The identification of liquid ethane in Titan's Ontario Lacus

Titan was once thought to have global oceans of light hydrocarbons on its surface, but after 40 close flybys of Titan by the Cassini spacecraft, it has become clear that no such oceans exist. There are, however, features similar to terrestrial lakes and seas, and widespread evidence for fluvial erosion, presumably driven by precipitation of liquid methane from Titan's dense, nitrogen-dominated atmosphere. Here we report infrared spectroscopic data, obtained by the Visual and Infrared Mapping Spectrometer (VIMS) on board the Cassini spacecraft, that strongly indicate that ethane, probably in liquid solution with methane, nitrogen and other low-molecular-mass hydrocarbons, is contained within Titan's Ontario Lacus.     

Episodic outgassing as the origin of atmospheric methane on Titan

Saturn's largest satellite, Titan, has a massive nitrogen atmosphere containing up to 5 per cent methane near its surface. Photochemistry in the stratosphere would remove the present-day atmospheric methane in a few tens of millions of years. Before the Cassini-Huygens mission arrived at Saturn, widespread liquid methane or mixed hydrocarbon seas hundreds of metres in thickness were proposed as reservoirs from which methane could be resupplied to the atmosphere over geologic time. Titan fly-by observations and ground-based observations rule out the presence of extensive bodies of liquid hydrocarbons at present, which means that methane must be derived from another source over Titan's history. Here we show that episodic outgassing of methane stored as clathrate hydrates within an icy shell above an ammonia-enriched water ocean is the most likely explanation for Titan's atmospheric methane. The other possible explanations all fail because they cannot explain the absence of surface liquid reservoirs and/or the low dissipative state of the interior. On the basis of our models, we predict that future fly-bys should reveal the existence of both a subsurface water ocean and a rocky core, and should detect more cryovolcanic edifices.     

Release of volatiles from a possible cryovolcano from near-infrared imaging of Titan

Titan is the only satellite in our Solar System with a dense atmosphere. The surface pressure is 1.5 bar (ref. 1) and, similar to the Earth, N2 is the main component of the atmosphere. Methane is the second most important component, but it is photodissociated on a timescale of 10(7) years (ref. 3). This short timescale has led to the suggestion that Titan may possess a surface or subsurface reservoir of hydrocarbons to replenish the atmosphere. Here we report near-infrared images of Titan obtained on 26 October 2004 by the Cassini spacecraft. The images show that a widespread methane ocean does not exist; subtle albedo variations instead suggest topographical variations, as would be expected for a more solid (perhaps icy) surface. We also find a circular structure approximately 30 km in diameter that does not resemble any features seen on other icy satellites. We propose that the structure is a dome formed by upwelling icy plumes that release methane into Titan's atmosphere.     

The lakes of Titan

The surface of Saturn's haze-shrouded moon Titan has long been proposed to have oceans or lakes, on the basis of the stability of liquid methane at the surface. Initial visible and radar imaging failed to find any evidence of an ocean, although abundant evidence was found that flowing liquids have existed on the surface. Here we provide definitive evidence for the presence of lakes on the surface of Titan, obtained during the Cassini Radar flyby of Titan on 22 July 2006 (T16). The radar imaging polewards of 70 degrees north shows more than 75 circular to irregular radar-dark patches, in a region where liquid methane and ethane are expected to be abundant and stable on the surface. The radar-dark patches are interpreted as lakes on the basis of their very low radar reflectivity and morphological similarities to lakes, including associated channels and location in topographic depressions. Some of the lakes do not completely fill the depressions in which they lie, and apparently dry depressions are present. We interpret this to indicate that lakes are present in a number of states, including partly dry and liquid-filled. These northern-hemisphere lakes constitute the strongest evidence yet that a condensable-liquid hydrological cycle is active in Titan's surface and atmosphere, in which the lakes are filled through rainfall and/or intersection with the subsurface 'liquid methane' table.     

Methane storms on Saturn's moon Titan

The presence of dry fluvial river channels and the intense cloud activity in the south pole of Titan over the past few years suggest the presence of methane rain. The nitrogen atmosphere of Titan therefore appears to support a methane meteorological cycle that sculptures the surface and controls its properties. Titan and Earth are the only worlds in the Solar System where rain reaches the surface, although the atmospheric cycles of water and methane are expected to be very different. Here we report three-dimensional dynamical calculations showing that severe methane convective storms accompanied by intense precipitation may occur in Titan under the right environmental conditions. The strongest storms grow when the methane relative humidity in the middle troposphere is above 80 per cent, producing updrafts with maximum velocities of 20 m s(-1), able to reach altitudes of 30 km before dissipating in 5-8 h. Raindrops of 1-5 mm in radius produce precipitation rainfalls on the surface as high as 110 kg m(-2) and are comparable to flash flood events on Earth.     

Rain, winds and haze during the Huygens probe's descent to Titan's surface

The irreversible conversion of methane into higher hydrocarbons in Titan's stratosphere implies a surface or subsurface methane reservoir. Recent measurements from the cameras aboard the Cassini orbiter fail to see a global reservoir, but the methane and smog in Titan's atmosphere impedes the search for hydrocarbons on the surface. Here we report spectra and high-resolution images obtained by the Huygens Probe Descent Imager/Spectral Radiometer instrument in Titan's atmosphere. Although these images do not show liquid hydrocarbon pools on the surface, they do reveal the traces of once flowing liquid. Surprisingly like Earth, the brighter highland regions show complex systems draining into flat, dark lowlands. Images taken after landing are of a dry riverbed. The infrared reflectance spectrum measured for the surface is unlike any other in the Solar System; there is a red slope in the optical range that is consistent with an organic material such as tholins, and absorption from water ice is seen. However, a blue slope in the near-infrared suggests another, unknown constituent. The number density of haze particles increases by a factor of just a few from an altitude of 150 km to the surface, with no clear space below the tropopause. The methane relative humidity near the surface is 50 per cent.     

No oceans on Titan from the absence of a near-infrared specular reflection

With its substantial atmosphere of nitrogen, hydrocarbons and nitriles, Saturn's moon Titan is a unique planetary satellite. Photochemical processing of the gaseous constituents produces an extended haze that obscures the surface. Soon after the Voyager fly-bys in 1980 and 1981 photochemical models led to the conclusion that there should be enough liquid methane/ethane/nitrogen to cover the surface to a depth of several hundred metres. Recent Earth-based radar echoes imply that surface liquid may be present at a significant fraction of the locations sampled. Here we present ground-based observations (at near-infrared wavelengths) and calculations showing that there is no evidence thus far for surface liquid. Combined with the specular signatures from radar observations, we infer mechanisms that produce very flat solid surfaces, involving a substance that was liquid in the past but is not in liquid form at the locations we studied.     

Long-term decline of global atmospheric ethane concentrations and implications for methane

After methane, ethane is the most abundant hydrocarbon in the remote atmosphere. It is a precursor to tropospheric ozone and it influences the atmosphere's oxidative capacity through its reaction with the hydroxyl radical, ethane's primary atmospheric sink. Here we present the longest continuous record of global atmospheric ethane levels. We show that global ethane emission rates decreased from 14.3 to 11.3 teragrams per year, or by 21 per cent, from 1984 to 2010. We attribute this to decreasing fugitive emissions from ethane's fossil fuel source--most probably decreased venting and flaring of natural gas in oil fields--rather than a decline in its other major sources, biofuel use and biomass burning. Ethane's major emission sources are shared with methane, and recent studies have disagreed on whether reduced fossil fuel or microbial emissions have caused methane's atmospheric growth rate to slow. Our findings suggest that reduced fugitive fossil fuel emissions account for at least 10-21 teragrams per year (30-70 per cent) of the decrease in methane's global emissions, significantly contributing to methane's slowing atmospheric growth rate since the mid-1980s.     

D to H ratio and the origin and evolution of Titan's atmosphere

A value of 1.7 x 10(-3) has been reported for the ratio of CH3D to CH4 in the stratosphere of the saturnian moon Titan. A lower value of 6 x 10(-4) for this ratio in the deeper part of Titan's atmosphere was reported by de Bergh et al. For comparison we note that the CH3D to CH4 ratio on Saturn and Jupiter is 8.7 x 10(-5) and 6.7 x 10(-5), respectively. We estimate the uncertainties in all these observations and data reduction to be about a factor of 2. Despite these uncertainties it appears that Titan's atmosphere is enriched in deuterium by a factor of > or = 3 relative to Jupiter and Saturn. Potential causative factors examined here for this enrichment are condensation to form tropospheric methane clouds, fractionation occurring over a hypothetical CH4-C2H6 ocean and between the ocean and the clathrate crust beneath, fractionation which occurred during the formation of Titan and fractionation occurring as a result of the evolution of Titan's atmosphere. We conclude that the greater part of the observed fractionation is probably derived from the formation of Titan and the subsequent evolution of Titan's atmosphere driven by photochemistry.     

Stable methane hydrate above 2 GPa and the source of Titan's atmospheric methane

Methane hydrate is thought to have been the dominant methane-containing phase in the nebula from which Saturn, Uranus, Neptune and their major moons formed. It accordingly plays an important role in formation models of Titan, Saturn's largest moon. Current understanding assumes that methane hydrate dissociates into ice and free methane in the pressure range 1-2 GPa (10-20 kbar), consistent with some theoretical and experimental studies. But such pressure-induced dissociation would have led to the early loss of methane from Titan's interior to its atmosphere, where it would rapidly have been destroyed by photochemical processes. This is difficult to reconcile with the observed presence of significant amounts of methane in Titan's present atmosphere. Here we report neutron and synchrotron X-ray diffraction studies that determine the thermodynamic behaviour of methane hydrate at pressures up to 10 GPa. We find structural transitions at about 1 and 2 GPa to new hydrate phases which remain stable to at least 10 GPa. This implies that the methane in the primordial core of Titan remained in stable hydrate phases throughout differentiation, eventually forming a layer of methane clathrate approximately 100 km thick within the ice mantle. This layer is a plausible source for the continuing replenishment of Titan's atmospheric methane.     

The abundances of constituents of Titan's atmosphere from the GCMS instrument on the Huygens probe

Saturn's largest moon, Titan, remains an enigma, explored only by remote sensing from Earth, and by the Voyager and Cassini spacecraft. The most puzzling aspects include the origin of the molecular nitrogen and methane in its atmosphere, and the mechanism(s) by which methane is maintained in the face of rapid destruction by photolysis. The Huygens probe, launched from the Cassini spacecraft, has made the first direct observations of the satellite's surface and lower atmosphere. Here we report direct atmospheric measurements from the Gas Chromatograph Mass Spectrometer (GCMS), including altitude profiles of the constituents, isotopic ratios and trace species (including organic compounds). The primary constituents were confirmed to be nitrogen and methane. Noble gases other than argon were not detected. The argon includes primordial 36Ar, and the radiogenic isotope 40Ar, providing an important constraint on the outgassing history of Titan. Trace organic species, including cyanogen and ethane, were found in surface measurements.     

Direct detection of variable tropospheric clouds near Titan's south pole

Atmospheric conditions on Saturn's largest satellite, Titan, allow the possibility that it could possess a methane condensation and precipitation cycle with many similarities to Earth's hydrological cycle. Detailed imaging studies of Titan have hitherto shown no direct evidence for tropospheric condensation clouds, although there has been indirect spectroscopic evidence for transient clouds. Here we report images and spectra of Titan that show clearly transient clouds, concentrated near the south pole, which is currently near the point of maximum solar heating. The discovery of these clouds demonstrates the existence of condensation and localized moist convection in Titan's atmosphere. Their location suggests that methane cloud formation is controlled seasonally by small variations in surface temperature, and that the clouds will move from the south to the north pole on a 15-year timescale.     

Methane drizzle on Titan

Saturn's moon Titan shows landscapes with fluvial features suggestive of hydrology based on liquid methane. Recent efforts in understanding Titan's methane hydrological cycle have focused on occasional cloud outbursts near the south pole or cloud streaks at southern mid-latitudes and the mechanisms of their formation. It is not known, however, if the clouds produce rain or if there are also non-convective clouds, as predicted by several models. Here we show that the in situ data on the methane concentration and temperature profile in Titan's troposphere point to the presence of layered optically thin stratiform clouds. The data indicate an upper methane ice cloud and a lower, barely visible, liquid methane-nitrogen cloud, with a gap in between. The lower, liquid, cloud produces drizzle that reaches the surface. These non-convective methane clouds are quasi-permanent features supported by the global atmospheric circulation, indicating that methane precipitation occurs wherever there is slow upward motion. This drizzle is a persistent component of Titan's methane hydrological cycle and, by wetting the surface on a global scale, plays an active role in the surface geology of Titan.     

Possible tropical lakes on Titan from observations of dark terrain

Titan has clouds, rain and lakes--like Earth--but composed of methane rather than water. Unlike Earth, most of the condensable methane (the equivalent of 5?m depth globally averaged) lies in the atmosphere. Liquid detected on the surface (about 2?m deep) has been found by radar images only poleward of 50° latitude, while dune fields pervade the tropics. General circulation models explain this dichotomy, predicting that methane efficiently migrates to the poles from these lower latitudes. Here we report an analysis of near-infrared spectral images of the region between 20°?N and 20°?S latitude. The data reveal that the lowest fluxes in seven wavelength bands that probe Titan's surface occur in an oval region of about 60?×?40?km(2), which has been observed repeatedly since 2004. Radiative transfer analyses demonstrate that the resulting spectrum is consistent with a black surface, indicative of liquid methane on the surface. Enduring low-latitude lakes are best explained as supplied by subterranean sources (within the last 10,000 years), which may be responsible for Titan's methane, the continual photochemical depletion of which furnishes Titan's organic chemistry.     

Biosignatures as revealed by spectropolarimetry of Earthshine

Low-resolution intensity spectra of Earth's atmosphere obtained from space reveal strong signatures of life ('biosignatures'), such as molecular oxygen and methane with abundances far from chemical equilibrium, as well as the presence of a 'red edge' (a sharp increase of albedo for wavelengths longer than 700?nm) caused by surface vegetation. Light passing through the atmosphere is strongly linearly polarized by scattering (from air molecules, aerosols and cloud particles) and by reflection (from oceans and land). Spectropolarimetric observations of local patches of Earth's sky light from the ground contain signatures of oxygen, ozone and water, and are used to characterize the properties of clouds and aerosols. When applied to exoplanets, ground-based spectropolarimetry can better constrain properties of atmospheres and surfaces than can standard intensity spectroscopy. Here we report disk-integrated linear polarization spectra of Earthshine, which is sunlight that has been first reflected by Earth and then reflected back to Earth by the Moon. The observations allow us to determine the fractional contribution of clouds and ocean surface, and are sensitive to visible areas of vegetation as small as 10 per cent. They represent a benchmark for the diagnostics of the atmospheric composition, mean cloud height and surfaces of exoplanets.     

A wind origin for Titan's haze structure

Titan, the largest moon of Saturn, is the only satellite in the Solar System with a dense atmosphere. Titan's atmosphere is mainly nitrogen with a surface pressure of 1.5 atmospheres and a temperature of 95 K (ref. 1). A seasonally varying haze, which appears to be the main source of heating and cooling that drives atmospheric circulation, shrouds the moon. The haze has numerous features that have remained unexplained. There are several layers, including a 'polar hood', and a pronounced hemispheric asymmetry. The upper atmosphere rotates much faster than the surface of the moon, and there is a significant latitudinal temperature asymmetry at the equinoxes. Here we describe a numerical simulation of Titan's atmosphere, which appears to explain the observed features of the haze. The critical new factor in our model is the coupling of haze formation with atmospheric dynamics, which includes a component of strong positive feedback between the haze and the winds.     

Subducted banded iron formations as a source of ultralow-velocity zones at the core-mantle boundary

Ultralow-velocity zones (ULVZs) are regions of the Earth's core-mantle boundary about 1-10 kilometres thick exhibiting seismic velocities that are lower than radial-Earth reference models by about 10-20 per cent for compressional waves and 10-30 per cent for shear waves. It is also thought that such regions have an increased density of about 0-20 per cent (ref. 1). A number of origins for ULVZs have been proposed, such as ponding of dense silicate melt, core-mantle reaction zones or underside sedimentation from the core. Here we suggest that ULVZs might instead be relics of banded iron formations subducted to the core-mantle boundary between 2.8 and 1.8 billion years ago. Consisting mainly of interbedded iron oxides and silica, such banded iron formations were deposited in the world's oceans during the late Archaean and early Proterozoic eras. We argue that these layers, as part of the ocean floor, would be recycled into the Earth's interior by subduction, sink to the bottom of the mantle and may explain all of the observed features of ULVZs.     

Large differences in tropical aerosol forcing at the top of the atmosphere and Earth's surface

The effect of radiative forcing by anthropogenic aerosols is one of the largest sources of uncertainty in climate predictions. Direct observations of the forcing are therefore needed, particularly for the poorly understood tropical aerosols. Here we present an observational method for quantifying aerosol forcing to within +/-5 per cent. We use calibrated satellite radiation measurements and five independent surface radiometers to quantify the aerosol forcing simultaneously at the Earth's surface and the top of the atmosphere over the tropical northern Indian Ocean. In winter, this region is covered by anthropogenic aerosols of sulphate, nitrate, organics, soot and fly ash from the south Asian continent. Accordingly, mean clear-sky solar radiative heating for the winters of 1998 and 1999 decreased at the ocean surface by 12 to 30 Wm(-2), but only by 4 to 10 Wm(-2) at the top of the atmosphere. This threefold difference (due largely to solar absorption by soot) and the large magnitude of the observed surface forcing both imply that tropical aerosols might slow down the hydrological cycle.     

甲烷在镁表面上的氧化偶联

XPS和UPS研究结果表明,在金属镁表面氧化过程中存在的过渡态氧O~(δ-)对甲烷有很强的脱氢活性,生成CH_x(x=1,2,3)和深度氧化吸附态CO_3~(2-),以质谱和色谱研究结果表明,CHx偶联生成乙烷和乙烯,CO_3~(2-)热分解生成CO和CO_?。     

Heterogeneous chemistry in the atmosphere of Mars

Hydrogen radicals are produced in the martian atmosphere by the photolysis of water vapour and subsequently initiate catalytic cycles that recycle carbon dioxide from its photolysis product carbon monoxide. These processes provide a qualitative explanation for the stability of the atmosphere of Mars, which contains 95 per cent carbon dioxide. Balancing carbon dioxide production and loss based on our current understanding of the gas-phase chemistry in the martian atmosphere has, however, proven to be difficult. Interactions between gaseous chemical species and ice cloud particles have been shown to be key factors in the loss of polar ozone observed in the Earth's stratosphere, and may significantly perturb the chemistry of the Earth's upper troposphere. Water-ice clouds are also commonly observed in the atmosphere of Mars and it has been suggested previously that heterogeneous chemistry could have an important impact on the composition of the martian atmosphere. Here we use a state-of-the-art general circulation model together with new observations of the martian ozone layer to show that model simulations that include chemical reactions occurring on ice clouds lead to much improved quantitative agreement with observed martian ozone levels in comparison with model simulations based on gas-phase chemistry alone. Ozone is readily destroyed by hydrogen radicals and is therefore a sensitive tracer of the chemistry that regulates the atmosphere of Mars. Our results suggest that heterogeneous chemistry on ice clouds plays an important role in controlling the stability and composition of the martian atmosphere.