Macromolecular organic compounds from the depths of Enceladus.

Saturn's moon Enceladus harbours a global water ocean 1 , which lies under an ice crust and above a rocky core 2 . Through warm cracks in the crust 3 a cryo-volcanic plume ejects ice grains and vapour into space4-7 that contain materials originating from the ocean8,9. Hydrothermal activity is suspected to occur deep inside the porous core10-12, powered by tidal dissipation 13 . So far, only simple organic compounds with molecular masses mostly below 50 atomic mass units have been observed in plume material6,14,15. Here we report observations of emitted ice grains containing concentrated and complex macromolecular organic material with molecular masses above 200 atomic mass units. The data constrain the macromolecular structure of organics detected in the ice grains and suggest the presence of a thin organic-rich film on top of the oceanic water table, where organic nucleation cores generated by the bursting of bubbles allow the probing of Enceladus' organic inventory in enhanced concentrations.

A new upper limit to the field-aligned potential near Titan.

Neutral particles dominate regions of the Saturn magnetosphere and locations near several of Saturn's moons. Sunlight ionizes neutrals, producing photoelectrons with characteristic energy spectra. The Cassini plasma spectrometer electron spectrometer has detected photoelectrons throughout these regions, where photoelectrons may be used as tracers of magnetic field morphology. They also enhance plasma escape by setting up an ambipolar electric field, since the relatively energetic electrons move easily along the magnetic field. A similar mechanism is seen in the Earth's polar wind and at Mars and Venus. Here we present a new analysis of Titan photoelectron data, comparing spectra measured in the sunlit ionosphere at ~1.4 Titan radii (RT) and at up to 6.8 RT away. This results in an upper limit on the potential of 2.95 V along magnetic field lines associated with Titan at up to 6.8 RT, which is comparable to some similar estimates for photoelectrons seen in Earth's magnetosphere.

Organic Biosignature Degradation in Hydrothermal and Serpentinizing Environments: Implications for Life Detection on Icy Moons and Mars.

Evidence of liquid water is a primary indicator of habitability on the icy moons in our outer solar system as well as on terrestrial planets such as Mars. If liquid water-containing environments host life, some of its organic remains can be fossilized and preserved as organic biosignatures. However, inorganic materials may also be present and water-assisted organic-inorganic reactions can transform the organic architecture of biological remains. Our understanding of the fate of these organic remains can be assisted by experimental simulations that monitor the chemical changes that occur in microbial organic matter due to the presence of water and minerals. We performed hydrothermal experiments at temperatures between 100°C and 300°C involving lipid-rich microbes and natural serpentinite mineral mixtures generated by the subaqueous hydrothermal alteration of ultramafic rock. The products reveal what the signals of life may look like when subjected to water-organic-inorganic reactions. Straight- and branched-chain lipids in unaltered samples are joined by cyclization and aromatization products in hydrothermally altered samples. Hydrothermal reactions produce distinct products that are not present in the starting materials, including small, single-ring, heteroatomic, and aromatic compounds such as indoles and phenols. Hydrothermal reactions in the presence of serpentinite minerals lead to significant reduction of these organic structures and their replacement by diketopiperazines (DKPs) and dihydropyrazines (DHPs), which may be compounds that are distinct to organic-inorganic reactions. Given that the precursors of DKPs and DHPs are normally lost during early diagenesis, the presence of these compounds can be an indicator of coexisting recent life and hydrothermal processing in the presence of minerals. However, laboratory experiments reveal that the formation and preservation of these compounds can only occur within a distinct temperature window. Our findings are relevant to life detection missions that aim to access hydrothermal and serpentinizing environments in the subsurfaces of icy moons and Mars.

Mass Spectrometric Fingerprints of Bacteria and Archaea for Life Detection on Icy Moons.

The icy moons of the outer Solar System display evidence of subsurface liquid water and, therefore, potential habitability for life. Flybys of Saturn's moon Enceladus by the Cassini spacecraft have provided measurements of material from plumes that suggest hydrothermal activity and the presence of organic matter. Jupiter's moon Europa may have similar plumes and is the target for the forthcoming Europa Clipper mission that carries a high mass resolution and high sensitivity mass spectrometer, called the MAss Spectrometer for Planetary EXploration (MASPEX), with the capability for providing detailed characterization of any organic materials encountered. We have performed a series of experiments using pyrolysis-gas chromatography-mass spectrometry to characterize the mass spectrometric fingerprints of microbial life. A range of extremophile Archaea and Bacteria have been analyzed and the laboratory data converted to MASPEX-type signals. Molecular characteristics of protein, carbohydrate, and lipid structures were detected, and the characteristic fragmentation patterns corresponding to these different biological structures were identified. Protein pyrolysis fragments included phenols, nitrogen heterocycles, and cyclic dipeptides. Oxygen heterocycles, such as furans, were detected from carbohydrates. Our data reveal how mass spectrometry on Europa Clipper can aid in the identification of the presence of life, by looking for characteristic bacterial fingerprints that are similar to those from simple Earthly organisms.

Hydrothermal Processing of Microorganisms: Mass Spectral Signals of Degraded Biosignatures for Life Detection on Icy Moons.

Life detection missions to the outer solar system are concentrating on the icy moons of Jupiter and Saturn and their inferred subsurface oceans. Access to evidence of habitability, and possibly even life, is facilitated by the ejection of subsurface material in plumes and outgassing fissures. Orbiting spacecraft can intersect the plume material or detect past sputtered remnants of outgassed products and analyze the contents using instruments such as mass spectrometers. Hydrothermalism has been proposed for the subsurface environments of icy moons, and the organic remains of any associated life would be expected to suffer some degradation through hydrothermalism, radiolysis, or spacecraft flyby impact fragmentation. Hydrothermalism is treated here for the first time in the context of the Europa Clipper mission. To assess the influence of hydrothermalism on the ability of orbiting mass spectrometers to detect degrading signals of life, we have subjected Earth microorganisms to laboratory hydrothermal processing. The processed microorganism samples were then analyzed using gas chromatography-mass spectrometry (GC-MS), and mass spectra were generated. Certain compound classes, such as carbohydrates and proteins, are significantly altered by hydrothermal processing, resulting in small one-ring and two-ring aromatic compounds such as indoles and phenols. However, lipid fragments, such as fatty acids, retain their fidelity, and their provenance is easily recognized as biological in origin. Our data indicate that mass spectrometry measurements in the plumes of icy moons, using instruments such as the MAss Spectrometer for Planetary Exploration (MASPEX) onboard the upcoming Europa Clipper mission, can reveal the presence of life even after significant degradation by hydrothermal processing has taken place.

Science Objectives for Flagship-Class Mission Concepts for the Search for Evidence of Life at Enceladus.

Cassini revealed that Saturn's Moon Enceladus hosts a subsurface ocean that meets the accepted criteria for habitability with bio-essential elements and compounds, liquid water, and energy sources available in the environment. Whether these conditions are sufficiently abundant and collocated to support life remains unknown and cannot be determined from Cassini data. However, thanks to the plume of oceanic material emanating from Enceladus' south pole, a new mission to Enceladus could search for evidence of life without having to descend through kilometers of ice. In this article, we outline the science motivations for such a successor to Cassini, choosing the primary science goal to be determining whether Enceladus is inhabited and assuming a resource level equivalent to NASA's Flagship-class missions. We selected a set of potential biosignature measurements that are complementary and orthogonal to build a robust case for any life detection result. This result would be further informed by quantifications of the habitability of the environment through geochemical and geophysical investigations into the ocean and ice shell crust. This study demonstrates that Enceladus' plume offers an unparalleled opportunity for in situ exploration of an Ocean World and that the planetary science and astrobiology community is well equipped to take full advantage of it in the coming decades.

Microchannel plate detector detection efficiency to monoenergetic electrons between 3 and 28 keV.

An unshielded microchannel plate (MCP) detector with an ultrafine pore diameter of 2 µm was irradiated by an electron beam to determine the detection efficiency of electrons for creating detector signals, or counts. Tested electron energies spanned a range of 3 kiloelectron volts (keV) to 28 keV. Higher detection efficiencies were measured at the lower end of this energy range, 0.376 counts per incident electron at 3 keV down to 0.155 at 15 keV with an increase to 0.217 at 18 keV and then another decrease down to 0.15 counts per incident electron at 28 keV. The increase at 18 keV is attributed to primary electron interaction with the L shell electrons of lead (Pb), leading to an increase in secondary electron and X-ray generation within the MCP and thus an increase in detection efficiency. For the electron beam directed normal to the MCP surface, the lowest efficiency of 0.15 counts per incident electron was observed at 28 keV. Detection efficiency was also tested as a function of incident angle with angular steps of 5°. Detection efficiency was more sensitive to the angle of incidence as the incident electron energy decreased. The detection efficiency at 3 keV decreased from 0.376 counts per electron at the zero degree angle (normal incidence to MCP surface) to 0.027 counts per electron at an incident angle of 50° (average in both orientations). At 28 keV, the decrease in detection efficiency as a function of increasing angle was less pronounced, ranging from 0.15 counts per electron at zero degrees to 0.08 counts per electron at 50° (average in both orientations). Experimental data showed lower detection efficiencies compared with previously published data.

Enceladus Plume Structure and Time Variability: Comparison of Cassini Observations.

During three low-altitude (99, 66, 66 km) flybys through the Enceladus plume in 2010 and 2011, Cassini's ion neutral mass spectrometer (INMS) made its first high spatial resolution measurements of the plume's gas density and distribution, detecting in situ the individual gas jets within the broad plume. Since those flybys, more detailed Imaging Science Subsystem (ISS) imaging observations of the plume's icy component have been reported, which constrain the locations and orientations of the numerous gas/grain jets. In the present study, we used these ISS imaging results, together with ultraviolet imaging spectrograph stellar and solar occultation measurements and modeling of the three-dimensional structure of the vapor cloud, to constrain the magnitudes, velocities, and time variability of the plume gas sources from the INMS data. Our results confirm a mixture of both low and high Mach gas emission from Enceladus' surface tiger stripes, with gas accelerated as fast as Mach 10 before escaping the surface. The vapor source fluxes and jet intensities/densities vary dramatically and stochastically, up to a factor 10, both spatially along the tiger stripes and over time between flyby observations. This complex spatial variability and dynamics may result from time-variable tidal stress fields interacting with subsurface fissure geometry and tortuosity beyond detectability, including changing gas pathways to the surface, and fluid flow and boiling in response evolving lithostatic stress conditions. The total plume gas source has 30% uncertainty depending on the contributions assumed for adiabatic and nonadiabatic gas expansion/acceleration to the high Mach emission. The overall vapor plume source rate exhibits stochastic time variability up to a factor ∼5 between observations, reflecting that found in the individual gas sources/jets. Key Words: Cassini at Saturn-Geysers-Enceladus-Gas dynamics-Icy satellites. Astrobiology 17, 926-940.

Laboratory Studies of Methane and Its Relationship to Prebiotic Chemistry.

To examine how prebiotic chemical evolution took place on Earth prior to the emergence of life, laboratory experiments have been conducted since the 1950s. Methane has been one of the key molecules in these investigations. In earlier studies, strongly reducing gas mixtures containing methane and ammonia were used to simulate possible reactions in the primitive atmosphere of Earth, producing amino acids and other organic compounds. Since Earth's early atmosphere is now considered to be less reducing, the contribution of extraterrestrial organics to chemical evolution has taken on an important role. Such organic molecules may have come from molecular clouds and regions of star formation that created protoplanetary disks, planets, asteroids, and comets. The interstellar origin of organics has been examined both experimentally and theoretically, including laboratory investigations that simulate interstellar molecular reactions. Endogenous and exogenous organics could also have been supplied to the primitive ocean, making submarine hydrothermal systems plausible sites of the generation of life. Experiments that simulate such hydrothermal systems where methane played an important role have consequently been conducted. Processes that occur in other Solar System bodies offer clues to the prebiotic chemistry of Earth. Titan and other icy bodies, where methane plays significant roles, are especially good targets. In the case of Titan, methane is both in the atmosphere and in liquidospheres that are composed of methane and other hydrocarbons, and these have been studied in simulation experiments. Here, we review the wide range of experimental work in which these various terrestrial and extraterrestrial environments have been modeled, and we examine the possible role of methane in chemical evolution. Key Words: Methane-Interstellar environments-Submarine hydrothermal systems-Titan-Origin of life. Astrobiology 17, 786-812.

Cassini finds molecular hydrogen in the Enceladus plume: Evidence for hydrothermal processes.

Saturn's moon Enceladus has an ice-covered ocean; a plume of material erupts from cracks in the ice. The plume contains chemical signatures of water-rock interaction between the ocean and a rocky core. We used the Ion Neutral Mass Spectrometer onboard the Cassini spacecraft to detect molecular hydrogen in the plume. By using the instrument's open-source mode, background processes of hydrogen production in the instrument were minimized and quantified, enabling the identification of a statistically significant signal of hydrogen native to Enceladus. We find that the most plausible source of this hydrogen is ongoing hydrothermal reactions of rock containing reduced minerals and organic materials. The relatively high hydrogen abundance in the plume signals thermodynamic disequilibrium that favors the formation of methane from CO2 in Enceladus' ocean.

Analysis of Titan tholin pyrolysis products by comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry.

The reddish brown haze that surrounds Titan, Saturn's largest moon, is thought to consist of tholin-like organic aerosols. Tholins are complex materials of largely unknown structure. The very high peak capacity and structured chromatograms obtained from comprehensive two-dimensional GC (GC x GC) are attractive attributes for the characterization of tholin pyrolysis products. In this report, GC x GC with time-of-flight MS detection and a flash pyrolysis inlet is used to characterize tholin pyrolysis products. Identified pyrolysis products include low-molecular-weight nitriles, alkyl substituted pyrroles, linear and branched hydrocarbons, alkyl-substituted benzenes and PAH compounds. The pyrolysis of standards found in tholin pyrolysate showed that little alteration occurred and thus these structures are likely present in the tholin material.

Analysis of human breath samples with a multi-bed sorption trap and comprehensive two-dimensional gas chromatography (GCxGC).

A multi-bed sorption trap designed to quantitatively collect volatile organic compounds from large-volume vapor samples and inject them into a gas chromatograph is combined with a comprehensive two-dimensional gas chromatograph (GCxGC) for the analysis of organic compounds in human breath samples. The first-column effluent of the GCxGC is modulated by a single-stage, resistively-heated and air-cooled segment of 0.18-mm i.d. stainless steel column using the same stationary phase as the first column. Cooling gas is provided by a two-stage conventional refrigeration system, and thus no consumables other than carrier gas and electric power are required. The sorption trap uses four discreet beds, three containing different grades of graphitized carbon and one containing a carbon molecular sieve. The ordering of the beds in the trap tube is from the weakest to strongest adsorbent during sample collection. Breath samples are collected in gas sampling bags, and samples are passed through the trap at a flow rate of about 50 cm3/min. After sample collection, hydrogen carrier gas flow is initiated in the direction opposite to the sample collection flow, and the metal trap tube is resistively heated to inject a sample plug into the GCxGC. Performance data for the combined GCxGC/sorption-trap instrument is described, and human breath-sample chromatograms are presented.

A compact E × B filter: A multi-collector cycloidal focusing mass spectrometer.

A compact E × B mass spectrometer is presented. The mass spectrometer presented is termed a "perfect focus" mass spectrometer as the resolution of the device is independent of both the initial direction and energy of the ions (spatial and energy independent). The mass spectrometer is small in size (∼10.7 in.(3)) and weight (∼2 kg), making it an attractive candidate for portability when using small, permanent magnets. A multi-collector Faraday cup design allows for the detection of multiple ion beams in discrete collectors simultaneously; providing the opportunity for isotope ratio monitoring. The mass resolution of the device is around 400 through narrow collector slits and the sensitivity of the device follows expected theoretical calculations of the ion current produced in the electron impact ion source. Example mass spectra obtained from the cycloidal focusing mass spectrometer are presented as well as information on mass discrimination based on instrumental parameters and isotope ratio monitoring of certain ion signals in separate Faraday cups.

Detection of argon in the coma of comet 67P/Churyumov-Gerasimenko.

Comets have been considered to be representative of icy planetesimals that may have contributed a significant fraction of the volatile inventory of the terrestrial planets. For example, comets must have brought some water to Earth. However, the magnitude of their contribution is still debated. We report the detection of argon and its relation to the water abundance in the Jupiter family comet 67P/Churyumov-Gerasimenko by in situ measurement of the Rosetta Orbiter Spectrometer for Ion and Neutral Analysis (ROSINA) mass spectrometer aboard the Rosetta spacecraft. Despite the very low intensity of the signal, argon is clearly identified by the exact determination of the mass of the isotope (36)Ar and by the (36)Ar/(38)Ar ratio. Because of time variability and spatial heterogeneity of the coma, only a range of the relative abundance of argon to water can be given. Nevertheless, this range confirms that comets of the type 67P/Churyumov-Gerasimenko cannot be the major source of Earth's major volatiles.

Negative ions at Titan and Enceladus: recent results.

The detection of heavy negative ions (up to 13 800 amu) in Titan's ionosphere is one of the tantalizing new results from the Cassini mission. These heavy ions indicate for the first time the existence of heavy hydrocarbon and nitrile molecules in this primitive Earth-like atmosphere. These ions were suggested to be precursors of aerosols in Titan's atmosphere and may precipitate to the surface as tholins. We present the evidence for and the analysis of these heavy negative ions at Titan. In addition we examine the variation of the maximum mass of the Titan negative ions with altitude and latitude for the relevant encounters so far, and we discuss the implications for the negative ion formation process. We present data from a recent set of encounters where the latitude was varied between encounters, with other parameters fixed. Models are beginning to explain the low mass negative ions, but the formation process for the higher mass ions is still not understood. It is possible that the structures may be chains, rings or even fullerenes. Negative ions, mainly water clusters in this case, were seen during Cassini's recent close flybys of Enceladus. We present mass spectra from the Enceladus plume, showing water clusters and additional species. As at Titan, the negative ions indicate chemical complexities which were unknown before the Cassini encounters, and are indicative of a complex balance between neutrals and positively and negatively charged ions.

At-column heating and a resistively heated, liquid-cooled thermal modulator for a low-resource bench-top GC x GC.

A transportable GC x GC instrument is under development for on-site applications that would benefit from the enhanced resolution and powers of detection, which can be achieved by this method. In the present study, a low-resource GC x GC instrument using an electrically heated and liquid-cooled single-stage thermal modulator that requires no cryogenic materials is evaluated. The instrument also uses at-column heating, thus eliminating the need for a convection oven to house the two columns. The stainless-steel modulator tube is coated with PDMS, which can be heated to 350 degrees C for sample injection into the second-dimension column. The modulator is cooled to -30 degrees C by a 100 mL/min flow of PEG by means of a commercial liquid chiller and a small recirculating pump. Resistive heating of the modulator tube is provided by a programmable power supply, which uses a voltage program that results in increasing modulator temperature during an analysis. This, together with more rapid cooling by the use of a liquid cooling medium, results in reduced solute breakthrough following each heating cycle as the modulator cools to a temperature where quantitative trapping resumes. As a result, modulated peak widths at half-height of less than 40 ms are observed. Design and performance details are presented along with chromatograms of gasoline and an essential oil sample.

Cassini ion and neutral mass spectrometer: Enceladus plume composition and structure.

The Cassini spacecraft passed within 168.2 kilometers of the surface above the southern hemisphere at 19:55:22 universal time coordinated on 14 July 2005 during its closest approach to Enceladus. Before and after this time, a substantial atmospheric plume and coma were observed, detectable in the Ion and Neutral Mass Spectrometer (INMS) data set out to a distance of over 4000 kilometers from Enceladus. INMS data indicate that the atmospheric plume and coma are dominated by water, with significant amounts of carbon dioxide, an unidentified species with a mass-to-charge ratio of 28 daltons (either carbon monoxide or molecular nitrogen), and methane. Trace quantities (<1%) of acetylene and propane also appear to be present. Ammonia is present at a level that does not exceed 0.5%. The radial and angular distributions of the gas density near the closest approach, as well as other independent evidence, suggest a significant contribution to the plume from a source centered near the south polar cap, as distinct from a separately measured more uniform and possibly global source observed on the outbound leg of the flyby.

Electrically heated, air-cooled thermal modulator and at-column heating for comprehensive two-dimensional gas chromatography.

An instrument for comprehensive two-dimensional gas chromatography (GCxGC) is described using an electrically heated and air-cooled thermal modulator requiring no cryogenic materials or compressed gas for modulator operation. In addition, at-column heating is used to eliminate the need for a convection oven and to greatly reduce the power requirements for column heating. The single-stage modulator is heated by current pulses from a dc power supply and cooled by a conventional two-stage refrigeration unit. The refrigeration unit, together with a heat exchanger and a recirculating pump, cools the modulator to about -30 degrees C. The modulator tube is silica-lined stainless steel with an internal film of dimethylpolysiloxane. The modulator tube is 0.18 mm i.d. x 8 cm in length. The modulator produces an injection plug width as small as 15 ms.

Ion neutral mass spectrometer results from the first flyby of Titan.

The Cassini Ion Neutral Mass Spectrometer (INMS) has obtained the first in situ composition measurements of the neutral densities of molecular nitrogen, methane, molecular hydrogen, argon, and a host of stable carbon-nitrile compounds in Titan's upper atmosphere. INMS in situ mass spectrometry has also provided evidence for atmospheric waves in the upper atmosphere and the first direct measurements of isotopes of nitrogen, carbon, and argon, which reveal interesting clues about the evolution of the atmosphere. The bulk composition and thermal structure of the moon's upper atmosphere do not appear to have changed considerably since the Voyager 1 flyby.