Titan's Surface Research Articles

Stable Carbon Isotope Fractionation during Bacterial Acetylene Fermentation: Potential for Life Detection in Hydrocarbon-Rich Volatiles of Icy Planet(oid)s.

We report the first study of stable carbon isotope fractionation during microbial fermentation of acetylene (C2H2) in sediments, sediment enrichments, and bacterial cultures. Kinetic isotope effects (KIEs) averaged 3.7 ± 0.5‰ for slurries prepared with sediment collected at an intertidal mudflat in San Francisco Bay and 2.7 ± 0.2‰ for a pure culture of Pelobacter sp. isolated from these sediments. A similar KIE of 1.8 ± 0.7‰ was obtained for methanogenic enrichments derived from sediment collected at freshwater Searsville Lake, California. However, C2H2 uptake by a highly enriched mixed culture (strain SV7) obtained from Searsville Lake sediments resulted in a larger KIE of 9.0 ± 0.7‰. These are modest KIEs when compared with fractionation observed during oxidation of C1 compounds such as methane and methyl halides but are comparable to results obtained with other C2 compounds. These observations may be useful in distinguishing biologically active processes operating at distant locales in the Solar System where C2H2 is present. These locales include the surface of Saturn's largest moon Titan and the vaporous water- and hydrocarbon-rich jets emanating from Enceladus. Key Words: Acetylene—Fermentation—Isotope fractionation—Enceladus—Life detection. Astrobiology 15, 977–986.

Growth of Novel Ceramic Layers on Metals via Chemical and Heat Treatments for Inducing Various Biological Functions

The present authors’ systematic studies on growth of novel ceramic layers on Ti metal and its alloys by chemical and heat treatments for inducing bone-bonding bioactivity and some other biological functions are reviewed. Ti metal formed an apatite on its surface in a simulated body fluid, when heat-treated after exposure to strong acid solutions to form rutile surface layer, or to strong alkali solutions to form sodium titanate surface layer. Both types of Ti metal tightly bonded to the living bone. The alkali and heat treatment was applied to the surface Ti metal of an artificial hip joint and successfully used in the clinic since 2007. The acid and heat treatments was applied to porous Ti metal to induce osteoconductivity as well as osteoinductivity. The resulting product was successfully used in clinical trials for spinal fusion devices. For the Ti-based alloys, the alkali and heat treatment was little modified to form calcium titanate surface layer. Bone-growth promoting Mg, Sr, and Zn ions as well as the antibacterial Ag ion were successfully incorporated into the calcium titanate layer.

Titan's asymmetric lake distribution mediated by methane transport due to atmospheric eddies

AbstractThe hemispheric asymmetry of Titan's surface methane has been proposed to be a consequence of orbital forcing affecting Titan's hydrologic cycle, but the mechanism behind asymmetrical transport of moisture remains to be examined. Using general circulation model simulations of Titan's atmosphere, we show that atmospheric moisture transport by three‐dimensional tropospheric eddies is critical in generating Titan's surface liquid asymmetry. Comparison of axisymmetric and three‐dimensional simulations demonstrates that a significant asymmetry only develops in the latter case. Analysis of the components of the three‐dimensional moisture transport reveals that nonaxisymmetric eddies transport methane away from the poles and into the midlatitudes, where they transfer moisture into the cross‐equatorial transport by the mean meridional circulation, producing an atmospheric “bucket brigade.” Because these high‐latitude, baroclinic eddies are more intense in the south than in the north, the net transport is preferentially northward, with the northern hemisphere gaining surface liquid at the expense of the southern hemisphere.

Radar scattering of linear dunes and mega-yardangs: Application to Titan

The Ku-band (13.8GHz – 2.2cm) RADAR instrument onboard the Cassini-Huygens spacecraft has revealed the richness of the surface of Titan, as numerous seas, lakes, rivers, cryo-volcanic flows and vast dune fields have been discovered. Linear dunes are a major geomorphological feature present on Titan, covering up to 17% of its surface, mainly in equatorial regions. However, the resolution of the RADAR instrument is not good enough to allow a detailed study of the morphology of these features. In addition, other linear wind-related landforms, such as mega-yardangs (linear wind-abraded ridges formed in cohesive rocks), are likely to present a comparable radar signature that could be confused with the one of dunes. We conducted a comparative study of the radar radiometry of both linear dunes and mega-yardangs, based on representative terrestrial analogues: the linear dunes located in the Great Sand Sea in western Egypt and in the Namib Desert in Namibia, and the mega-yardangs observed in the Lut Desert in eastern Iran and in the Borkou Desert in northern Chad. We analysed the radar scattering of both terrestrial linear dunes and mega-yardangs, using high-resolution radar images acquired by the X-band (9.6GHz – 3.1cm) sensor of the TerraSAR-X satellite. Variations seen in the radar response of dunes are the result of a contrast between the dune and interdune scattering, while for mega-yardangs these variations are the result of a contrast between ridges and erosion valleys. We tested a simple surface scattering model, with parameters derived from the local topography and surface roughness estimates, to accurately reproduce the radar signal variations for both landforms. It appears that we can discriminate between two types of dunes – bare interdunes as in Egypt and sand-covered interdunes as in Namibia, and between two types of mega-yardangs – young yardangs as in Iran and older ones as in Chad. We applied our understanding of the radar scattering to the analysis of Cassini RADAR T8 acquisitions over the Belet Sand Sea on Titan, and show that the linear dunes encountered there are likely to be of both Egyptian and Namibian type. We also show that the radar-bright linear features observed in Cassini RADAR T64 and T83 acquisitions are very likely to be mega-yardangs, possible remnants of ancient lake basins at mid-latitude, formed when Titan’s climate was different.

Investigation of the growth and local stoichiometric point group symmetry of titania nanotubes during potentiostatic anodization of titanium in phosphate electrolytes

Potentiostatic anodization of commercially pure, 50µm-thick titanium (Ti) foil was performed in aqueous, phosphate electrolytes at increasing experimental timeframes at a fixed applied potential for the synthesis of titania nanotube arrays (TNAs). High resolution scanning electron microscopy images, combined with energy dispersive spectroscopy and x-ray diffraction spectra reveal that anodization of the Ti foil in a 1M NaF+0.5M H3PO4 electrolyte for 4h yields a titanate surface with pore diameters ranging between 100 and 500nm. The presence of rods on the Ti foil surface with lengths exceeding 20µm and containing high concentrations of phosphor on the exterior was also detected at these conditions, along with micro-sized coral reef-like titanate balls. We propose that the formation of these structures play a major role during the anodization process and impedes nanotube growth during the anodization process. High spatially resolved scanning transmission electron microscopy-electron energy loss spectroscopy (STEM-EELS) performed along the length of a single anodized TiO2 nanotube reveals a gradual evolution of the nanotube crystallinity, from a rutile-rich bottom to a predominantly anatase TiO2 structure along its length.

Incubator proof miniaturized Holomonitor to in situ monitor cancer cells exposed to green tea polyphenol and preosteoblast cells adhering on nanostructured titanate surfaces: validity of the measured parameters and their corrections.

The in situ observation of cell movements and morphological parameters over longer periods of time under physiological conditions is critical in basic cell research and biomedical applications. The quantitative phase-contrast microscope applied in this study has a remarkably small size, therefore it can be placed directly into a humidified incubator. Here, we report on the successful application of this M4 Holomonitor to observe cancer cell motility, motility speed, and migration in the presence of the green tea polyphenol, epigallocatechin gallate, as well as to monitor the adhesion of preosteoblast cells on nanostructured titanate coatings, relevant for biomedical applications. A special mechanical stage was developed to position the sample into that range of the optical arrangement where digital autofocusing works with high reproducibility and precision. By in-depth analyzing the obtained single cell morphological parameters, we show that the limited vertical resolution of the optical setup results in underestimated single cell contact area and volume and overestimated single cell averaged thickness. We propose a simple model to correct the recorded data to obtain more precise single cell parameters. We compare the results with the kinetic data recorded by a surface sensitive optical biosensor, optical waveguide lightmode spectroscopy.

Transition from Order to Configurational Disorder for Surface Reconstructions on SrTiO_{3}(111).

There is growing interest in ternary oxide surfaces due to their role in areas ranging from substrates for low power electronics to heterogeneous catalysis. Descriptions of these surfaces to date focus on low-temperature explanations where enthalpy dominates, and less on the implications of configurational entropy at high temperatures. We report here the structure of three members of the n×n (2≤n≤4) reconstructions of the strontium titanate (111) surface using a combination of transmission electron diffraction, density functional theory modeling, and scanning tunneling microscopy. The surfaces contain a mixture of the tetrahedral TiO_{4} units found on the (110) surface sitting on top of octahedral TiO_{5}[] (where [] is a vacant octahedral site), and TiO_{6} units in the second layer that are similar to those found on the (001) surface. We find clear evidence of a transition from the ordered enthalpy-dominated 3×3 and 4×4 structures to a configurational entropy-dominated 2×2 structure that is formed at higher temperatures. This changes many aspects of how oxide surfaces should be considered, with significant implications for oxide growth.

Spectral properties of Titan's impact craters imply chemical weathering of its surface.

We examined the spectral properties of a selection of Titan's impact craters that represent a range of degradation states. The most degraded craters have rims and ejecta blankets with spectral characteristics that suggest that they are more enriched in water ice than the rims and ejecta blankets of the freshest craters on Titan. The progression is consistent with the chemical weathering of Titan's surface. We propose an evolutionary sequence such that Titan's craters expose an intimate mixture of water ice and organic materials, and chemical weathering by methane rainfall removes the soluble organic materials, leaving the insoluble organics and water ice behind. These observations support the idea that fluvial processes are active in Titan's equatorial regions.

Modeling nitrogen and methane with ethane and propane gas hydrates at low temperatures (173–290 K) with applications to Titan

The FREZCHEM model was primarily designed for cold temperatures (173–298K) and high pressures (1–1000bars). Nitrogen gas (95.0%) and methane gas (5.0%) are major gases on the surface of Titan. Recently, we added nitrogen and methane gas hydrates to FREZCHEM model on Titan; and nitrogen–methane gas hydrates formed on Titan at 178K. The other common but less abundant gases on Titan are ethane (C2H6) and propane (C3H8) that can also form gas hydrates with nitrogen and methane. The specific objectives of this study were to (1) add ethane and propane to gas hydrates, including mixtures with nitrogen, methane, and carbon dioxide, and (2) explore the potential roles of gas hydrates on Titan. At 273K, the Ln(gas hydrates) were 5.095 for N2, 3.217 for CH4, 2.327 for CO2, 1.288 for C2H6, and 0.281 for C3H8. At 173K, the Ln(gas hydrates) were −4.968 for N2, −6.102 for CH4, −7.803 for CO2, −5.125 for C2H6, and −5.512 for C3H8. Apparently C2H6 and C3H8 gas hydrates change less at lower temperatures than N2, CH4, and CO2 gas hydrates. In previous papers, we added three mixed CH4–CO2, N2–CH4, and N2–CO2 binary gas hydrates. In this paper, we added ethane and propane to include new binary gas hydrate mixtures of N2–C2H6, N2–C3H8, C2H6–C3H8, CH4–C2H6, CH4–C3H8, CO2–C2H6, and CO2–C3H8. Today, there are ten binary gas hydrates in the FREZCHEM model. In the text, how to cope with more than two species is described. Simulations from 273K to 173K used a surface Titan pressure of 1.467 bars with a major gas of nitrogen (94.24%), a minor gas of methane (5.65%), and extremely minor gases of ethane (0.0038%), and propane (0.000343%). Eventually at 178K, N2·6H2O formed with 0.17694mol, CH4·6H2O formed with 0.04101mol, C2H6·6H2O formed with 6.48e−6mol, and C3H8·6H2O formed with 9.36e−7mol. Based on the atmospheric conditions of Titan, the trace gases of ethane and propane led to low gas hydrate precipitations of ethane and propane with nitrogen and methane. However, the gas concentrations could be very different in an ocean of Titan that could be 50 to 175km beneath the surface where the temperatures may increase as high as 260K. Methane gas hydrates are likely dominant beneath the surface of Titan with some minor contributions from nitrogen, ethane, and propane. Below the surface of Titan in the ocean and icy shell, gas hydrates clearly depend on the gas concentrations of methane, nitrogen, ethane, and propane as well as temperature and pressure.

Heat Rejection in the Titan Surface Environment: Potential Impact on Science Investigations

Practical long-lived exploration systems on and near the surface of Saturn’s moon Titan likely would require radioisotope power systems and could usefully exploit the waste heat from such systems to maintain benign internal operating temperatures. However, the heat must still be rejected, and the understanding of heat transfer conditions to the atmosphere, as well as to liquid and solid surfaces, is summarized. This waste heat may perturb the environment in several ways that would compromise scientific measurements. The potential meteorological disturbances introduced by various power levels are discussed, and the effects of heat flux on surface materials are assessed. It is found that a heat output of or higher requires a mast of 1 m or more be deployed away from a lander to avoid significant wind measurement perturbations. Even heat leaks of only through the hull of a vehicle immersed in Titan’s liquid hydrocarbon seas may cause significant effervescence and fog generation.

13C and 15N fractionation of CH4/N2 mixtures during photochemical aerosol formation: Relevance to Titan

The ratios of the stable isotopes that comprise each chemical species in Titan’s atmosphere provide critical information towards understanding the processes taking place within its modern and ancient atmosphere. Several stable isotope pairs, including 12C/13C and 14N/15N, have been measured in situ or probed spectroscopically by Cassini-borne instruments, space telescopes, or through ground-based observations. Current attempts to model the observed isotope ratios incorporate fractionation resulting from atmospheric diffusion, hydrodynamic escape, and primary photochemical processes. However, the effect of a potentially critical pathway for isotopic fractionation – organic aerosol formation and subsequent deposition onto the surface of Titan – has not been considered due to insufficient data regarding fractionation during aerosol formation. To better understand the nature of this process, we have conducted a laboratory study to measure the isotopic fractionation associated with the formation of Titan aerosol analogs, commonly referred to as ‘tholins’, via far-UV irradiation of several methane (CH4) and dinitrogen (N2) mixtures. Analysis of the δ13C and δ15N isotopic signatures of the photochemical aerosol products using an isotope ratio mass spectrometer (IRMS) show that fractionation direction and magnitude are dependent on the initial bulk composition of the gas mixture. In general, the aerosols showed enrichment in 13C and 14N, and the observed fractionation trends can provide insight into the chemical mechanisms controlling photochemical aerosol formation.

Gas Chromatography Analysis of Discharge Products in N2‐CH4 Gas Mixture at Atmospheric Pressure: Study of Mimic Titan's Atmosphere

AbstractIn this paper, we report presence of various organic products formed in a flowing atmospheric glow discharge fed by gas mixture containing 1‐5 % of methane in nitrogen, which mimics the Titan's atmosphere. Gaseous products from the discharge exhaust were analysed by Gas Chromatography with Mass Spectrometry (GC‐MS). The experimental results revealed C2H2, HCN, and CH3CN as the major products. Various hydrocarbons and nitriles were the other determined gaseous products. Whilst many of these compounds have been predicted and/or observed in the Titan atmosphere, the present plasma experiments provide evidence of both the chemical complexity of Titan atmospheric processes and the mechanisms by which larger species grow prior to form the dust that should cover much of the Titan's surface. (© 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

Solubility of polyethers in hydrocarbons at low temperatures. A model for potential genetic backbones on warm titans.

Ethers are proposed here as the repeating backbone linking units in linear genetic biopolymers that might support Darwinian evolution in hydrocarbon oceans. Hydrocarbon oceans are found in our own solar system as methane mixtures on Titan. They may be found as mixtures of higher alkanes (propane, for example) on warmer hydrocarbon-rich planets in exosolar systems ("warm Titans"). We report studies on the solubility of several short polyethers in propane over its liquid range (from 85 to 231 K, or -188 °C to -42 °C). These show that polyethers are reasonably soluble in propane at temperatures down to ca. 200 K. However, their solubilities drop dramatically at still lower temperatures and become immeasurably low below 170 K, still well above the ∼ 95 K in Titan's oceans. Assuming that a liquid phase is essential for any living system, and genetic biopolymers must dissolve in that biosolvent to support Darwinism, these data suggest that we must look elsewhere to identify linear biopolymers that might support genetics in Titan's surface oceans. However, genetic molecules with polyether backbones may be suitable to support life in hydrocarbon oceans on warm Titans, where abundant organics and environments lacking corrosive water might make it easier for life to originate.

Localized versus itinerant states created by multiple oxygen vacancies in SrTiO3

Oxygen vacancies in strontium titanate surfaces (SrTiO3) have been linked to the presence of a two-dimensional electron gas with unique behavior. We perform a detailed density functional theory study of the lattice and electronic structure of SrTiO3 slabs with multiple oxygen vacancies, with a main focus on two vacancies near a titanium dioxide terminated SrTiO3 surface. We conclude based on total energies that the two vacancies preferably inhabit the first two layers, i.e. they cluster vertically, while in the direction parallel to the surface, the vacancies show a weak tendency towards equal spacing. Analysis of the nonmagnetic electronic structure indicates that oxygen defects in the surface TiO2 layer lead to population of Ti states and thus itinerancy of the electrons donated by the oxygen vacancy. In contrast, electrons from subsurface oxygen vacancies populate Ti eg states and remain localized on the two Ti ions neighboring the vacancy. We find that both the formation of a bound oxygen-vacancy state composed of hybridized Ti 3eg and 4p states neighboring the oxygen vacancy as well as the elastic deformation after extracting oxygen contribute to the stabilization of the in-gap state.

Investigating the mechanism of catalytic reduction of silver nitrate on the surface of barium titanate at room temperature: oxygen vacancies play a key role

The oxygen vacancies on BaTiO3 surface linked with the hydroxyl oxygen of ethylene glycol and catalyzed the reduction of AgNO3.

Experimental constraints on the composition and dynamics of Titan's polar lakes

Titan's polar lakes are thought to be predominantly composed of liquid ethane and methane; however, little is known on the ratio of these hydrocarbons in the lakes, and the stability and dynamics of these mixtures. Here we provide the first experimental constraints under Titan surface conditions of liquid hydrocarbon mixture evaporation. Our results are relevant to Titan's polar temperatures and pressures (∼92 K and 1.5 bar), and cover a wide range of methane–ethane compositions. We show that evaporation is negligible for pure ethane, but increases nearly linearly with increasing methane concentration. Early dissolution of N2 results in ternary mixtures evaporating, which is modeled by a ‘hybrid’ thermodynamic equilibrium approach combining Perturbed-Chain Statistical Associating Fluid Theory with a diffusion and buoyancy-driven mass flux model. The approach follows the experimental evaporation rate measurements presented in this study, and allows for the calculation of the corresponding liquid methane–ethane–nitrogen ratios. Such results along with Cassini inferred lake evaporation rates can be used to estimate the composition of Titan's polar liquids, and may have implications on their origin. Our results suggest that Ontario Lacus is predominantly composed of ethane (>50–80 mol%), indicating it may be a residual lake following extensive seasonal methane evaporation, and/or might be in contact with a subsurface liquid reservoir.

Imaging the evolution of d states at a strontium titanate surface.

Oxide electronics is a promising alternative to the conventional silicon-based semiconductor technology, owing to the rich functionalities of oxide thin films and heterostructures. In contrast to the silicon surface, however, the electronic structure of the SrTiO3 surface, the most important substrate for oxide thin films growth, is not yet completely understood. Here we report on the electronic states of a reconstructed (001) surface of SrTiO3 determined in real space, with scanning tunneling microscopy/spectroscopy and density functional theory calculations. We found a remarkable energy dependence of the spectroscopic image: Theoretical analysis reveals that symmetry breaking at the surface lifts the degeneracy in the t2g state (dxy, dyz, and dzx) of Ti 3d orbitals, whose anisotropic spatial distribution leads to a sharp transition in the spectroscopic image as a function of energy. The knowledge obtained here could be used to gain further insights into emergent phenomena at the surfaces and interfaces with SrTiO3.

Efficient Carbon Dioxide Electrolysis Based on Perovskite Cathode Enhanced with Nickel Nanocatalyst

The Mn-doped titanate can lead to the remarkable chemical adsorption of CO2 uncovering the tremendous potential for direct high temperature CO2 electrolysis. Unfortunately, the application of this material is still limited by insufficient carbon dioxide splitting and electrocatalytic activity. This study reports the improved electrocatalytic activity and Faraday efficiency of composite cathode with exsolution of nickel nanocrystals on the surface of doped titanate for CO2 electrolysis. The electrical conductivity has been enhanced in the presence of metallic Ni in contrast to bare Mn doped titanate and further correlated to the electrochemical performance of the composite cathodes. Promising electrode polarization has been demonstrated based on the titanate with nickel nanoparticles and the Faraday efficiency is improved for the direct CO2 electrolysis at high temperatures.

Dynamical modelling of river deltas on Titan and Earth

The surface of Titan hosts a unique Earth-like environment with lakes and rivers, and active ‘hydrologic’ cycle of methane. We investigate sediment transport in Titanian rivers and deposition in Titanian lakes with particular attention to formation of river deltas. The obtained results are compared with analogous terrestrial processes. The numerical model based on Navier–Stokes equations for depth-integrated two dimensional turbulent flow and additional equations for bed-load and suspended-load sediment transport was used in our research. It is found that transport of icy grains in Titanian rivers is more effective than silicate grains of the same size in terrestrial rivers for the same assumed total discharge. This effect is explained theoretically using dimensionless form of equations or comparing forces acting on the grains. Our calculations confirm previous results (Burr et al., 2006. Icarus. 181, 235–242). We calculate also models with organic sediments of different densities, namely 1500 and 800kgm−3. We found substantial differences between materials of varying densities on Titan, but they are less pronounced than differences between Titan and Earth.

Insights into Titan's geology and hydrology based on enhanced image processing of Cassini RADAR data

The Cassini Synthetic Aperture Radar has been acquiring images of Titan's surface since October 2004. To date, 59% of Titan's surface has been imaged by radar, with significant regions imaged more than once. Radar data suffer from speckle noise hindering interpretation of small-scale features and comparison of reimaged regions for change detection. We present here a new image analysis technique that combines a denoising algorithm with mapping and quantitative measurements that greatly enhance the utility of the data and offers previously unattainable insights. After validating the technique, we demonstrate the potential improvement in understanding of surface processes on Titan and defining global mapping units, focusing on specific landforms including lakes, dunes, mountains, and fluvial features. Lake shorelines are delineated with greater accuracy. Previously unrecognized dissection by fluvial channels emerges beneath shallow methane cover. Dune wavelengths and interdune extents are more precisely measured. A significant refinement in producing digital elevation models is shown. Interactions of fluvial and aeolian processes with topographic relief is more precisely observed and understood than previously. Benches in bathymetry are observed in northern sea Ligeia Mare. Submerged valleys show similar depth suggesting that they are equilibrated with marine benches. These new observations suggest a liquid level increase in the northern sea, which may be due to changes on seasonal or longer timescales.