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NASA NTRS2018

Stable Isotope Fractionation in Titan Aerosol Formation

Stable isotope ratio measurements are a powerful tool used to understand both ancient and modern planetary processes. Instruments on the Cassini- Huygens spacecraft along with ground-based observations have measured several isotope pairs, including C-13/C-12 and N-15/N-14, in Titan's atmosphere. This includes isotopic measurements of the major atmospheric species, CH4 and N2, along with HCN, HC3N, C2H2. C2H6 and C4H2. However, the isotopic fractionation of Titan's organic aerosol has not conclusively been measured and therefore the effect of aerosol formation as an isotopic fractionation pathway in Titan's atmosphere has not been considered. Laboratory studies have measured the carbon and/or nitrogen isotopic fractionation of Titan aerosol analogs. [18] found that the carbon fractionation of photochemical organic aerosol analogs are more enriched in C-13. This enrichment in the aerosol analogs is opposite of what is predicted for photochemical products by the kinetic isotope effect. Additionally, both [16] and [18] found that the nitrogen fractionation in the organic aerosol analogs are opposite of what is observed in Titan's atmospheric N2 and HCN, with the aerosol analogs being a light nitrogen sink. Here we monitor the gas phase during photochemical aerosol analog production as a function of reaction time. In a recirculation experiment, the isotopic fractionation of carbon within the gas-phase products is measured as the CH4 reservoir is depleted. This allows us to monitor the isotopic fractionation pathway during photochemical aerosol analog formation.

Ugelow, M. S.↗

NASA NTRS2019

Detection of Propadiene on Titan

The atmosphere of Titan, the largest moon of Saturn, is rich in organic molecules, and it has been suggested that the moon may serve as an analog for the pre-biotic Earth due to its highly reducing chemistry and existence of global hazes. Photochemical models of Titan have predicted the presence of propadiene (historically referred to as allene), CH2CCH2, an isomer of the well-measured propyne (also called methylacetylene) CH3CCH, but its detection has remained elusive due to insufficient spectroscopic knowledge of the molecule. This has recently been remedied with an updated spectral line list. Here we present the first unambiguous detection of the molecule in any astronomical object, observed with the Texas Echelle Cross Echelle Spectrograph on the NASA Infrared Telescope Facility in 2017 July. We model its emission line near 12 μm and measure a volume mixing ratio of (6.9 ± 0.8) × 10(exp −10) at 175 km, assuming a vertically increasing abundance profile as predicted in photochemical models. Cassini measurements of propyne made during 2017 April indicate that the abundance ratio of propyne to propadiene is 8.2 ± 1.1 at the same altitude. This initial measurement of the molecule in Titan's stratosphere paves the way toward constraining the amount of atomic hydrogen available on Titan, as well as future mapping of propadiene on Titan from 8 m and larger ground-based observatories, and future detection on other planetary bodies.

Propadiene or allene↗

NASA NTRS2018

Organic Ices in Titan's Stratosphere

Titan’s stratospheric ice clouds are by far the most complex of any observed in the solar system, with over a dozen organic vapors condensing out to form a suite of pure and co-condensed ices, typically observed at high winter polar latitudes. Once these stratospheric ices are formed, they will diffuse throughout Titan’s lower atmosphere and most will eventually precipitate to the surface, where they are expected to contribute to Titan’s regolith. Early and important contributions were first made by the InfraRed Interferometer Spectrometer (IRIS) on Voyager 1, followed by notable contributions from IRIS’ successor, the Cassini Composite InfraRed Spectrometer (CIRS), and to a lesser extent, from Cassini’s Visible and Infrared Mapping Spectrometer (VIMS) and the Imaging Science Subsystem (ISS) instruments. All three remote sensing instruments made new ice cloud discoveries, combined with monitoring the seasonal behaviors and time evolution throughout Cassini’s 13-year mission tenure. A significant advance by CIRS was the realization that co-condensing chemical compounds can account for many of the CIRS-observed stratospheric ice cloud spectral features, especially for some that were previously puzzling, even though some of the observed spectral features are still not well understood. Relevant laboratory transmission spectroscopy efforts began just after the Voyager encounters, and have accelerated in the last few years due to new experimental efforts aimed at simulating co-condensed ices in Titan’s stratosphere. This review details the current state of knowledge regarding the organic ice clouds in Titan’s stratosphere, with perspectives from both observational and experimental standpoints.

Astronomy↗

NASA NTRS2018

Organic Ices in Titan's Stratosphere

C. M. Anderson↗

NASA NTRS2019

Mapping the Zonal Structure of Titan’s Northern Polar Vortex

Saturn exhibits an obliquity of 26.7° such that the largest moon, Titan, experiences seasonal variations including the formation of a polar vortex in the winter hemisphere. Titan’s polar vortex is characterised by cold stratospheric temperatures due to the lack of insolation over the winter pole, and an increase in trace gas abundance as a result of complex organic chemistry in the upper atmosphere combined with polar subsidence. Meridional variations in temperature and gas abundance across the vortex have previously been investigated, but there has not yet been any in-depth study of the zonal variations in the temperature or composition of the northern vortex. Here we present the first comprehensive two-dimensional seasonal mapping of Titan’s northern winter vortex. Using 18 nadir mapping sequences observed by the Composite InfraRed Spectrometer (CIRS) instrument on-board Cassini, we investigate the evolution of the vortex over almost half a Titan year, from late winter through to mid summer (L(sub s) = 326 - 86°, 2007-2017). We find the stratospheric symmetry axis to be tilted from the solid body rotation axis by around 3.5°, although our results for the azimuthal orientation of the tilt are inconclusive. We find that the northern vortex appears to remain zonally uniform in both temperature and composition at all times. A comparison with vortices observed on Earth, Mars, and Venus shows that large-scale wave mechanisms that are important on other terrestrial planets are not as significant in Titan’s atmosphere. This allows the northern vortex to be more symmetrical and persist longer throughout the annual cycle compared to other terrestrial planets.

Jason Sharkey↗

NASA NTRS2019

Titan's Neutral Atmosphere Seasonal Variations up to the End of the Cassini Mission

In this paper we report new results concerning the seasonal atmospheric evolution near Titan's poles and equator in terms of temperature and composition using nadir spectra acquired by the Cassini Composite Infrared Spectrometer (CIRS) at high spectral resolution during the last year of the Cassini mission in 2017 complementing previous investigations covering almost two Titan seasons. In recent previous papers (Coustenis et al., 2016, 2018), we have reported on monitoring of Titan's stratosphere near the poles after the mid-2009 northern spring equinox. In particular we have reported on the observed strong temperature decrease and compositional enhancement above Titan's southern polar latitudes since 2012 and until 2014 of several trace species, such as complex hydrocarbons and nitriles, which were previously observed only at high northern latitudes. This effect accompanied the transition of Titan's seasons from northern winter in 2002 to northern summer in 2017, while at that latter time, the southern hemisphere was entering winter. Our new data, acquired in 2017 and analyzed here, are important because they are the only ones recorded since 2014 close to the south pole in the mid-infrared nadir mode at high resolution. A large temperature increase in the southern polar stratosphere (by 10–50 K in the 0.1 mbar–0.01 mbar pressure range) is found associated with a change in the temperature profile's shape. The 2017 observations also show a related significant decrease in most of the southern abundances which must have started sometime between 2014 and 2017. For the north, the spectra indicate a continuation of the decrease of the abundances which we first reported to have started in 2015 and small temperature variations. We discuss comparisons with other results and with current photochemical and dynamical models which could be updated and improved by the new constraints set by the findings presented here.

A Coustenis↗

NASA NTRS2021

Titan’s Global Radiant Energy Budget During the Cassini Epoch (2004-2017)

Radiant energies of planets and moons are of wide interest in the fields of geoscience and planetary science. Based on long-term multiinstrument observations from the Cassini spacecraft, we provide here the first observational study of Titan's global radiant energy budget and its seasonal variations. Our results show that Titan's radiant energy budget is not balanced over the Cassini era (2004–2017) with the absorbed solar energy (1.208 ± 0.008) × 10^(23) J larger than the emitted thermal energy (1.174 ± 0.005) × 10^(23) J. The energy imbalance is 2.9 ± 0.8% of the emitted thermal energy. Titan's global radiant energy budget is not balanced either at the timescales of Earth's years and Titan's seasons. In particular, the energy imbalance can be beyond 10% of the emitted thermal energy at the timescale of an Earth year. The energy imbalance revealed in this study has important impacts on Titan, which should be examined further by theories and models.

Ellen C. Creecy↗

NASA NTRS2020

Terrain Relative Navigation for Guided Descent on Titan

Titan’s dense atmosphere, low gravity, and high winds at high altitudes create descent times of >90 minutes with standard entry/descent/landing (EDL) architectures and result in large unguided landing ellipses, with 99% values of 110x110 km and 149x72 km in recent Titan lander proposals. Enabling precision landing on Titan could increase science return for the types of missions proposed to date and make additional types of landing sites accessible, opening up new possibilities for science investigations. Precision landing on Titan has unique challenges, because the hazy atmosphere makes it difficult to see the surface and because it requires guided descent with divert ranges that are one to two orders of magnitude larger than needed for other target bodies, i.e. up to on the order of 100 km. It is conceivable that such a divert capability could be provided economically by a parafoil or other steerable aerodynamic decelerator deployed several 10s of km above the surface. The long descent times lead to large inertial navigation errors, hence a need for terrain relative navigation (TRN). This would require a TRN capability that can operate at such altitudes, despite challenges of seeing the surface sufficiently clearly and of depending on map products that are two orders of magnitude lower in spatial resolution than those for Mars and airless bodies. We then develop algorithms for map matching and feature tracking with descent images and test these with synthetic images created from Cassini/Huygens data sets and our radiative transfer model. We also introduce new possibilities for TRN based on the potential to discriminate some specific types of terrain onboard in descent imagery, such as lake vs adjacent ground and dune vs interdune. We use sensor measurement noise models in simulations of state estimation with an extended Kalman filter that includes coordinates of a set of tracked features in the state vector. Case studies were done for two notional landing sites, one in a site with only dry ground and one in a Titan lake district. In both cases, the filter error model shows 3 position error at touchdown on the order of 2 km. More work is needed to validate these results with higher fidelity camera models and larger data sets, but this is very promising.

Matthies, Larry↗

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↗

DOE OSTI2024

Photocatalytic Hydrogen Evolution Using Mesoporous Honeycomb Iron Titanate

Mesoporous honeycomb iron titanate using a sol-gel, evaporation-induced self-assembly method is synthesized. A triblock copolymer, F127, serves as a structure-directing agents, with iron chloride and titanium (IV) isopropoxide as inorganic precursors. The strong intermolecular force of attraction among urea, metal precursors, and polymer led to the formation of the mesoporous honeycomb structure. The study of physicochemical properties using different techniques reveals the formation of microstructures with a remarkable degree of porosity. The amorphous iron titanate outperforms the photochemical generation of H 2 due to its disorderly structural arrangement and incomplete crystal formation. The randomness on the structure provides more area for catalytic reaction by providing more contact with the reactant and superior light absorption capability. The high amount of hydrogen gas, 40.66 mmolg -1 h -1 , is observed in the investigation over 3 h of activity for the iron titanate honeycomb sample. This yield is a more significant amount compared to the obtained for the commercially available TiO 2 (23.78 mmolg -1 h -1 ). The iron titanate materials synthesized with low-cost materials and methods are very effective and have the potential for hydrogen generation.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

NASA NTRS2008

Wind-Based Navigation of a Hot-air Balloon on Titan: A Feasibility Study

Current analysis of data streamed back to Earth by the Cassini spacecraft features Titan as one of the most exciting places in the solar system. NASA centers and universities around the US, as well as the European Space Agency, are studying the possibility of sending, as part of the next mission to this giant moon of Saturn, a hot-air balloon (Montgolfier-type) for further and more in-depth exploration. The basic idea would be to design a reliable, semi-autonomous, and yet cheap Montgolfier capable of using continuous flow of waste heat from a power source to lift the balloon and sustain its altitude in the Titan environment. In this paper we study the problem of locally navigating a hot-air balloon in the nitrogen-based Titan atmosphere. The basic idea is to define a strategy (i.e. design of a suitable guidance system) that allows autonomous and semi-autonomous navigation of the balloon using the available (and partial) knowledge of the wind structure blowing on the saturnian satellite surface. Starting from first principles we determined the appropriate thermal and dynamical models describing (a) the vertical dynamics of the balloon and (b) the dynamics of the balloon moving on a vertical plane (2-D motion). Next, various non-linear fuzzy-based control strategies have been evaluated, analyzed and implemented in MATLAB to numerically simulate the capability of the system to simultaneously maintain altitude, as well as a scientifically desirable trajectory. We also looked at the ability of the balloon to perform station keeping. The results of the simulation are encouraging and show the effectiveness of such a system to cheaply and effectively perform semiautonomous exploration of Titan.

balloon dynamics↗

NASA NTRS2014

Amino Acids Generated from Hydrated Titan Tholins: Comparison with Miller-Urey Electric Discharge Products

Various analogues of Titan haze particles (termed tholins) have been made in the laboratory. In certain geologic environments on Titan, these haze particles may come into contact with aqueous ammonia (NH3) solutions, hydrolyzing them into molecules of astrobiological interest. A Titan tholin analogue hydrolyzed in aqueous NH3 at room temperature for 2.5 years was analyzed for amino acids using highly sensitive ultra-high performance liquid chromatography coupled with fluorescence detection and time-of-flight mass spectrometry (UHPLC-FDToF-MS) analysis after derivatization with a fluorescent tag. We compare here the amino acids produced from this reaction sequence with those generated from room temperature Miller-Urey (MU) type electric discharge reactions. We find that most of the amino acids detected in low temperature MU CH4N2H2O electric discharge reactions are generated in Titan simulation reactions, as well as in previous simulations of Triton chemistry. This argues that many processes provide very similar mixtures of amino acids, and possibly other types of organic compounds, in disparate environments, regardless of the order of hydration. Although it is unknown how life began, it is likely that given reducing conditions, similar materials were available throughout the early Solar System and throughout the universe to facilitate chemical evolution.

Astrobiology aEuro" Titan↗

NASA NTRS2014

Big Impacts and Transient Oceans on Titan

We have studied the thermal consequences of very big impacts on Titan [1]. Titan's thick atmosphere and volatile-rich surface cause it to respond to big impacts in a somewhat Earth-like manner. Here we construct a simple globally-averaged model that tracks the flow of energy through the environment in the weeks, years, and millenia after a big comet strikes Titan. The model Titan is endowed with 1.4 bars of N2 and 0.07 bars of CH4, methane lakes, a water ice crust, and enough methane underground to saturate the regolith to the surface. We assume that half of the impact energy is immediately available to the atmosphere and surface while the other half is buried at the site of the crater and is unavailable on time scales of interest. The atmosphere and surface are treated as isothermal. We make the simplifying assumptions that the crust is everywhere as methane saturated as it was at the Huygens landing site, that the concentration of methane in the regolith is the same as it is at the surface, and that the crust is made of water ice. Heat flow into and out of the crust is approximated by step-functions. If the impact is great enough, ice melts. The meltwater oceans cool to the atmosphere conductively through an ice lid while at the base melting their way into the interior, driven down in part through Rayleigh-Taylor instabilities between the dense water and the warm ice. Topography, CO2, and hydrocarbons other than methane are ignored. Methane and ethane clathrate hydrates are discussed quantitatively but not fully incorporated into the model.

methane↗

NASA NTRS2013

Large Abundances of Polycyclic Aromatic Hydrocarbons in Titan's Upper Atmosphere

In this paper, we analyze the strong unidentified emission near 3.28 micron in Titan's upper daytime atmosphere recently discovered by Dinelli et al.We have studied it by using the NASA Ames PAH IR Spectroscopic Database. The polycyclic aromatic hydrocarbons (PAHs), after absorbing UV solar radiation, are able to emit strongly near 3.3 micron. By using current models for the redistribution of the absorbed UV energy, we have explained the observed spectral feature and have derived the vertical distribution of PAH abundances in Titan's upper atmosphere. PAHs have been found to be present in large concentrations, about (2-3) × 10(exp 4) particles / cubic cm. The identified PAHs have 9-96 carbons, with a concentration-weighted average of 34 carbons. The mean mass is approx 430 u; the mean area is about 0.53 sq. nm; they are formed by 10-11 rings on average, and about one-third of them contain nitrogen atoms. Recently, benzene together with light aromatic species as well as small concentrations of heavy positive and negative ions have been detected in Titan's upper atmosphere. We suggest that the large concentrations of PAHs found here are the neutral counterpart of those positive and negative ions, which hence supports the theory that the origin of Titan main haze layer is located in the upper atmosphere.

PAH↗

NASA NTRS2015

Phase 1 Final Report: Titan Submarine

The conceptual design of a submarine for Saturn's moon Titan was a funded NASA Innovative Advanced Concepts (NIAC) Phase 1 for 2014. The proposal stated the desire to investigate what science a submarine for Titan's liquid hydrocarbon seas might accomplish and what that submarine might look like. Focusing on a flagship class science system (100 kg), it was found that a submersible platform can accomplish extensive science both above and below the surface of the Kraken Mare. Submerged science includes mapping using side-looking sonar, imaging and spectroscopy of the lake, as well as sampling of the lake's bottom and shallow shoreline. While surfaced, the submarine will not only sense weather conditions (including the interaction between the liquid and atmosphere) but also image the shoreline, as much as 2 km inland. This imaging requirement pushed the landing date to Titan's next summer period (2047) to allow for lighted conditions, as well as direct-to-Earth communication, avoiding the need for a separate relay orbiter spacecraft. Submerged and surfaced investigation are key to understanding both the hydrological cycle of Titan as well as gather hints to how life may have begun on Earth using liquid, sediment, and chemical interactions. An estimated 25 Mb of data per day would be generated by the various science packages. Most of the science packages (electronics at least) can be safely kept inside the submarine pressure vessel and warmed by the isotope power system.The baseline 90-day mission would be to sail submerged and surfaced around and through Kraken Mare investigating the shoreline and inlets to evaluate the sedimentary interaction both on the surface and then below. Depths of Kraken have yet to be sensed (Ligeia to the north is thought to be 200 m (656 ft) deep), but a maximum depth of 1,000 m (3,281 ft) for Kraken Mare was assumed for the design). The sub would spend 20 d at the interface between Kraken Mare and Ligeia Mare for clues to the drainage of liquid methane into the currently predicted predominantly ethane Kraken Mare. During an extended ninety-day mission, it would transit the throat of Kraken (now Seldon Fretum) and perform similar explorations in other areas of Kraken Mare. Once this half year of exploration is completed the submarine could be tasked to revisit points of interest and perhaps do a complete sonar mapping of the seas. All in all, the submarine could explore over 3,000 km (1,864 mi) in its primary mission at an average speed of 0.3 meters per second.

Titan↗

NASA NTRS2015

Titan Submarine: Exploring The Depths of Kraken Mare

The conceptual design of a submarine for Saturn's moon Titan was a funded NASA Innovative Advanced Concepts (NIAC) Phase I for 2014. The effort investigated what science a submarine for Titan's liquid hydrocarbon approximately 93 Kelvin (-180 degrees Centigrade) seas might accomplish and what that submarine might look like. Focusing on a flagship class science system (approximately100 kilograms) it was found that a submersible platform can accomplish extensive and exciting science both above and below the surface of the Kraken Mare The submerged science includes mapping using side looking sonar, imaging and spectroscopy of the sea at all depths, as well as sampling of the sea's bottom and shallow shoreline. While surfaced the submarine will not only sense weather conditions (including the interaction between the liquid and atmosphere) but also image the shoreline, as much as 2 kilometers inland. This imaging requirement pushed the landing date to Titan's next summer period (approximately 2047) to allow for continuous lighted conditions, as well as direct-to-Earth (DTE) communication, avoiding the need for a separate relay orbiter spacecraft. Submerged and surfaced investigation are key to understanding both the hydrological cycle of Titan as well as gather hints to how life may have begun on Earth using liquid/sediment/chemical interactions. An estimated 25 megabits of data per day would be generated by the various science packages. Most of the science packages (electronics at least) can be safely kept inside the submarine pressure vessel and warmed by the isotope power system. This paper discusses the results of Phase I as well as the plans for Phase II.

submarine↗

NASA NTRS2016

Titan-Like Exoplanets: Variations in Geometric Albedo and Effective Transit Height with Haze Production Rate

Extensive studies characterizing Titan present an opportunity to study the atmospheric properties of Titan-like exoplanets. Using an existing model of Titan's atmospheric haze, we computed geometric albedo spectra and effective transit height spectra for six values of the haze production rate (zero haze to twice present) over a wide range of wavelengths (0.2-2 microns). In the geometric albedo spectra, the slope in the UV-visible changes from blue to red when varying the haze production rate values from zero to twice the current Titan value. This spectral feature is the most effective way to characterize the haze production rates. Methane absorption bands in the visible-NIR compete with the absorbing haze, being more prominent for smaller haze production rates. The effective transit heights probe a region of the atmosphere where the haze and gas are optically thin and that is thus not effectively probed by the geometric albedo. The effective transit height decreases smoothly with increasing wavelength, from 376 km to 123 km at 0.2 and 2 microns, respectively. When decreasing the haze production rate, the methane absorption bands become more prominent, and the effective transit height decreases with a steeper slope with increasing wavelength. The slope of the geometric albedo in the UV-visible increases smoothly with increasing haze production rate, while the slope of the effective transit height spectra is not sensitive to the haze production rate other than showing a sharp rise when the haze production rate increases from zero. We conclude that geometric albedo spectra provide the most sensitive indicator of the haze production rate and the background Rayleigh gas. Our results suggest that important and complementary information can be obtained from the geometric albedo and motivates improvements in the technology for direct imaging of nearby exoplanets.

Geometric albedo↗

NASA NTRS2014

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. TheHC3N 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 approx.. greater than 400 km), whereas HC3N is abundant at a broader range of altitudes (z approx. equal to 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 approx. greater than 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 × 10(exp 13) per sq.cm and 2.3 × 10(exp 14) per sq.cm, respectively.

ALMA Telescope↗