Abundance Measurements of Titan's Stratospheric HCN, HC3_3N, C3_3H4_4, and CH3_3CN from ALMA Observations

Previous investigations have employed more than 100 close observations of Titan by the Cassini orbiter to elucidate connections between the production and distribution of Titan's vast, organic-rich chemical inventory and its atmospheric dynamics. However, as Titan transitions into northern summer, the lack of incoming data from the Cassini orbiter presents a potential barrier to the continued study of seasonal changes in Titan's atmosphere. In our previous work (Thelen et al., 2018), we demonstrated that the Atacama Large Millimeter/submillimeter Array (ALMA) is well suited for measurements of Titan's atmosphere in the stratosphere and lower mesosphere (~100-500 km) through the use of spatially resolved (beam sizes <1'') flux calibration observations of Titan. Here, we derive vertical abundance profiles of four of Titan's trace atmospheric species from the same 3 independent spatial regions across Titan's disk during the same epoch (2012 to 2015): HCN, HC$_3$N, C$_3$H$_4$, and CH$_3$CN. We find that Titan's minor constituents exhibit large latitudinal variations, with enhanced abundances at high latitudes compared to equatorial measurements; this includes CH$_3$CN, which eluded previous detection by Cassini in the stratosphere, and thus spatially resolved abundance measurements were unattainable. Even over the short 3-year period, vertical profiles and integrated emission maps of these molecules allow us to observe temporal changes in Titan's atmospheric circulation during northern spring. Our derived abundance profiles are comparable to contemporary measurements from Cassini infrared observations, and we find additional evidence for subsidence of enriched air onto Titan's south pole during this time period. Continued observations of Titan with ALMA beyond the summer solstice will enable further study of how Titan's atmospheric composition and dynamics respond to seasonal changes.Comment: 15 pages, 16 figures, 2 tables. Accepted for publication in Icarus, September 201

Ethyl cyanide on Titan: Spectroscopic detection and mapping using ALMA

We report the first spectroscopic detection of ethyl cyanide (C$_2$H$_5$CN) in Titan's atmosphere, obtained using spectrally and spatially resolved observations of multiple emission lines with the Atacama Large Millimeter/submillimeter array (ALMA). The presence of C$_2$H$_5$CN in Titan's ionosphere was previously inferred from Cassini ion mass spectrometry measurements of C$_2$H$_5$CNH$^+$. Here we report the detection of 27 rotational lines from C$_2$H$_5$CN (in 19 separate emission features detected at $>3\sigma$ confidence), in the frequency range 222-241 GHz. Simultaneous detections of multiple emission lines from HC$_3$N, CH$_3$CN and CH$_3$CCH were also obtained. In contrast to HC$_3$N, CH$_3$CN and CH$_3$CCH, which peak in Titan's northern (spring) hemisphere, the emission from C$_2$H$_5$CN is found to be concentrated in the southern (autumn) hemisphere, suggesting a distinctly different chemistry for this species, consistent with a relatively short chemical lifetime for C$_2$H$_5$CN. Radiative transfer models show that most of the C$_2$H$_5$CN is concentrated at altitudes 300-600 km, suggesting production predominantly in the mesosphere and above. Vertical column densities are found to be in the range (2-5)$\times10^{14}$ cm$^{-2}$.Comment: Published in 2015, ApJL, 800, L1

ALMA measurements of the HNC and HC3N distributions in Titan's atmosphere

We present spectrally and spatially resolved maps of HNC and HC3N emission from Titan's atmosphere, obtained using the Atacama Large Millimeter/submillimeter Array on 2013 November 17. These maps show anisotropic spatial distributions for both molecules, with resolved emission peaks in Titan's northern and southern hemispheres. The HC3N maps indicate enhanced concentrations of this molecule over the poles, consistent with previous studies of Titan's photochemistry and atmospheric circulation. Differences between the spectrally integrated flux distributions of HNC and HC3N show that these species are not co-spatial. The observed spectral line shapes are consistent with HNC being concentrated predominantly in the mesosphere and above (at altitudes z ≳ 400 km), whereas HC3N is abundant at a broader range of altitudes (z ≈ 70-600 km). From spatial variations in the HC3N line profile, the locations of the HC3N emission peaks are shown to be variable as a function of altitude. The peaks in the integrated emission from HNC and the line core (upper atmosphere) component of HC3N (at z ≳ 300 km) are found to be asymmetric with respect to Titan's polar axis, indicating that the mesosphere may be more longitudinally variable than previously thought. The spatially integrated HNC and HC3N spectra are modeled using the NEMESIS planetary atmosphere code and the resulting best-fitting disk-averaged vertical mixing ratio profiles are found to be in reasonable agreement with previous measurements for these species. Vertical column densities of the best-fitting gradient models for HNC and HC3N are 1.9 × 1013 cm-2 and 2.3 × 1014 cm-2, respectively

Detection of Cyclopropenylidene on Titan with ALMA

We report the first detection on Titan of the small cyclic molecule cyclopropenylidene (c-C3H2) from high-sensitivity spectroscopic observations made with the Atacama Large Millimeter/submillimeter Array. Multiple lines of cyclopropenylidene were detected in two separate data sets: ~251 GHz in 2016 (Band 6) and ~352 GHz in 2017 (Band 7). Modeling of these emissions indicates abundances of 0.50 ± 0.14 ppb (2016) and 0.28 ± 0.08 (2017) for a 350 km step model, which may either signify a decrease in abundance, or a mean value of 0.33 ± 0.07 ppb. Inferred column abundances are (3–5) × 1012 cm−2 in 2016 and (1–2) × 1012 cm−2 in 2017, similar to photochemical model predictions. Previously the C3H${}_{3}^{+}$ ion has been measured in Titan's ionosphere by Cassini's Ion and Neutral Mass Spectrometer (INMS), but the neutral (unprotonated) species has not been detected until now, and aromatic versus aliphatic structure could not be determined by the INMS. Our work therefore represents the first unambiguous detection of cyclopropenylidene, the second known cyclic molecule in Titan's atmosphere along with benzene (C6H6) and the first time this molecule has been detected in a planetary atmosphere. We also searched for the N-heterocycle molecules pyridine and pyrimidine finding nondetections in both cases, and determining 2σ upper limits of 1.15 ppb (c-C5H5N) and 0.85 ppb (c-C4H4N2) for uniform abundances above 300 km. These new results on cyclic molecules provide fresh constraints on photochemical pathways in Titan's atmosphere, and will require new modeling and experimental work to fully understand the implications for complex molecule formation

Saturn's atmospheric response to the large influx of ring material inferred from Cassini INMS measurements

During the Grand Finale stage of the Cassini mission, organic-rich ring material was discovered to be flowing into Saturn's equatorial upper atmosphere at a surprisingly large rate. Through a series of photochemical models, we have examined the consequences of this ring material on the chemistry of Saturn's neutral and ionized atmosphere. We find that if a substantial fraction of this material enters the atmosphere as vapor or becomes vaporized as the solid ring particles ablate upon atmospheric entry, then the ring-derived vapor would strongly affect the composition of Saturn's ionosphere and neutral stratosphere. Our surveys of Cassini infrared and ultraviolet remote-sensing data from the final few years of the mission, however, reveal none of these predicted chemical consequences. We therefore conclude that either (1) the inferred ring influx represents an anomalous, transient situation that was triggered by some recent dynamical event in the ring system that occurred a few months to a few tens of years before the 2017 end of the Cassini mission, or (2) a large fraction of the incoming material must have been entering the atmosphere as small dust particles less than ~100 nm in radius, rather than as vapor or as large particles that are likely to ablate. Future observations or upper limits for stratospheric neutral species such as HC$_3$N, HCN, and CO$_2$ at infrared wavelengths could shed light on the origin, timing, magnitude, and nature of a possible vapor-rich ring-inflow event.Comment: accepted in Icaru

The Origin of Titan’s External Oxygen:Further Constraints from ALMA Upper Limits on CS and CH₂NH

Titan's atmospheric inventory of oxygen compounds (H2O, CO2, CO) are thought to result from photochemistry acting on externally supplied oxygen species (O+, OH, H2O). These species potentially originate from two main sources: (1) cryogenic plumes from the active moon Enceladus and (2) micrometeoroid ablation. Enceladus is already suspected to be the major O+ source, which is required for CO creation. However, photochemical models also require H2O and OH influx to reproduce observed quantities of CO2 and H2O. Here, we exploit sulphur as a tracer to investigate the oxygen source because it has very different relative abundances in micrometeorites (S/O ~ 10−2) and Enceladus' plumes (S/O ~ 10−5). Photochemical models predict most sulphur is converted to CS in the upper atmosphere, so we use Atacama Large Millimeter/submillimeter Array (ALMA) observations at ~340 GHz to search for CS emission. We determined stringent CS 3σ stratospheric upper limits of 0.0074 ppb (uniform above 100 km) and 0.0256 ppb (uniform above 200 km). These upper limits are not quite stringent enough to distinguish between Enceladus and micrometeorite sources at the 3σ level and a contribution from micrometeorites cannot be ruled out, especially if external flux is toward the lower end of current estimates. Only the high-flux micrometeorite source model of Hickson et al. can be rejected at 3σ. We determined a 3σ stratospheric upper limit for CH2NH of 0.35 ppb, which suggests cosmic rays may have a smaller influence in the lower stratosphere than predicted by some photochemical models. Disk-averaged C3H4 and C2H5CN profiles were determined and are consistent with previous ALMA and Cassini/CIRS measurements

Spatial variations in Titan's atmospheric temperature:ALMA and <i>Cassini </i>comparisons from 2012 to 2015

Submillimeter emission lines of carbon monoxide (CO) in Titan's atmosphere provide excellent probes of atmospheric temperature due to the molecule's long chemical lifetime and stable, well constrained volume mixing ratio. Here we present the analysis of 4 datasets obtained with the Atacama Large Millimeter/Submillimeter Array (ALMA) in 2012, 2013, 2014, and 2015 that contain strong CO rotational transitions. Utilizing ALMA's high spatial resolution in the 2012, 2014, and 2015 observations, we extract spectra from 3 separate regions on Titan's disk using datasets with beam sizes ranging from 0.35 × 0.28'' to 0.39 × 0.34''. Temperature profiles retrieved by the NEMESIS radiative transfer code are compared to Cassini Composite Infrared Spectrometer (CIRS) and radio occultation science results from similar latitude regions. Disk-averaged temperature profiles stay relatively constant from year to year, while small seasonal variations in atmospheric temperature are present from 2012 to 2015 in the stratosphere and mesosphere (~100-500 km) of spatially resolved regions. We measure the stratopause (320 km) to increase in temperature by 5 K in northern latitudes from 2012 to 2015, while temperatures rise throughout the stratosphere at lower latitudes. We observe generally cooler temperatures in the lower stratosphere (~100 km) than those obtained through Cassini radio occultation measurements, with the notable exception of warming in the northern latitudes and the absence of previous instabilities; both of these results are indicators that Titan's lower atmosphere responds to seasonal effects, particularly at higher latitudes. While retrieved temperature profiles cover a range of latitudes in these observations, deviations from CIRS nadir maps and radio occultation measurements convolved with the ALMA beam-footprint are not found to be statistically significant, and discrepancies are often found to be less than 5 K throughout the atmosphere. ALMA's excellent sensitivity in the lower stratosphere (60-300 km) provides a highly complementary dataset to contemporary CIRS and radio science observations, including altitude regions where both of those measurement sets contain large uncertainties. The demonstrated utility of CO emission lines in the submillimeter as a tracer of Titan's atmospheric temperature lays the groundwork for future studies of other molecular species - particularly those that exhibit strong polar abundance enhancements or are pressure-broadened in the lower atmosphere, as temperature profiles are found to consistently vary with latitude in all three years by up to 15 K

Saturn’s atmospheric response to the large influx of ring material inferred from Cassini INMS measurements

During the Grand Finale stage of the Cassini mission, organic-rich ring material was discovered to be flowing into Saturn’s equatorial upper atmosphere at a surprisingly large rate. Through a series of photochemical models, we have examined the consequences of this ring material on the chemistry of Saturn’s neutral and ionized atmosphere. We find that if a substantial fraction of this material enters the atmosphere as vapor or becomes vaporized as the solid ring particles ablate upon atmospheric entry, then the ring-derived vapor would strongly affect the composition of Saturn’s ionosphere and neutral stratosphere. Our surveys of Cassini infrared and ultraviolet remote-sensing data from the final few years of the mission, however, reveal none of these predicted chemical consequences. We therefore conclude that either (1) the inferred ring influx represents an anomalous, transient situation that was triggered by some recent dynamical event in the ring system that occurred a few months to a few tens of years before the 2017 end of the Cassini mission, or (2) a large fraction of the incoming material must have been entering the atmosphere as small dust particles less than 100 nm in radius, rather than as vapor or as large particles that are likely to ablate. Future observations or upper limits for stratospheric neutral species such as HCN, HCN, and CO at infrared wavelengths could shed light on the origin, timing, magnitude, and nature of a possible vapor-rich ring-inflow event