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Probing Titan's Complex Atmospheric Chemistry Using the Atacama Large Millimeter/Submillimeter Array

Titan is Saturn's largest moon, with a thick (1.45 bar) atmosphere composed primarily of molecular nitrogen and methane. Atmospheric photochemistry results in the production of a wide range of complex organic molecules, including hydrocarbons, nitriles, aromatics and other species of possible pre-biotic relevance. Titan's carbon-rich atmosphere may be analogous to that of primitive terrestrial planets throughout the universe, yet its origin, evolution and complete chemical inventory are not well understood. Here we present spatially-resolved maps of emission from C2H5CN, HNC, HC3N, CH3CN and CH3CCH in Titan's atmosphere, observed using the Atacama Large Millimeter/submillimeter Array (ALMA) in 2012-2013. These data show previously-undetected spatial structures for the observed species and provide the first spectroscopic detection of C2H5CN on Titan. Our maps show spatially resolved peaks in Titan's northern and southern hemispheres, consistent with photochemical production and transport in the upper atmosphere followed by subsidence over the poles. The HNC emission peaks are offset from the polar axis, indicating that Titan's mesosphere may be more longitudinally variable than previously thought.

Titan↗

Miniature Cryogenic Valves for a Titan Lake Sampling System

The Cassini mission has revealed Titan to be one of the most Earthlike worlds in the Solar System complete with many of the same surface features including lakes, river channels, basins, and dunes. But unlike Earth, the materials and fluids on Titan are composed of cryogenic organic compounds with lakes of liquid methane and ethane. One of the potential mission concepts to explore Titan is to land a floating platform on one of the Titan Lakes and determine the local lake chemistry. In order to accomplish this within the expected mass volume and power budgets there is a need to pursue the development for a low power lightweight cryogenic valves which can be used along with vacuum lines to sample lake liquid and to distribute to various instruments aboard the Lander. To meet this need we have initiated the development of low power cryogenic valves and actuators based on a single crystal piezoelectric flextensional stacks produced by TRS Ceramics Inc. Since the origin of such high electromechanical properties of Relaxor-PT single crystals is due to the polarization rotation effect, (i.e., intrinsic contributions), the strain per volt decrease at cryogenic temperatures is much lower than in standard Lead Zirconate Titanate (PZT) ceramics. This makes them promising candidates for cryogenic actuators with regards to the stroke for a given voltage. This paper will present our Titan Lake Sampling and Sample Handling system design and the development of small cryogenic piezoelectric valves developed to meet the system specifications.

Piezoelectric Devices↗

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↗

Mapping the seasonal variability of Titan’s upper atmospheric gases using ALMA

We present a study of the impact of seasonal effects on the spatial distribution of Titan’s atmospheric gases HNC, CH3CN, and HC3N over a timescale of less than a Titan month (9 Earth months). These molecules are synthesized primarily in the upper and middle atmosphere as a result of CH4 and N2 photochemistry, and are redistributed around Titan’s globe as a result of diffusion and zonal and meridional circulation. With observations from the Atacama Large Millimeter/submillimeter Array (ALMA) obtained in August 2016 [1] and May 2017 [2], we produced high-resolution, spectrally and spatially resolved maps of the emission from these gases. These observations are contemporaneous with the end of the Cassini mission (around the time of the northern summer solstice), allowing for studies of seasonal variations in Titan’s organic chemistry through analysis of the production, destruction, and transport of complex molecules. We observed a strong reduction of 41% ± 4% in the HC3N flux coming from the north pole, while CH3CN and HNC remained relatively stable (within errors) over the 9 month period of our observations. In the south pole, CH3CN presented a 31% ± 10% increase, while HNC saw a reduction of 20% ± 8%, and HC3N remained fairly stable (within errors). The HNC emission comes primarily from the highest (thermospheric) altitudes, and is distributed more uniformly about Titan’s limb than HC3N and CH3CN; the latter two molecules show strong polar enhancements due to meridional circulation. The steep decline in the HC3N north polar concentration is consistent its short photochemical lifetime (compared to HNC and CH3CN), combined with a reduction in meridional transport of gases produced at lower latitudes, towards the northern (summer) pole. The loss of emission of HC3N in the northern hemisphere is also consistent with the breakdown of Titan’s northern polar vortex during the onset of the northern summer, leading to a loss of confinement of these species [3].

Titan↗

A Saturnian gas ring and the recycling of Titan's atmosphere

Atoms which escape Titan's atmosphere are unlikely to possess escape velocity from Saturn and can orbit the planet until lost by ionization or collision with Titan. It is predicted that a toroidal ring of between 1 and 1,000 atoms or molecules per cubic centimeter exists around Saturn at a distance of about 10 times the radius of the visible rings. This torus may be detectable from earth orbit and detection or nondetection of it may provide some information about the presence or absence of a Saturnian magnetic field, and the exospheric temperature and atmospheric escape rate of Titan. It is estimated that, if Titan has a large exosphere, 97% or more of the escaping atoms can be recaptured by Titan, thereby decreasing the effective net atmospheric loss rate by up to two orders of magnitude. It is shown that, if Saturn has a magnetic field comparable to Jupiter's the magnetospheric plasma can supply Titan with hydrogen at a rate comparable to the loss rates in some of the models of Trafton (1972) and Sagan (1973).

Mcdonough, T. R.↗

Experimental basis for a Titan probe organic analysis

The recent Voyager flyby of Titan produced evidence for at least nine organic compounds in that atmosphere that are heavier than methane. Several models of Titan's atmosphere, as well as laboratory simulations, suggest the presence of organics considerably more complex that those observed. To ensure that the in situ measurements are definitive with respect to Titan's atmosphere, experiment concepts, and the related instrumentation, must be carefully developed specifically for such a mission. To this end, the possible composition of the environment to be analyzed must be bracketed and model samples must be provided for instrumentation development studies. Laboratory studies to define the optimum flight experiment and sampling strategy for a Titan entry probe are currently being conducted. Titan mixtures are being subjected to a variety of energy sources including high voltage electron from a DC discharge, high current electric shock, and laser detonation. Gaseous and solid products are produced which are then analyzed. Samples from these experiements are also provided to candidate flight experiments as models for instrument development studies. Preliminary results show that existing theoretical models for chemistry in Titan's atmosphere cannot adequetely explain the presence and abundance of all trace gases observed in these experiments.

Mckay, C. P.↗

Titan atmospheric composition by hypervelocity shock layer analysis

The Cassini Mission, a NASA/ESA cooperative project which includes a deployment of probe into the atmosphere of Titan, is described, with particular attention given to the shock radiometer experiment planned for the Titan probe for the analysis of Titan's atmosphere. Results from a shock layer analysis are presented, demonstrating that the mole fractions of the major species (N2, CH4, and, possibly Ar) in the Titan atmosphere can be successfully determined by the Titan-probe radiometer, by measuring the intensity of the CN(violet) radiation emitted in the shock layer during the high velocity portion of the probe entry between 200 and 400 km altitude. It is shown that the sensitivity of the CN(violet) radiation makes it possible to determine the mole fractions of N2, CH4, and Ar to about 0.015, 0.003, and 0.01, respectively, i.e., much better than the present uncertainties in the composition of Titan atmosphere.

Nelson, H. F.↗

Observing the surface of Titan through near-infrared windows in its atmosphere

Possibilities of observing the surface of Titan through near infrared windows in the atmosphere are explored. Studies of Titan's near infrared spectrum are discussed with particular attention being given to the opacity of Titan's atmosphere, infrared spectra of candidate materials of Titan's surface, and ground based studies of Titan's surface. Instruments on board Cassini which will have the capability to observe Titan in the near infrared are presented together with what they may observe. These instruments include the descent imager/spectral radiometer, the Huygens probe and the visible infrared mapping spectrometer, and the imaging science subsystem.

Griffith, Caitlin A.↗

One-dimensional multispecies magnetohydrodynamic models of the ramside ionosphere of Titan

The interaction of the Saturnian magnetosphere with the ionosphere of Titan has much in common with the solar wind interaction with nonmagnetic bodies in general. A one-dimensional magnetohydrodynamic model was developed, for radial distances of 1.3 to 2 Titan radii (R(sub T)), to study the dynamics of H2CN(+), C(sub n) H(sub m) (+) (n, m greater than z), C2H5(+), and CH5(+), in the ramside ionosphere of Titan. For the case of a dayside ramside ionosphere (solar zenith angle of 60 degs) we found that the external magnetospheric plasma interacting with Titan's ionosphere produced a very broad region of ionospheric magnetic field whose peak field strength was approximately 26 nT. The ionosphere was magnetized well below the ionospheric peak, allowing ionizing Saturnian magnetospheric electrons access to this region. The sources of ionization and the electron temperature profiles incorporated into the model depend on the relative locations of Titan, Saturn, and the Sun. The calculated electron and ion density profiles as well as the magnetic field profile also depend on the relative positions of Titan, Saturn, and the Sun.

Keller, C. N.↗

Surface-atmosphere interactions on Titan compared with those on the pre-biotic Earth

The surface and atmosphere of Titan constitute a system which is potentially as complex as that of the Earth, with the possibility of precipitation, surface erosion due to liquids, chemistry in large surface or subsurface hydrocarbon resevoirs, surface expressions of internal activity, and occasional major impacts leading to crustal melting. While none of the above have been observed as yet, the composition, density and thermal properties of Titan's atmosphere make it uniquely suited in the outer solar system as a place where such processes may occur. The one attribute of the Earth not expected on Titan is biological activity, which has had a profound effect on the evolution of the Earth's surface-atmosphere system. The earliest environment of Titan could have been warm enough for liquid ammonia-water solutions to exist on or near surface; pre-biotic organic processes may have taken place in such an environment. After a few hundred million years surface ammonia-water would have disappeard. Therefore, study of Titan through Cassini/Huygens mission, planned for launch in 1997, primarily affords the opportunity to understand planet-side surface-atmophsre interactions in the presence of fluids but in the absence of life. More speculative is the possibility that endogenic and exogenic heating continue to provide short-lived environments on Titan wherein pre-biotic organic processes in the presence of water happen.

Lunine, J. I.↗

The physical nature of Titan's aerosols: Laboratory simulations

The atmosphere of Titan is known to contain aerosols, as evidenced by the Voyager observations of at least three haze layers. Such aerosols can have significant effects on the reflection spectrum of Titan and on the chemistry and thermal structure of its atmosphere. To investigate some of these effects laboratory simulations of the chemistry of Titan's atmosphere have been done. The results of these studies show that photolysis of acetylene, ethylene, and hydrogen cyanide, known constituents of Titan's atmosphere, yields sub-micron sized spheres, with mean diameters ranging from 0.4 to 0.8 micron, depending on the pressures of the reactant gases. Most of the spheres are contained in near-linear aggregates. The formation of the aggregates is consistent with models of Titan's reflection spectrum and polarization, which are best fit with non-spherical particles. At room temperature, the particles are very sticky, but their properties at low temperatures on Titan are presently not known.

Scattergood, T. W.↗

The Greenhouse and Anti-Greenhouse Effects on Titan

Titan is the largest moon of Saturn and is the only moon in the solar system with a substantial atmosphere. Its atmosphere is mostly made of nitrogen, with a few percent CH4, 0.1% H2 and an uncertain level of Ar (less than 10%). The surface pressure is 1.5 atms and the surface temperature is 95 K, decreasing to 71 at the tropopause before rising to stratospheric temperatures of 180 K. In pressure and composition Titan's atmosphere is the closest twin to Earth's. The surface of Titan remains unknown, hidden by the thick smog layer, but it may be an ocean of liquid methane and ethane. Titan's atmosphere has a greenhouse effect which is much stronger than the Earth's - 92% of the surface warming is due to greenhouse radiation. However an organic smog layer in the upper atmosphere produces an anti-greenhouse effect that cuts the greenhouse warming in half - removing 35% of the incoming solar radiation. Models suggest that during its formation Titan's atmosphere was heated to high temperatures due to accretional energy. This was followed by a cold Triton-like period which gradually warmed to the present conditions. The coupled greenhouse and haze anti-greenhouse may be relevant to recent suggestions for haze shielding of a CH4 - NH3 early atmosphere on Earth or Mars. When the NASA/ESA mission to the Saturn System, Cassini, launches in a few years it will carry a probe that will be sent to the surface of Titan and show us this world that is strange and yet in many ways similar to our own.

McKay, C. P.↗

Simulations of Titan's Brightness by a Two-Dimensional Haze Model

We have used a 2-D microphysics model to study the effects of atmospheric motions on the albedo of Titan's thick haze layer. We compare our results to the observed variations of Titan's brightness with season and latitude. We use two wind fields. The first is an analytic solution to the simplified equations of motion. The second is based on the preliminary results of a Titan GCM. Seasonally varying wind fields, of typical horizontal velocity 1 cm/ s at optical depth unity, are capable of producing the observed change in geometric albedo of about 10% over the Titan year. Neither of the two wind fields can adequately reproduce the latitudinal distribution of the contrast seen by Voyager. At visible wavelengths, where only haze opacity is radiatively important, upwelling produces darkening by increasing the particle size at optical depth unity. This is due to the suspension of larger particles as well as the removal of smaller particles from the top of the atmosphere. From our results it can be inferred that the circulation on Titan just prior to the time of Voyager was upwelling in the northern hemisphere and downwelling in the southern hemisphere with broad regions of uniform wind separated by a sharp transition at 10 deg. S. At UV wavelengths and at 0.89 microns the albedo is determined by the competing effects of the gas and the haze material. Gas is bright in the UV and dark at 0.89 microns. Haze transport at high altitudes controls the UV albedo and transport at low altitude controls the 0.89 microns albedo. Comparisons between the hemispheric contrast at UV and IR wavelengths can be diagnostic of the vertical structure of the wind field on Titan. Infrared albedo features, which are in the lower atmosphere and persist for many rotations could reflect the haze distribution set up by a seasonally varying circulation rather than surface features as assumed in some observational studies.

Hutzell, W.↗

Nitrogen Chemistry in Titan's Upper Atmosphere

In Titan's upper atmosphere N2 is dissociated to N by solar UV and high energy electrons. This flux of N provides for interesting organic chemistry in the lower atmosphere of Titan. Previously the main pathway for the loss of this N was thought to be the formation of HCN, followed by diffusion of this HCN to lower altitudes leading ultimately to condensation. However, recent laboratory simulations of organic chemistry in Titan's atmosphere suggest that formation of the organic haze may be an important sink for atmospheric N. Because estimates of the eddy diffusion profile on Titan have been based on the HCN profile, inclusion of this additional sink for N will affect estimates for all transport processes in Titan's atmosphere. This and other implications of this sink for the N balance on Titan are considered.

McKay, Christopher P.↗

Liquid Hydrocarbons on Titan's Surface? How Cassini ISS Observations Fit into the Story (So Far)

Titan is the only satellite in our Solar System with a substantial atmosphere, the origins and evolution of which are still not well understood. Its primary (greater than 90%) component is nitrogen, with a few percent methane and lesser amounts of other species. Methane and ethane are stable in the liquid state under the temperature and pressure conditions in Titan s lower atmosphere and at the surface; indeed, clouds, likely composed of methane, have been detected. Photochemical processes acting in the atmosphere convert methane into more complex hydrocarbons, creating Titan s haze and destroying methane over relatively short timescales. Therefore, it has been hypothesized that Titan s surface has reservoirs of liquid methane which serve to resupply the atmosphere. Early observations of Titan s surface revealed albedo patterns which have been interpreted as dark hydrocarbon liquids occupying topographically low regions between higher-standing exposures of bright, water-ice bedrock, although this is far from being the only explanation for the observed albedo contrast. Observations made by the Imaging Science Subsystem during Cassini's approach to Saturn and its first encounters with Titan show the bright and dark regions in greater detail but have yet to resolve the question of whether there are liquids on the surface.

Turtle, E. P.↗

Impact Craters on Titan? Cassini RADAR View

Titan is a planet-size (diameter of 5,150 km) satellite of Saturn that is currently being investigated by the Cassini spacecraft. Thus far only one flyby (Oct. 26, 2004; Ta) has occurred when radar images were obtained. In February, 2005, and approximately 20 more times in the next four years, additional radar swaths will be acquired. Each full swath images about 1% of Titan s surface at 13.78 GHz (Ku-band) with a maximum resolution of 400 m. The Ta radar pass [1] demonstrated that Titan has a solid surface with multiple types of landforms. However, there is no compelling detection of impact craters in this first radar swath. Dione, Tethys and other satellites of Saturn are intensely cratered, there is no way that Titan could have escaped a similar impact cratering past; thus there must be ongoing dynamic surface processes that erase impact craters (and other landforms) on Titan. The surface of Titan must be very young and the resurfacing rate must be significantly higher than the impact cratering rate.

Wood, Charles A.↗

Environmental Conditions and Threatened and Endangered Species Populations near the Titan, Atlas, and Delta Launch Complexes, Cape Canaveral Air Station

Launches of Delta, Atlas, and Titan rockets from Cape Canaveral Air Station (CCAS) have potential environmental effects. These could occur from direct impacts of launches or indirectly from habitat alterations. This report summarizes a three-year study (1 995-1 998) characterizing the environment, with particular attention to threatened and endangered species, near Delta, Atlas, and Titan launch facilities. Cape Canaveral has been modified by Air Force development and by 50 years of fire suppression. The dominant vegetation type around the Delta and Atlas launch complexes is coastal oak hammock forest. Oak scrub is the predominant upland vegetation type near the Titan launch complexes. Compositionally, these are coastal scrub communities that has been unburned for > 40 years and have developed into closed canopy, low-stature forests. Herbaceous vegetation around active and inactive facilities, coastal strand and dune vegetation near the Atlantic Ocean, and exotic vegetation in disturbed areas are common. Marsh and estuarine vegetation is most common west of the Titan complexes. Launch effects to vegetation include scorch, acid, and particulate deposition. Discernable, cumulative effects are limited to small areas near the launch complexes. Water quality samples were collected at the Titan, Atlas, and Delta launch complexes in September 1995 (wet season) and January 1996 (dry season). Samples were analyzed for heavy metals, chloride, total organic carbon, calcium, iron, magnesium, sodium, total alkalinity, pH, and conductivity. Differences between fresh, brackish, and saline surface waters were evident. The natural buffering capacity of the environment surrounding the CCAS launch complexes is adequate for neutralizing acid deposition in rainfall and launch deposition. Populations of the Florida Scrub-Jay (Aphelocoma coerulescens), a Federally-listed, threatened species, reside near the launch complexes. Thirty-seven to forty-one scrub-jay territories were located at Titan, Atlas, and Delta launch complexes between 1995 and 1997. No direct impacts to scrub-jays were observed as a result of normal launches. The explosion of the Delta rocket in January 1997 caused direct impacts to the habitat of several scrub-jays families, from fire and debris; however, no scrub-jay mortality was observed. Mortality exceeded reproductive output at all areas over the course of the study. Populations of the southeastern beach mouse (Peromyscus polionotus niveiventris) populations, a Federally listed, threatened species, reside near all the launch complexes. Hurricane Erin and several other tropical storms impacted several areas at the inception of the study in 1995 causing coastal habitat alterations as a result of salt-water intrusion. Both the habitat and the beach mice populations recovered during the course of the study. No direct impacts to southeastern beach mice were observed as a result of normal launch operations. Direct impacts were observed to the habitat as a result of the explosion of the Delta rocket in January 1997. This alteration of the habitat resulted in a shift in use with the mice moving on to the newly burned part of the site. Waterbirds use wetlands and aquatic systems near the launch complexes. Species include the Federally-listed, endangered Wood Stork (Mycferia americana) and several state-listed species of special concern including the Snowy Egret (Egretfa thula fhula), Reddish Egret (Egreffa rufescens rufescens), White Ibis (Eudocimus albus), Roseate Spoonbill (Ajaia ajaja), Tricolored Heron (Egreffa tricolor ruficolis), and Little Blue Heron (Egreffa caerulea). No impacts to these populations resulting from any launch operations were observed. Gopher tortoises (Gopherus polyphemus) also occur around the launch complexes. Most of those observed appeared to be in good condition; however, upper respiratory tract disease is known to occur in the population. Cape Canaveral Air Station, including areas near active launch colexes, remains important habitat for a variety of native plants and animals including threatened and endangered species. Direct negative effects of current launch systems appear limited. Additional monitoring of these populations and habitats is required to determine if subtle, long-term changes are occurring, to determine if new launch systems and facilities cause other effects, and to determine the effects of habitat restoration and management.

Oddy, Donna M.↗

Solar Electric and Chemical Propulsion Technology Applications to a Titan Orbiter/Lander Mission

Several advanced propulsion technology options were assessed for a conceptual Titan Orbiter/Lander mission. For convenience of presentation, the mission was broken into two phases: interplanetary and Titan capture. The interplanetary phase of the mission was evaluated for an advanced Solar Electric Propulsion System (SEPS), while the Titan capture phase was evaluated for state-of-art chemical propulsion (NTO/Hydrazine), three advanced chemical propulsion options (LOX/Hydrazine, Fluorine/Hydrazine, high Isp mono-propellant), and advanced tank technologies. Hence, this study was referred to as a SEPS/Chemical based option. The SEPS/Chemical study results were briefly compared to a 2002 NASA study that included two general propulsion options for the same conceptual mission: an all propulsive based mission and a SEPS/Aerocapture based mission. The SEP/Chemical study assumed identical science payload as the 2002 NASA study science payload. The SEPS/Chemical study results indicated that the Titan mission was feasible for a medium launch vehicle, an interplanetary transfer time of approximately 8 years, an advanced SEPS (30 kW), and current chemical engine technology (yet with advanced tanks) for the Titan capture. The 2002 NASA study showed the feasibility of the mission based on a somewhat smaller medium launch vehicle, an interplanetary transfer time of approximately 5.9 years, an advanced SEPS (24 kW), and advanced Aerocapture based propulsion technology for the Titan capture. Further comparisons and study results were presented for the advanced chemical and advanced tank technologies.

Cupples, Michael↗