New planetary atmosphere simulations: application to the organic aerosols of Titan.

The atmosphere of Titan partly consists of hazes and aerosol particles. Experimental simulation is one of the powerful approaches to study the processes which yield these particles, and their chemical composition. It provides laboratory analogues, sometimes called tholins. Development and optimization of experimental tools were undertaken in order to perform chemical and physical analyses of analogues under conditions free from contamination. A "Titan aerosol generator" was developed in the frame of the Cassini-Huygens mission, in order to produce Titan's aerosol analogues within conditions closer to those of the titanian atmosphere: cold plasma simulation system, low pressure and low temperature. The direct current (DC) glow discharge is produced by applying a DC voltage between two conductive electrodes inserted into the gas mixture-model of the studied atmosphere- at low pressure. A high-impedance power supply is used to provide the electrical field. All the system is installed in a glove box, which protect samples from any contamination. Finally the research program expected with this new material is presented.     

Solid organic matter in the atmosphere and on the surface of outer Solar System bodies.

Many bodies in the outer Solar System display the presence of low albedo materials. These materials, evident on the surface of asteroids, comets, Kuiper Belt objects and their intermediate evolutionary step, Centaurs, are related to macromolecular carbon bearing materials such as polycyclic aromatic hydrocarbons and organic materials such as methanol and related light hydrocarbons, embedded in a dark, refractory, photoprocessed matrix. Many planetary rings and satellites around the outer gaseous planets display such component materials. One example, Saturn's largest satellite, Titan, whose atmosphere is comprised of around 90% molecular nitrogen N2 and less than 10% methane CH4, displays this kind of low reflectivity material in its atmospheric haze. These materials were first recorded during the Voyager 1 and 2 flybys of Titan and showed up as an optically thick pinkish orange haze layer. These materials are broadly classified into a chemical group whose laboratory analogs are termed "tholins", after the Greek word for "muddy". Their analogs are produced in the laboratory via the irradiation of gas mixtures and ice mixtures by radiation simulating Solar ultraviolet (UV) photons or keV charged particles simulating particles trapped in Saturn's magnetosphere. Fair analogs of Titan tholin are produced by bombarding a 9:1 mixture of N2:CH4 with charged particles and its match to observations of both the spectrum and scattering properties of the Titan haze is very good over a wide range of wavelengths. In this paper, we describe the historical background of laboratory research on this kind of organic matter and how our laboratory investigations of Titan tholin compare. We comment on the probable existence of polycyclic aromatic hydrocarbons in the Titan Haze and how biological and nonbiological racemic amino acids produced from the acid hydrolysis of Titan tholins make these complex organic compounds prime candidates in the evolution of terrestrial life and extraterrestrial life in our own Solar System and beyond. Finally, we also compare the spectrum and scattering properties of our resulting tholin mixtures with those observed on Centaur 5145 Pholus and the dark hemisphere of Saturn's satellite Iapetus in order to demonstrate the widespread distribution of similar organics throughout the Solar System.     

Organic chemistry in Titan's atmosphere: new data from laboratory simulations at low temperature.

Many experiments have already been carried out to simulate organic chemistry on Titan, the largest satellite of Saturn. They can provide fruitful information on the nature of minor organic constituents likely to be present in Titan's atmosphere, both in gas and aerosol phases. Indeed, all the organic compounds but one already detected in Titan's atmosphere have been identified in simulation experiments. The exception, C4N2, as well as other compounds expected in Titan from theoretical modeling, such as other N-organics, and polyynes, first of all C6H2, have never been detected in experimental simulation thus far. All these compounds are thermally unstable, and the temperature conditions used during the simulation experiments were not appropriate. We have recently started a new program of simulation experiments with temperature conditions close to that of Titan's environment. It also uses dedicated analytical techniques and procedures compatible with the analysis of organics only stable at low temperatures, as well solid products of low stability in the presence of O2 and H2O. Spark discharge of N2-CH4 gas mixtures was carried out at low temperature in the range 100-150 K. Products were analysed by FTIR, GC and GC-MS techniques. GC-peaks were identified by their mass spectrum, and, in most cases, by comparison of the retention time and mass spectrum with standard ones. We report here the first detection in Titan simulation experiments of C6H2 and HC5N. Their abundance is a few percent relative to C4H2 and HC3N, respectively. Preliminary data on the solid products indicate an elemental composition corresponding to (H11C11N)n. These results open new prospects in the modeling of Titan's haze making.     

New insights into Titan's organic chemistry in the gas and aerosol phases.

Titan, the largest satellite of Saturn, with a dense atmosphere very rich in organics, and many couplings in the various parts of its "geofluid", is a reference for studying prebiotic chemistry on a planetary scale. New data have been obtained from experiments simulating this organic chemistry (gas and aerosol phases), within the right ranges of temperature and a careful avoiding of any chemical contamination. They show a very good agreement with the observational data, demonstrating for the first time the formation of all the organic species already detected in Titan atmosphere including, at last, C4N2, together with many other species not yet detected in Titan. This strongly suggests the presence of more complex organics in Titan's atmosphere and surface, including high molecular weight polyynes and cyanopolyynes. The NASA-ESA Cassini-Huygens mission has been successfully launched in October 1997. The Cassini spacecraft will reach the Saturn system in 2004 and become an orbiter around Saturn, while the Huygens probe will penetrate into Titan's atmosphere. In situ measurements, in particular from Huygens GC-MS and ACP instruments, will provide a detailed analysis of the organics present in the air, aerosols, and surface. This very ambitious mission should yield much information of crucial importance for our knowledge of the complexity of Titan's chemistry, and, more generally for the field of exobiology.     

Super rogue wave catalysis in Titan’s ionosphere

Super rogue ion-acoustic waves are proposed as a physical catalyst for the heavy hydrocarbon ions formation in the Titan ionosphere. We justified that analytically and numerically by probing a Titan referenced plasma system, consists of the most abundant positive ions and superthermal electrons. A solution of the nonlinear Schrödinger equation (NLSE) has provided us by the plasma (un) stable regions at altitude 900–1200 km from the Titan surface with superthermal parameter values, relative ion to electron densities, and temperature ratio variations. Our results are not only agreed with the Cassini data but also predict a chemistry independent approach for the heavy hydrocarbons’ formation conditions.     

不同热解温度下酚醛树脂复合材料渗透率测试

为了获得不同热解温度下酚醛树脂复合材料渗透率,设计搭建了复合材料气体渗透过程实验测量装置,提出了一种测量复合材料渗透率的方法,基于达西定律获得了复合材料渗透率。以不同热解温度下酚醛树脂复合材料为研究对象,进行了气体渗透过程实验测量,获得了材料上下表面气体压力变化曲线,同时得到了渗透过材料的气体流量,进而通过达西定律得出材料的渗透率。结果表明,该实验装置能够实现复杂孔隙复合材料的渗透率的测量。整体上,热解温度越高,渗透率越大。热解温度为400℃,渗透率量级在10-13;600℃和800℃时,渗透率量级在10-11。材料渗透率K和热解温度T满足K=9.7×10-14T-4×10-11。该实验结果为该类材料的渗透和热质扩散性能分析提供了基础物性数据。      

A facility for simulating Titan’s environment

As a result of measurements acquired by the Cassini–Huygens mission of Titan’s near surface atmospheric composition and temperature, Titan conditions can now be simulated in the laboratory and samples can subsequently be subjected to those conditions. Titan demonstrates an active hydrological-like cycle with its thick atmosphere, dynamic clouds, polar lakes of methane and ethane, moist regolith, and extensive fluvial erosive features. Unlike Earth, Titan’s hydrological-like cycle likely involves several constituents, primarily methane and ethane. Here the properties of a new Titan simulation facility are presented, including conceptual methodology, design, implementation, and performance results. The chamber maintains Titan’s surface temperature and pressure, and the sample cryogenic liquids undergoing experimentation are condensed within the chamber itself. During the experiments, the evaporation rates of the sample liquids are directly determined by continually measuring mass. Constituents are analyzed utilizing a Fourier Transform Infrared Spectroscopy (FTIR), and vapor concentrations are determined using a gas chromatograph fitted with a Flame Ionization Detector (FID). All pertinent data is logged via computer. Under laboratory conditions, the direct measurements of the evaporation rates of methane, ethane, and mixtures thereof can be achieved. Among the processes to be studied are the effects of regolith on transport from the subsurface to the atmosphere, the freezing point depression effects of dissolved nitrogen, and the solubility of various relevant organic compounds.     

The low temperature organic chemistry of Titan's geofluid.

Organic chemistry on Titan and prebiotic chemistry on Earth involve the same N-containing organics: nitriles and their oligomers. Couplings of their chemistry in the three parts of Titan's geofluid (atmosphere, aerosols and surface) seem to play a key role in the organic chemical evolution of the planet. If liquid water was present on Titan, then a prebiotic chemistry, involving eutectics, similar to that of the early Earth, may have occurred. However, liquid water is currently absent and a prebiotic chemistry based only on N-organics may be evolving now on Titan. The other consequence of the low temperatures of Titan is the possible formation of organics unstable at room temperature and very reactive. So far, these compounds have not been systematically searched for in experimental studies of Titan's organic chemistry. C4N2 has already been detected on Titan. Powerful reactants in organic chemistry, CH2N2, and CH3N3, may be also present. They exhibit spectral signatures in the mid-IR strong enough to allow their detection at the 10-100 ppb level. They may be detectable on future IR spectra (ISO and Cassini) of Titan.     

From Titan’s tholins to Titan’s aerosols: Isotopic study and chemical evolution at Titan’s surface

In the present work, we focused on the possible isotopic fractionation of carbon during the processes involved in the formation of Titan’s tholins. We present the first results obtained on the ¹²C/¹³C isotopic ratios measured on Titan’s tholins synthesized in laboratory with cold plasma discharges. Measurements of isotopic ratio ¹²C/¹³C, done both on tholins and on the initial gas mixture (N₂:CH₄ (98:2)) used to produce them, do not show any evident deficit or enrichment in ¹³C relatively to ¹²C in the synthesized tholins, compared to the initial gas mixture. This observation allows to go further in the analyses of the ACP experiment data, including part of the Cassini–Huygens mission.     

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 microns, 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.     

The organic aerosols of Titan

A dark reddish organic solid, called tholin, is synthesized from simulated Titanian atmospheres by irradiation with high energy electrons in a plasma discharge. The visible reflection spectrum of this tholin is found to be similar to that of high altitude aerosols responsible for the albedo and reddish color of Titan. The real (n) and imaginary (k) parts of the complex refractive index of thin films of Titan tholin prepared by continuous D.C. discharge through a 0.9 N₂/0.1 CH₄ gas mixture at 0.2 mb is determined from x-ray to microwave frequencies. Values of n (1.65) and k (0.004 to 0.08) in the visible are consistent with deductions made by ground-based and spaceborne observations of Titan. Many infrared absorption features are present in k(λ), including the 4.6 μm nitrile band. Molecular analysis of the volatile component of this tholin was performed by sequential and non-sequential pyrolytic gas chromatography/mass spectrometry. More than one hundred organic compounds are released; tentative identifications include saturated and unsaturated aliphatic hydrocarbons, substituted polycyclic aromatics, nitriles, amines, pyrroles, pyrazines, pyridines, pyrimidines, and the purine, adenine. In addition, acid hydrolysis produces a racemic mixture of biological and non-biological amino acids. Many of these molecules are implicated in the origin of life on Earth, suggesting Titan as a contemporary laboratory environment for prebiological organic chemistry on a planetary scale.     

An engineering model of Titan surface winds for Dragonfly landed operations

Winds near the ground on Titan for the Dragonfly landing site (near Selk crater, 10°N) for the mid-2030s (Titan late southern summer, L_s ~ 310°) are estimated for mission design purposes. Prevailing winds due to the global circulation are typically 0.5 m/s, and do not exceed 1 m/s. Local terrain-induced flows such as slope winds appear to be similarly capped at 1 m/s. At various landing sites and times, these two contributions will vectorially combine to yield steady winds (for part of a Titan day, Tsol) of up to 2.0 m/s, but typically less – the slope wind component will be small in the mid-morning. In early afternoon, as on Earth and Mars, solar-driven convection in the planetary boundary layer will cause wind fluctuations of the order of 0.1 m/s, varying with a typical timescale of ~1000 s. Occasionally this convection organizes into coherent ‘dust devil’ vortices: detectable vortices with speeds of 1 m/s are predicted about once per Titan day. We have introduced the convective velocity scale combined with the advection time of PBL cells as a metric to derive the frequency of occurrence of gusts associated with convective vortices (‘dust devils’). Maximum possible vortex winds on Titan of 2.8 m/s may be expected only once per 40 Tsols, and define the maximum wind (4.8 m/s at 10 m height) that Dragonfly must tolerate without damage. The applicability of different wind combinations, scaled to the height of relevant Dragonfly components above the ground (e.g. the maximum corresponds to 3.9 m/s at 1.3 m height) by a logarithmic wind profile, to Dragonfly design and operations are discussed.     

Boundary layer aerosol retrieval from thermal infrared nadir sounding – Preliminary results

A non-empirical algorithm is presented to retrieve the optical depth in the 750–1250 cm⁻¹ spectral range, of aerosol located in the boundary layer over the ocean, from nadir high-resolution radiance spectra in the thermal infrared. The algorithm is based on a line-by-line radiative transfer forward model and used the Optimal Estimation Method for the retrieval. Its performance strongly depends on the quality of the a priori temperature and H₂O atmospheric profiles. To demonstrate the relevance of the algorithm, distributions of maritime aerosol parameters have been retrieved from IMG/ADEOS data for December 1996, using the algorithm with the LBLRTM radiative transfer code, and ERA40 (ECMWF) a priori atmospheric profiles and surface conditions.     

IR and UV spectroscopic data for polyynes: predictions for long carbon chain compounds in Titan's atmosphere.

A better understanding of the complex organic chemistry occurring in the methane rich atmosphere of Titan can be achieved via the comparison of observations with results obtained by theoretical models. Available observations are still few but their analysis requires the knowledge of a large set of data, namely frequencies and absolute band intensities. Cross sections are also needed to develop the chemical schemes of photochemical models, in particular the schemes leading to the formation of haze particles visible on Titan. Unfortunately, some of these parameters are not well known, especially if one takes into account the extreme physical conditions of the studied object. This lack of data is particularly enhanced for polyynes because these compounds are highly unstable at the usual pressure and temperature conditions of a laboratory and therefore are very difficult to study. We have developed UV and IR studies, coupling experimental and theoretical approaches, in order to extrapolate the parameters available for short polyynes to longer carbon chains. In the mid-UV range, when the length of the chain increases, the absorption system of polyynes is shifted to longer wavelength and its oscillator strength increases linearly. In the IR range, with the increase of the number of carbon bonds, the positions of the CCC and CCH bending modes shift to lower energy, the latest converging rapidly to a fixed value of 620.5 cm-1 for an infinite length polyyne. Implications for detection and evolution of polyynes in Titan's atmosphere are emphasised.     

Quantum chemical calculations of infrared spectra for the identification of unknown compounds by GC/FTIR/MS in exobiological simulation experiments.

Gas chromatography/Fourier transform IR spectroscopy/mass spectrometry (GC/FTIR/MS) is a powerful tool for the separation and unambiguous identification of complex mixtures of organic compounds, where the use of two kinds of spectra allows to significantly increase identification reliability. The simplest situation is when acquired spectra can be found in IR and MS databases, or appropriate standards are available; but this is not always the case. Some simulation experiments related to the origins of life and exobiology (e.g., simulation of amino acid pyrolysis during atmospheric entry of space bodies) can be a typical example when one encounters with numerous unknown compounds. To assist their identification by GC/FTIR/MS, recently we suggested quantum chemical calculations of infrared spectra in order to compare them to IR spectra acquired experimentally. The present work summarizes the results obtained by semi-empirical and ab initio methods, discusses their advantages and limitations, considering as test compounds some cyclic amides and amidines derived from amino acids, saturated and unsaturated nitriles (including those of interest for the Titan atmospheric chemistry), acetylenes and some other nitrogen compounds.     

Interaction of Titan's atmosphere with Saturn's magnetosphere

The Voyager 1 measurements made during the Titan flyby reveal that Saturn's rotating magnetospheric plasma interacts directly with Titan's neutral atmosphere and ionosphere. This results from the lack of an intrinsic magnetic field at Titan. The interaction induces a magnetosphere which deflects the flowing plasma around Titan and forms a plasma wake downstream. Within the tail of the induced magnetosphere, ions of ionospheric origin flow away from Titan. Just outside Titan's magnetosphere, a substantial ion-exosphere forms from an extensive hydrogen-nitrogen exosphere. The exospheric ions are picked up and carried downstream into the wake by the plasma flowing around Titan. Mass loading produced by the addition of exospheric ions slows the wake plasma down considerably in the vicinity of the magnetopause.     

Scientific results from the pioneer Saturn infrared radiometer

The Pioneer 11 Infrared Radiometer instrument made observations of Saturn and its rings in broadband channels centered at 20 and 45 μm and obtained whole-disk information on Titan. A planetary average effective temperature of 96.5±2.5 K implies a total emission 2.8 times the absorbed sunlight. Correlation with radio science results implies that the molar fraction of H₂ is 90±3% (assuming the rest is He). Temperatures at the 1 bar level are 137 to 140 K; regions appearing cooler may be overlain by a cloud acting as a 124 K blackbody surface. A minimum temperature averaging 87 K is reached near 0.06 bars. Ring boundaries and optical depths are consistent with those at optical wavelengths. Ring temperatures are 64–86 K on the south (illuminated) side, ～54 K on the north (unilluminated) side, and at least 67 K in Saturn's shadow. There is evidence for a south to north drop in ring temperatures. Titan's 45 μm brightness temperature is 75±5 K.     

First estimations of the aerosol optical thickness using Langley Method at Southern Brazil (29.4°S, 53.8°W)

The first estimations of the aerosol optical thickness (AOT) using Langley Method at Southern Space Observatory (SSO) at Southern Brazil (29.4°S, 53.8°W) are presented. In addition to ozone and sulphur dioxide columns, AOT can be obtained using Brewer Spectrophotometer at specific wavelengths: 306.3, 310.1, 313.5, 316.8 and 320.1 nm. The AOT was obtained for the period from November/2002 to May/2003. Very low AOT averages were obtained, whose values were about 0.21 ± 0.03 at 306.3 nm, 0.21 ± 0.02 at 310.1 nm, 0.19 ± 0.02 at 313.5 nm, 0.20 ± 0.02 at 316.8 nm and 0.20 ± 0.02 at 320.0 nm for all period analysed. Different behaviour of AOT were obtained at two daily specific periods of aerosol accumulation, one in the afternoons from November/2002 to February/2003, caused mainly by a mild biomass burning season’s in the region and other in the mornings from March to May/2003, due the high relative humidity presented in the region studied.     

Remote sensing of aerosol and radiation from geostationary satellites

The paper presents a high-level overview of current and future remote sensing of aerosol and shortwave radiation budget carried out at the US National Oceanic and Atmospheric Administration (NOAA) from the US Geostationary Operational Environmental Satellite (GOES) series. The retrievals from the current GOES imagers are based on physical principles. Aerosol and radiation are estimated in separate processing from the comparison of satellite-observed reflectances derived from a single visible channel with those calculated from detailed radiative transfer. The radiative transfer calculation accounts for multiple scattering by molecules, aerosol and cloud and absorption by the major atmospheric gases. The retrievals are performed operationally every 30 min for aerosol and every hour for radiation for pixel sizes of 4-km (aerosol) and 15- to 50-km (radiation). Both retrievals estimate the surface reflectance as a byproduct from the time composite of clear visible reflectances assuming fixed values of the aerosol optical depth. With the launch of GOES-R NOAA will begin a new era of geostationary remote sensing. The Advanced Baseline Imager (ABI) onboard GOES-R will offer capabilities for aerosol remote sensing similar to those currently provided by the Moderate Resolution Imaging Spectroradiometer (MODIS) flown on the NASA Earth Observing System (EOS) satellites. The ABI aerosol algorithm currently under development uses a multi-channel approach to estimate the aerosol optical depth and aerosol model simultaneously, both over water and land. Its design is strongly inspired by the MODIS aerosol algorithm. The ABI shortwave radiation budget algorithm is based on the successful GOES Surface and Insolation Product system of NOAA and the NASA Clouds and the Earth’s Radiant Energy System (CERES), Surface and Atmospheric Radiation Budget (SARB) algorithm. In all phases of the development, the algorithms are tested with proxy data generated from existing satellite observations and forward simulations. Final assessment of the performance will be made after the launch of GOES-R scheduled in 2012.     

An aerobot for global in situ exploration of Titan

This paper describes the design and component testing of an aerobot that would be capable of global in situ exploration of Saturn’s moon, Titan, over a 6–12 month mission lifetime. The proposed aerobot is a propeller-driven, buoyant vehicle that resembles terrestrial airships. However, the extremely cold Titan environment requires the use of cryogenic materials of construction and careful thermal design for protection of temperature-sensitive payload elements. Multiple candidate balloon materials have been identified based on extensive laboratory testing at 77 K. The most promising materials to date are laminates comprised of polyester fabrics and/or films with areal densities in the range of 40–100 g/m². The aerobot hull is a streamlined ellipsoid 14 m in length with a maximum diameter of 3 m. The enclosed volume of 60 m³ is sufficient to float a mass of 234 kg at a maximum altitude of 8 km at Titan. Forward and aft ballonets are located inside the hull to enable the aerobot to descend to the surface while preserving a fully inflated streamlined shape. Altitude changes are effected primarily through thrust vectoring of the twin main propellers, with pressure modulated buoyancy change via the ballonets available as a slower backup option. A total of 100 W of electrical power is provided to the vehicle by a radioisotope power supply. Up to half of this power is available to the propulsion system to generate a top flight speed in the range of 1–2 m/s. This speed is expected to be greater than the near surface winds at Titan, enabling the aerobot to fly to and hover over targets of interest. A preliminary science payload has been devised for the aerobot to give it the capability for aerial imaging of the surface, atmospheric observations and sampling, and surface sample acquisition and analysis. Targeting, hovering, surface sample acquisition and vehicle health monitoring and automatic safing actions will all require significant on-board autonomy due to the over 2 h round trip light time between Titan and Earth. An autonomy architecture and a core set of perception, reasoning and control technologies is under development using a free-flying airship testbed of approximately the same size as the proposed Titan aerobot. Data volume from the Titan science mission is expected to be on the order of 100–300 Mbit per day transmitted either direct to Earth through an 0.8 m high gain antenna or via an orbiter relay using an omni-directional antenna on the aerobot.