide photodissociation

The aeronomic implications of a preliminary observation of weak OCS photoabsorption above 270 nm are investigated. It is argued that the measured cross section is consistent with a forbidden transition in this wavelength region. Model calculations are made for the OCS photodissociation rates in daylight, the OCS and SO2 distributions in the upper atmosphere, and the budgets of sulfur in the stratosphere and OCS in the troposphere, assuming various extrapolations of the measured OCS absorption cross sections and quantum yields to longer wavelengths. It is shown that weak OCS absorption above 300 nm can have important consequences for all of these quantities. Laboratory and field experiments are identified which might lead to a better understanding of the atmospheric OCS cycle.

Turco, R. P.↗