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NASA NTRS2018

Spatial and Seasonal Variations in C3Hx Hydrocarbon Abundance in Titan's Stratosphere from Cassini CIRS Observations

Of the C3Hx hydrocarbons, propane (C3H8) and propyne (methylacetylene, CH3C2H) were first detected in Titan’s atmosphere during the Voyager 1 flyby in 1980. Propene (propylene, C3H6) was first detected in 2013 with data from the Composite InfraRed Spectrometer (CIRS) instrument on Cassini. We present the first measured abundance profiles of propene on Titan from radiative transfer modeling, and compare our measurements to predictions derived from several photochemical models. Near the equator, propene is observed to have a peak abundance of 10 ppbv at a pressure of 0.2 mbar. Several photochemical models predict the amount at this pressure to be in the range 0.3–1 ppbv and also show a local minimum near 0.2 mbar which we do not see in our measurements. We also see that propene follows a different latitudinal trend than the other C3 molecules. While propane and propyne concentrate near the winter pole, transported via a global convective cell, propene is most abundant above the equator. We retrieve vertical abundances profiles between 125 km and 375 km for these gases for latitude averages between 60°S–20°S, 20°S–20°N, and 20°N–60°N over two time periods, 2004 through 2009 representing Titan’s atmosphere before the 2009 equinox, and 2012 through 2015 representing time after the equinox. Additionally, using newly corrected line data, we determined an updated upper limit for allene (propadiene, CH2CCH2, the isomer of propyne). We claim a 3-σ upper limit mixing ratio of 2.5 × 10(exp −9) within 30° of the equator. The measurements we present will further constrain photochemical models by refining reaction rates and the transport of these gases throughout Titan’s atmosphere.

Lombardo, Nicholas A.↗
NASA NTRS2018

Maps of Tethys' Thermophysical Properties

On 11th April 2015 Cassini's Composite Infrared Spectrometer (CIRS) made a series of observations of Tethys’ daytime anti-Saturn hemisphere over a nine-hour time period. During this time the sub-spacecraft position was remarkably stable (0.3° S to 3.9° S; 153.2° W to 221.8° W), and so these observations provide unprecedented coverage of diurnal temperature variations on Tethys’ anti-Saturn hemisphere. In 2012 a thermal anomaly was discovered at low latitudes on Tethys’ leading hemisphere; it appears cooler during the day and warmer at night than its surroundings (Howett et al., 2012) and is spatially correlated with a decrease in the IR3/UV3 visible color ratio (Schenk et al., 2011). The cause of this anomaly is believed to be surface alteration by high-energy electrons, which preferentially bombard low-latitudes of Tethys’ leading hemisphere (Schenk et al., 2011; Howett et al., 2012; Paranicas et al. 2014; Schaible et al., 2017). The thermal anomaly was quickly dubbed “Pac-Man” due to its resemblance to the 1980s video game icon. We use these daytime 2015 CIRS data, along with two sets of nighttime CIRS observations of Tethys (from 27 June 2007 and 17 August 2015) to make maps of bolometric Bond albedo and thermal inertia variations across the anti-Saturn hemisphere of Tethys (including the edge of its Pac-Man region). These maps confirm the presence of the Pac-Man thermal anomaly and show that while Tethys’ bolometric Bond albedo varies negligibly outside and inside the anomaly (0.69 plus or minus 0.02 inside, compared to 0.71 plus or minus 0.04 outside) the thermal inertia varies dramatically (29 plus or minus 10 J m−2 K−1 s−1/2 inside, compared to 9 plus or minus 4 J m−2 K−1 s−1/2 outside). These thermal inertias are in keeping with previously published values: 25 plus or minus 3 J m−2 K−1 s−1/2 inside, and 5 ± 1 J m−2 K−1 s−1/2 outside the anomaly (Howett et al., 2012). A detailed analysis shows that on smaller spatial-scales the bolometric Bond albedo does vary: increasing to a peak value at 180° W. For longitudes between approximately 100° W and approximately 160° W the thermal inertia increases from northern to southern latitudes, while the reverse is true for bolometric Bond albedo. The thermal inertia on Tethys generally increases towards the center of its leading hemisphere but also displays other notable small-scale variations. These thermal inertia and bolometric Bond albedo variations are perhaps due to differences in competing surface modification by E ring grains and high-energy electrons which both bombard Tethys’ leading hemisphere (but in different ways). A comparison between the observed temperatures and our best thermal model fits shows notable discrepancies in the morning warming curve, which may provide evidence of regional variations in surface roughness effects, perhaps again due to variations in surface alteration mechanisms.

Howett, C. J. A.↗
NASA NTRS2019

Ethane in Titan's Stratosphere from Cassini CIRS Far- and Mid-Infrared Spectra

The Cassini Composite Infrared Spectrometer (CIRS) observed thermal emission in the far- and mid-infrared (from 10 to 1500 cm(exp −1)), enabling spatiotemporal studies of ethane on Titan across the span of the Cassini mission from 2004 through 2017. Many previous measurements of ethane on Titan have relied on modeling the molecule’s mid-infrared ν(sub 12) band, centered on 822 cm(exp −1). Other bands of ethane at shorter and longer wavelengths were seen, but have not been modeled to measure ethane abundance. Spectral line lists of the far-infrared ν(sub 4) torsional band at 289 cm(exp −1) and the mid-infrared ν(sub 8) band centered at 1468 cm(exp −1) have recently been studied in the laboratory. We model CIRS observations of each of these bands (along with the ν(sub 12) band) separately and compare the retrieved mixing ratios from each spectral region. Nadir observations of the ν(sub 4) band probe the low stratosphere below 100 km. Our equatorial measurements at 289 cm(exp −1) show an abundance of (1.0±0.4)x10(exp −5) at 88 km from 2007 to 2017. This mixing ratio is consistent with measurements at higher altitudes, in contrast to the depletion that many photochemical models predict. Measurements from the ν(sub 12) and ν(sub 8) bands are comparable to each other, with the ν(sub 12) band probing an altitude range that extends deeper in the atmosphere. We suggest that future studies of planetary atmospheres may observe the ν(sub 8) band, enabling shorter wavelength studies of ethane. There may also be an advantage to observing both the ethane ν(sub 8) band and nearby methane ν(sub 4) band in the same spectral window.

Lombardo, Nicholas A.↗
NASA NTRS2019

Detailed Infrared Study of Amorphous to Crystalline Propionitrile Ices Relevant to Observed Spectra of Titan's Stratospheric Ice Clouds

We have conducted a comprehensive study of propionitrile (C2H5CN) ice from the amorphous to crystalline phase in order to provide detailed information on this specific cyanide, which may potentially contribute to the chemical composition of the Haystack ice cloud observed in Titan's stratosphere by the Cassini Composite InfraRed Spectrometer (CIRS). Infrared transmission spectra of thin films of pure propionitrile ices deposited at low temperature (30-160 K) were collected from 50 cm1 to 11,700 cm1 (200-0.85 m). The far-infrared spectral region was specifically targeted to compare with CIRS far-infrared limb spectra. The temperature and time evolution of C2H5CN ice was thoroughly investigated to better understand discrepancies reported in pre- viously published laboratory studies on the crystalline phase of C2H5CN. Specifically, we observe peculiar temperature and time-driven ice phase transitions, revealed by significant spectral variations in the ice, which stabilizes once a complete crystalline phase is achieved. From these results, the crystalline phase of propionitrile ice was identified at deposition temperatures greater than or equal to 135 K and < 140 K. Our findings corro- borate previous studies that ruled out pure propionitrile ice as the sole chemical identity of Titan's observed Haystack emission feature. In order to understand and identify the Haystack cloud, we have initiated co-de- position experiments that incorporate mixtures of Titan-relevant organics, many of which have corresponding vapors that are abundantly present in Titan's stratosphere. In this paper, we present the result of one example of a co-deposited ternary ice mixture containing 16% hydrogen cyanide (HCN), 23% C2H5CN, and 61% benzene (C6H6). Although this co-condensed ice mixture is the best fit thus far obtained to match the broad width of the Haystack, it is still not the appropriate chemical candidate. However, it reveals an intriguing result: the strong lattice mode of pure C2H5CN ice is drastically altered by the surrounding molecules as a result of mixing in a co- condensed phase. The laboratory results reported here on propionitrile ice may help to further constrain the chemical identification of Titan's stratospheric Haystack ice cloud, as well as improve on the current state of knowledge of Titan's stratospheric ice cloud chemistry.

Nna-Mvondo, Delphine↗
NASA NTRS2019

Titan Surface Temperatures During the Cassini Mission

By the close of the Cassini mission in 2017 the Composite Infrared Spectrometer had recorded surface brightnesstemperatures on Titan for 13 yr (almost half a Titan year). We mapped temperatures in latitude from pole to pole inseven time segments from northern mid-winter to northern summer solstice. At the beginning of the mission thewarmest temperatures were centered at 13 S where they peaked at 93.9 K. Temperatures fell off by about 4 Ktoward the north pole and 2 K toward the south pole. As the seasons progressed the warmest temperatures shiftednorthward, tracking the subsolar point, and at northern summer solstice were centered at 24 N. While moving norththe peak temperature decreased by about 1 K, reaching 92.8 K at solstice. At solstice the fall-off toward the northand south poles were 1 K and 3 K, respectively. Thus the temperature range was the same 2 K at the two poles. Ourobserved surface temperatures agree with recent general circulation model results that take account of methanehydrology and imply that hemispherical differences in Titan's topography may play a role in the north?southasymmetry on Titan.

Jennings, D. E.↗
NASA NTRSDate not supplied

Integrated laboratory, modeling and observational investigations of the condensation of benzene on Titan's stratospheric aerosols

Aerosols in Titan’s atmosphere play an important role in determining its thermal structure and can act as condensation nuclei for the formation of clouds. The global circulation of Titan’s atmosphere reversed within the two years following the northern spring equinox in August 2009, increasing the mixing ratios of benzene (C6H6) and other species at the South pole. A simultaneous strong cooling above the south pole (dropping temperatures below 120 K) resulted in conditions where molecules could condense at unusually high altitudes (>250 km). C6H6 and HCN ices have been detected by the Composite Infrared Spectrometer (CIRS) and the Visible and Infrared Mapping Spectrometer (VIMS), respectively, in the South polar cloud system, but the existing laboratory data is insufficient to allow models to reproduce the formation of the observed cloud system. We will present the preliminary results and the overall scope of a newly funded NASA SMD Cassini Data Analysis Program (CDAP) project which proposes to combine laboratory, modeling and observational studies to investigate the condensation of benzene on Titan’s aerosol as an important component of the cloud system that appeared during the autumn at 300 km above Titan’s South pole.

E. Sciamma-O’Brien↗
NASA NTRS2019

Detailed Infrared Study of Amorphous to Crystalline Propionitrile Ices Relevant to Observed Spectra of Titan's Stratospheric Ice Clouds

We have conducted a comprehensive study of propionitrile (C2H5CN) ice from the amorphous to crystalline phase in order to provide detailed information on this specific cyanide, which may potentially contribute to the chemical composition of the Haystack ice cloud observed in Titan’s stratosphere by the Cassini Composite InfraRed Spectrometer (CIRS). Infrared transmission spectra of thin films of pure propionitrile ices deposited at low temperature (30 – 160 K) were collected from 50 cm(exp -1) to 11700 cm(exp -1) (200 – 0.85 μm). The far-infrared spectral region was specifically targeted to compare with CIRS far-infrared limb spectra. The temperature and time evolution of C2H5CN ice was thoroughly investigated to better understand discrepancies reported in previously published laboratory studies on the crystalline phase of C2H5CN. Specifically, we observe peculiar temperature and time-driven ice phase transitions, revealed by significant spectral variations in the ice, which stabilizes once a complete crystalline phase is achieved. From these results, the crystalline phase of propionitrile ice was identified at deposition temperatures greater than or equal to 135 K and less than 140 K. Our findings corroborate previous studies that ruled out pure propionitrile ice as the sole chemical identity of Titan’s observed Haystack emission feature. As a result, we have initiated co-deposition experiments that incorporate mixtures of Titan relevant organics, many of which have corresponding vapors that are abundantly present in Titan's stratosphere. In this paper, we present the result of one example of a co-deposited trinary ice mixture containing 16% hydrogen cyanide (HCN), 23% C2H5CN, and 61% benzene (C6H6). Although this co-condensed ice mixture is the best fit thus far obtained to match the broad width of the Haystack, it is still not the appropriate chemical candidate. However, it reveals an intriguing result: the strong lattice mode of pure C2H5CN ice is drastically altered by the surrounding molecules as a result of mixing in a co-condensed phase. The laboratory results reported here on propionitrile ice may help to further constrain the chemical identification of Titan’s stratospheric Haystack ice cloud, as well as improve on the current state of knowledge of Titan's stratospheric ice cloud chemistry.

Delphine Nna-Mvondo↗
NASA NTRS2019

Detailed Infrared Study of Amorphous to Crystalline Propionitrile Ices Relevant to Observed Spectra of Titan's Stratospheric Ice Clouds

We have conducted a comprehensive study of propionitrile (C2H5CN) ice from the amorphous to crystalline phase in order to provide detailed information on this specific cyanide, which may potentially contribute to the chemical composition of the Haystack ice cloud observed in Titan's stratosphere by the Cassini Composite InfraRed spectrometer (CIRS). Infrared transmission spectra of thin films of pure propionitrile ices deposited at low temperature (30–160 K) were collected from 50 cm(exp −1) to 11,700 cm(exp −1) (200–0.85 μm). The far-infrared spectral region was specifically targeted to compare with CIRS far-infrared limb spectra. The temperature and time evolution of C2H5CN ice was thoroughly investigated to better understand discrepancies reported in previously published laboratory studies on the crystalline phase of C2H5CN. Specifically, we observe peculiar temperature and time-driven ice phase transitions, revealed by significant spectral variations in the ice, which stabilizes once a complete crystalline phase is achieved. From these results, the crystalline phase of propionitrile ice was identified at deposition temperatures greater than or equal to 135 K and <140 K. Our findings corroborate previous studies that ruled out pure propionitrile ice as the sole chemical identity of Titan's observed Haystack emission feature. In order to understand and identify the Haystack cloud, we have initiated co-deposition experiments that incorporate mixtures of Titan-relevant organics, many of which have corresponding vapors that are abundantly present in Titan's stratosphere. In this paper, we present the result of one example of a co-deposited ternary ice mixture containing 16% hydrogen cyanide (HCN), 23% C2H5CN, and 61% benzene (C6H6). Although this co-condensed ice mixture is the best fit thus far obtained to match the broad width of the Haystack, it is still not the appropriate chemical candidate. However, it reveals an intriguing result: the strong lattice mode of pure C2H5CN ice is drastically altered by the surrounding molecules as a result of mixing in a co-condensed phase. The laboratory results reported here on propionitrile ice may help to further constrain the chemical identification of Titan's stratospheric Haystack ice cloud, as well as improve on the current state of knowledge of Titan's stratospheric ice cloud chemistry.

Delphine Nna-Mvondo↗
NASA NTRS2019

Detailed infrared study of amorphous to crystalline propionitrile ices relevant to observed spectra of Titan's stratospheric ice clouds

We have conducted a comprehensive study of propionitrile (C2H5CN) ice from the amorphous to crystalline phase in order to provide detailed information on this specific cyanide, which may potentially contribute to the chemical composition of the Haystack ice cloud observed in Titan’s stratosphere by the Cassini Composite InfraRed Spectrometer (CIRS). Infrared transmission spectra of thin films of pure propionitrile ices deposited at low temperature (30 – 160 K) were collected from 50 cm-1 to 11,700 cm-1 (200 – 0.85 μm). The far-infrared spectral region was specifically targeted to compare with CIRS far-infrared limb spectra. The temperature and time evolution of C2H5CN ice was thoroughly investigated to better understand discrepancies reported in previously published laboratory studies on the crystalline phase of C2H5CN. Specifically, we observe peculiar temperature and time-driven ice phase transitions, revealed by significant spectral variations in the ice, which stabilizes once a complete crystalline phase is achieved. From these results, the crystalline phase of propionitrile ice was identified at deposition temperatures greater than or equal to 135 K and less than 140 K. Our findings corroborate previous studies that ruled out pure propionitrile ice as the sole chemical identity of Titan’s observed Haystack emission feature. As a result, we have initiated co-deposition experiments that incorporate mixtures of Titan-relevant organics, many of which have corresponding vapors that are abundantly present in Titan's stratosphere. In this paper, we present one example of a co-deposited trinary ice mixture containing 16% hydrogen cyanide (HCN), 23% C2H5CN, and 61% benzene (C6H6). Although this co-condensed ice mixture is a poor spectral match for the Haystack, it reveals an intriguing result: the strong lattice mode of pure C2H5CN ice is drastically altered by the surrounding molecules as a result of mixing in a co-condensed phase. The laboratory results reported here on propionitrile ice may help to further constrain the chemical identification of Titan’s stratospheric Haystack ice cloud, as well as improve on the current state of knowledge of Titan's stratospheric ice cloud chemistry.

Ices↗
NASA NTRS2018

Spatial and Seasonal Variations in C3Hx Hydrocarbon Abundance in Titan’s Stratosphere from Cassini CIRS Observations

Of the C3Hx hydrocarbons, propane (C3H8) and propyne (methylacetylene, CH3C2H) were first detected in Titan’s atmosphere during the Voyager 1 flyby in 1980. Propene (propylene, C3H6) was first detected in 2013 with data from the Composite InfraRed Spectrometer (CIRS) instrument on Cassini. We present the first measured abundance profiles of propene on Titan from radiative transfer modeling, and compare our measurements to predictions derived from several photochemical models. Near the equator, propene is observed to have a peak abundance of 10 ppbv at a pressure of 0.2 mbar. Several photochemical models predict the amount at this pressure to be in the range 0.3 - 1 ppbv and also show a local minimum near 0.2 mbar which we do not see in our measurements. We also see that propene follows a different latitudinal trend than the other C3 molecules. While propane and propyne concentrate near the winter pole, transported via a global convective cell, propene is most abundant above the equator. We retrieve vertical abundances profiles between 125 km and 375 km for these gases for latitude averages between 60◦S to 20◦S, 20◦S to 20◦N, and 20◦N to 60◦N over two time periods, 2004 through 2009 representing Titan’s atmosphere before the 2009 equinox, and 2012 through 2015 representing time after the equinox. Additionally, using newly corrected line data, we determined an updated upper limit for allene (propadiene, CH2CCH2), the isomer of propyne). The measurements we present will further constrain photochemical models, by refining reaction rates and the transport of these gases throughout Titan’s atmosphere.

Nicholas A. Lombardo↗
NASA NTRS2019

Ethane in Titan's Stratosphere from Cassini CIRS Far- and Mid-infrared Spectra

The Cassini Composite Infrared Spectrometer (CIRS) observed thermal emission in the far- and mid-infrared (from 10 to 1500 cm−1), enabling spatiotemporal studies of ethane on Titan across the span of the Cassini mission from 2004 through 2017. Many previous measurements of ethane on Titan have relied on modeling the molecule's mid-infrared ν12 band, centered on 822 cm−1. Other bands of ethane at shorter and longer wavelengths were seen, but have not been modeled to measure ethane abundance. Spectral line lists of the far-infrared ν4 torsional band at 289 cm−1 and the mid-infrared ν8 band centered at 1468 cm−1 have recently been studied in the laboratory. We model CIRS observations of each of these bands (along with the ν12 band) separately and compare the retrieved mixing ratios from each spectral region. Nadir observations of the ν4 band probe the low stratosphere below 100 km. Our equatorial measurements at 289 cm−1 show an abundance of (1.0 ± 0.4) × 10−5 at 88 km from 2007 to 2017. This mixing ratio is consistent with measurements at higher altitudes, in contrast to the depletion that many photochemical models predict. Measurements from the ν12 and ν8 bands are comparable to each other, with the ν12 band probing an altitude range that extends deeper in the atmosphere. We suggest that future studies of planetary atmospheres may observe the ν8 band, enabling shorter wavelength studies of ethane. There may also be an advantage to observing both the ethane ν8 band and nearby methane ν4 band in the same spectral window.

Nicholas A Lombardo↗
NASA NTRS2020

Temperature and Chemical Species Distributions in the Middle Atmosphere Observed during Titan's Late Northern Spring to Early Summer

We present a study of the seasonal evolution of Titan’s thermal field and distributions of haze, C2H2, C2H4, C2H6, CH3C2H, C3H8, C4H2, C6H6, HCN, and HC3N from March 2015 (Ls = 66°) to September 2017 (Ls = 93°) (i.e., from the last third of northern spring to early summer). We analyzed thermal emission of Titan’s atmosphere acquired by the Cassini Composite Infrared Spectrometer with limb and nadir geometry to retrieve the stratospheric and mesospheric temperature and mixing ratios pole-to-pole meridional cross sections from 5 mbar to 50 μbar (120–650 km). The southern stratopause varied in a complex way and showed a global temperature increase from 2015 to 2017 at high-southern latitudes. Stratospheric southern polar temperatures, which were observed to be as low as 120 K in early 2015 due to the polar night, showed a 30 K increase (at 0.5 mbar) from March 2015 to May 2017 due to adiabatic heating in the subsiding branch of the global overturning circulation. All photochemical compounds were enriched at the south pole by this subsidence. Polar cross sections of these enhanced species, which are good tracers of the global dynamics, highlighted changes in the structure of the southern polar vortex. These high enhancements combined with the unusually low temperatures (<120 K) of the deep stratosphere resulted in condensation at the south pole between 0.1 and 0.03 mbar (240–280 km) of HCN, HC3N, C6H6 and possibly C4H2 in March 2015 (Ls = 66°). These molecules were observed to condense deeper with increasing distance from the south pole. At high-northern latitudes, stratospheric enrichments remaining from the winter were observed below 300 km between 2015 and May 2017 (Ls = 90°) for all chemical compounds and up to September 2017 (Ls = 93°) for C2H2, C2H4, CH3C2H, C3H8, and C4H2. In September 2017, these local enhancements were less pronounced than earlier for C2H2, C4H2, CH3C2H, HC3N, and HCN, and were no longer observed for C2H6 and C6 H6, which suggests a change in the northern polar dynamics near the summer solstice. These enhancements observed during the entire spring may be due to confinement of this enriched air by a small remaining winter circulation cell that persisted in the low stratosphere up to the northern summer solstice, according to predictions of the Institut Pierre Simon Laplace Titan Global Climate Model (IPSL Titan GCM). In the mesosphere we derived a depleted layer in C2H2, HCN, and C2H6 from the north pole to mid-southern latitudes, while C4H2, C3H4, C2H4, and HC3N seem to have been enriched in the same region. In the deep stratosphere, all molecules except C2H4 were depleted due to their condensation sink located deeper than 5 mbar outside the southern polar vortex. HCN, C4H2, and CH3C2H volume mixing ratio cross section contours showed steep slopes near the mid-latitudes or close to the equator, which can be explained by upwelling air in this region. Upwelling is also supported by the cross section of the C2H4 (the only molecule not condensing among those studied here) volume mixing ratio observed in the northern hemisphere. We derived the zonal wind velocity up to mesospheric levels from the retrieved thermal field. We show that zonal winds were faster and more confined around the south pole in 2015 (Ls = 67−72°) than later. In 2016, the polar zonal wind speed decreased while the fastest winds had migrated toward low-southern latitudes.

S Vinatier↗
NASA NTRSDate not supplied

Compositional Analysis of Titan’s Atmosphere Using Spitzer Infrared Spectrograph Data

We present, for the first time, infrared spectra from the Spitzer Space Telescope’s Infrared Spectrograph (IRS) (2004-2008) of Titan in both the short wavelength-low resolution(SL, R=60~127,5.13-14.29 μm) and short wavelength-high resolution channels (SH, R=600, 9.89-19.51 μm) showing the emissions of CH4, C2H4, C2H2, C2H6, HCN, CO2, HC3N, C3H4, C4H2, and C3H8. Spitzer IRS data has been used to measure atmospheric composition of various Solar System bodies, including Neptune [1] and Uranus [2],[3]. Although Spitzer took multiple dedicated observations of Titan, none of the results have been modeled before. We conduct our own investigation of these datasets and search for new results. We retrieve temperature and gas composition profiles and compare the results obtained for Titan to those of the Cassini Composite Infrared Spectrometer (CIRS) and the Infrared Space Observatory Short Wavelength Spectrometer [4], and comment on the effect of spectral resolution on retrieved information content. We conclude by recommending gaps in current spectroscopic knowledge of molecular bands that could be addressed by theoretical and laboratory study to aid future astronomical studies of Titan, for example the James Webb Space Telescope (JWST) and the Stratospheric Observatory for Infrared Astronomy (SOFIA) Acknowledgments: Data analyzed in this project is public available online on the Spitzer Heritage Archive (sha.ipac.caltech.edu). This research has made use of the NASA/IPAC Infrared Science Archive, which is funded by the National Aeronautics and Space Administration and operated by the California Institute of Technology.

Titan↗
NASA NTRSDate not supplied

A Search for Butane in Titan’s Atmosphere using Cassini CIRS Infrared Spectra

The atmosphere of Saturn’s moon, Titan, is unlike any other. Photochemistry and ion chemistry in the upper atmosphere process the major atmospheric constituents, molecular nitrogen (N2) and methane (CH4), into larger and more complex molecules including hydrocarbons and nitriles. To date there are ten hydrocarbons heavier than methane that have been detected, including large quantities of the saturated hydrocarbons (alkanes) ethane (C2H6) and propane (C3H8). In addition to being significant trace gases of the atmosphere, these species condense, rain out and add to the volume of Titan’s hydrocarbon lakes and seas. The fourth lightest alkane, butane (C4H10),comes in two structural forms: an unbranched carbon chain (n-butane) and a branched chain (i-butane). The relative production rates of both these isomers are presently unknown, although the circumstantial case for butane to be present in detectable amounts is strong, based on photochemical models and from Cassini low-resolution mass spectrometry of the ionosphere. Butane, like its lighter siblings ethane and propane, is thought to be present in Titan’s lakes and seas where it may be active in forming molecular ‘co-crystals’ with acetylene (C2H2). We report on our recent attempts to detect both forms of butane in Titan’s atmosphere by analysis of Cassini infrared spectra collected during 2004-2017 by the Composite Infrared Spectrometer(CIRS) instrument. This multi-year effort has encompassed the collection of new laboratory spectra of both isomers at several institutions, followed by a concerted attempt to find their signatures in CIRS spectra. We search for butane by high precision modeling and removal of overlying emissions due to other, already-known gases to reveal signatures that match those of the butane isomers. The current status of the search will be discussed, including improved upper limits for both isomers, and directions of future research to detect both species.

Conor Nixon↗
NASA NTRS2022

New Constraints on Titan's Stratospheric n-Butane Abundance

Curiously, n-butane has yet to be detected at Titan, though it is predicted to be present in a wide range of abundances that span over 2.5 orders of magnitude. We have searched infrared spectroscopic observations of Titan for signals from n-butane (n-C4H10) in Titan's stratosphere. Three sets of Cassini Composite Infrared Spectrometer Focal Plane 4 (1050–1500 cm−1) observations were selected for modeling, having been collected from different flybys and pointing latitudes. We modeled the observations with the Nonlinear Optimal Estimator for MultivariatE Spectral AnalySIS radiative transfer tool. Temperature profiles were retrieved for each of the data sets by modeling the ν4 emission from methane near 1305 cm−1. Then, incorporating the temperature profiles, we retrieved abundances of all of Titan's known trace gases that are active in this spectral region, reliably reproducing the observations. We then systematically tested a set of models with varying abundances of n-butane, investigating how the addition of this gas affected the fits. We did this for several different photochemically predicted abundance profiles from the literature, as well as for a constant-with-altitude profile. Ultimately, though we did not produce any firm detection of n-butane, we derived new upper limits on its abundance specific to the use of each profile and to multiple different ranges of stratospheric altitudes. These results will tightly constrain the C4 chemistry of future photochemical modeling of Titan's atmosphere and also motivate the continued search for n-butane and its isomer, isobutane.

Brendan L. Steffens↗
NASA NTRS2010

Saturn's Atmospheric Composition from Observations by the Cassini/Composite Infrared Spectrometer

Thermal emission infrared observation of Saturn s atmosphere are being made by the Composite Infrared Spectrometer (CIRS) aboard the Cassini spacecraft since its insertion in Saturn s orbit on July 2nd, 2004. The measurements made in both limb and nadir modes of observations consist of infrared spectra in the 10-1400/cm region with a variable spectral resolution of 0.53/cm and 2.8/cm, and exhibit rotational and vibrational spectral features that may be analyzed for retrieval of the thermal structure and constituent distribution of Saturn s atmosphere. In this paper, we present a comprehensive analysis of the CIRS infrared observed spectra for retrieval of Saturn s atmospheric composition focusing on the distributions of some selected hydrocarbons, phosphine, ammonia, and possible determination of the isotopic ratios of some species with sufficiently strong isolated spectral features. A comparison of the retrieved constituent distributions with the available data in the literature will be made.

Abbas, M. M.↗
NASA NTRS2011

Saturn Ring Data Analysis and Thermal Modeling

CIRS, VIMS, UVIS, and ISS (Cassini's Composite Infrared Specrtometer, Visual and Infrared Mapping Spectrometer, Ultra Violet Imaging Spectrometer and Imaging Science Subsystem, respectively), have each operated in a multidimensional observation space and have acquired scans of the lit and unlit rings at multiple phase angles. To better understand physical and dynamical ring particle parametric dependence, we co-registered profiles from these three instruments, taken at a wide range of wavelengths, from ultraviolet through the thermal infrared, to associate changes in ring particle temperature with changes in observed brightness, specifically with albedos inferred by ISS, UVIS and VIMS. We work in a parameter space where the solar elevation range is constrained to 12 deg - 14 deg and the chosen radial region is the B3 region of the B ring; this region is the most optically thick region in Saturn's rings. From this compilation of multiple wavelength data, we construct and fit phase curves and color ratios using independent dynamical thermal models for ring structure and overplot Saturn, Saturn ring, and Solar spectra. Analysis of phase curve construction and color ratios reveals thermal emission to fall within the extrema of the ISS bandwidth and a geometrical dependence of reddening on phase angle, respectively. Analysis of spectra reveals Cassini CIRS Saturn spectra dominate Cassini CIRS B3 Ring Spectra from 19 to 1000 microns, while Earth-based B Ring Spectrum dominates Earth-based Saturn Spectrum from 0.4 to 4 microns. From our fits we test out dynamical thermal models; from the phase curves we derive ring albedos and non-lambertian properties of the ring particle surfaces; and from the color ratios we examine multiple scattering within the regolith of ring particles.

Saturn's rings↗
DOE OSTI2020

A Performance Comparison of Low-Cost Near-Infrared (NIR) Spectrometers to a Conventional Laboratory Spectrometer for Rapid Biomass Compositional Analysis

The performance of a conventional laboratory near-infrared (NIR) spectrometer and two NIR spectrometer prototypes (a Texas Instruments NIRSCAN Nano evaluation model (EVM) and an InnoSpectra NIR-M-R2 spectrometer) are compared by collecting reflectance spectra of 270 well-characterized herbaceous biomass samples, building calibration models using the partial least squares (PLS-2) algorithm to predict five constituents of the samples from the reflectance spectra, and comparing the resulting model statistics. The prediction models developed using spectra from the Foss XDS spectrometer were slightly better than the prediction models developed using spectra from either the TI NIRSCAN Nano EVM and the InnoSpectra NIR-M-R2 as measured by the root mean square error (RMSECV) and the correlation coefficient (R 2 _cv) for “leave-one-out” cross-validation (CV). The models built from the two prototype units were not statistically significantly different from each other (p = 0.05). The Foss spectrometer has a larger wavelength range (400–2500 nm) compared with the two prototypes (900–1700 nm). When the spectra from the Foss XDS spectrometer were truncated so their wavelength range matched the wavelength range of the two prototype units, the resulting model was not statistically significantly different from the models from either prototype.

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