The MAss Spectrometer for Planetary EXploration (MASPEX) is a high-mass-resolution, high-sensitivity, multi-bounce time-of-flight mass spectrometer (MBTOF) capable of measuring minor species with abundances of sub-parts-per-million in Europa’s sputter-produced and radiolytically modified exosphere and in its oceanic plumes. The goal of the MASPEX-Europa investigation is to determine, through in-situ measurement of the exosphere and plume composition, whether the conditions for habitability exist or have existed on Europa. As conventionally defined, based on our knowledge of Earth life, the three fundamental conditions for habitability are: (1) the presence of liquid water; (2) the presence of organic compounds and the biogenic elements CHNOPS; and (3) a source of energy available for metabolic processes, which for Europa will most probably be chemosynthetic rather than photosynthetic. Condition (1) is already established by previous indirect (magnetic field) measurements, while MASPEX will contribute directly to the evaluation of condition (2) through highly specific compositional measurements in the Europan exosphere and plumes. The composition measurements will also contribute to the test of condition (3) through disequilibrium states of chemical reactions. Thus, the primary goal of MASPEX for Europa Clipper is to assess the habitability of Europa and specifically of its interior ocean. MASPEX has been developed successfully, and its calibration has demonstrated that it meets its specified requirements for sensitivity, dynamic range, and mass resolution. This paper reports the development of the MASPEX scientific investigation, the instrument, its performance, and calibration.

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.

During Cassini's Grand Finale, the spacecraft flew between Saturn's upper atmosphere and its innermost ring, the D ring. Throughout these final orbits, Cassini encountered material flowing from the D ring into Saturn's atmosphere. Here, we present a compositional analysis of this material using data collected by Cassini's Ion Neutral Mass Spectrometer. We confirm the identification of CH4, CO2, CO, N2, H2O, NH3, and organics in the ring material, and provide upper limits for organic compounds of interest. The H/C, O/C, N/C, and S/C ratios of ring material are constrained using three different kinds of model spectra: automated fits, hand fits of inorganics + hydrocarbons, and hand fits of inorganics + organics with priority given to O-, N-, and S-bearing organics. Additionally, we compare data from the final plunge to earlier orbits, and find that ring material can be divided into gas and dust constituents, with CO2 at the volatility boundary between the two phases. At increasing distance above the equatorial plane, the gas/dust molar ratio increases.

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 space(4-7) that contain materials originating from the ocean(8,9). Hydrothermal activity is suspected to occur deep inside the porous core(10-12), 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 material(6,14,15). 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 Europa plume source, if present, may produce a global exosphere with complex spatial structure and temporal variability in its density and composition. To investigate this interaction we have integrated a water plume source containing multiple organic and nitrite species into a Europan Monte Carlo exosphere model, considering the effect of Europa's gravity in returning plume ejecta to the surface, and the subsequent spreading of adsorbed and exospheric material by thermal desorption and re-sputtering across the entire body. We consider sputtered, radiolytic and potential plume sources, together with surface adsorption, regolith diffusion, polar cold trapping, and re-sputtering of adsorbed materials, and examine the spatial distribution and temporal evolution of the exospheric density and composition. These models provide a predictive basis for telescopic observations (e.g. HST, JWST) and planned missions to the Jovian system by NASA and ESA. We apply spacecraft trajectories to our model to explore possible exospheric compositions which may be encountered along proposed flybys of Europa to inform the spatial and temporal relationship of spacecraft measurements to surface and plume source compositions. For the present preliminary study, we have considered four cases: Case A: an equatorial flyby through a sputtered only exosphere (no plumes), Case B: a flyby over a localized sputtered 'macula' terrain enriched in non-ice species, Case C: a south polar plume with an Enceladus-like composition, equatorial flyby, and Case D: a south polar plume, flyby directly through the plume. (C) 2016 The Authors. Published by Elsevier Inc.

ABSTRACT Comets considered to be pristine objects contain key information about the early formation of the solar system. Their volatile components can provide clues about the origin and evolution of gases and ices in the comets. Measurements with ROSINA/RTOF at 67P/Churyumov–Gerasimenko have now allowed, for the first time, a direct in situ high-time resolution measurement of the most abundant cometary molecules originating directly from a comet’s nucleus over a long time-period, much longer than any previous measurements at a close distance to a comet between 3.1 and 2.3 au. We determine the local densities of H2O, CO2, and CO, and investigate their variabilities.

Titan's ionosphere is created when solar photons, energetic magnetospheric electrons or ions, and cosmic rays ionize the neutral atmosphere. Electron densities generated by current theoretical models are much larger than densities measured by instruments on board the Cassini orbiter. This model density overabundance must result either from overproduction or from insufficient loss of ions. This is the first of two papers that examines ion production rates in Titan's ionosphere, for the dayside and nightside ionosphere, respectively. The first (current) paper focuses on dayside ion production rates which are computed using solar ionization sources (photoionization and electron impact ionization by photoelectrons) between 1000 and 1400km. In addition to theoretical ion production rates, empirical ion production rates are derived from CH4, CH3+, and CH4+ densities measured by the INMS (Ion Neutral Mass Spectrometer) for many Titan passes. The modeled and empirical production rate profiles from measured densities of N-2(+) and CH4+ are found to be in good agreement (to within 20%) for solar zenith angles between 15 and 90 degrees. This suggests that the overabundance of electrons in theoretical models of Titan's dayside ionosphere is not due to overproduction but to insufficient ion losses.

Cassini Ion Neutral Mass Spectrometer (INMS) measurements from roughly a hundred Titan encounters over the Cassini mission yield neutral and ion densities systematically lower, by factors approximately 2 to 3, than estimates from several other spacecraft systems, including the Attitude and Articulation Control System, and Navigation system. In this paper we present a new INMS instrument sensitivity model, obtained by re-analyzing (1) the capture and transmission of neutral gas through the instrument, and (2) the detector gain reduction during pre-launch testing. By correcting for an under-estimation of gas leakage out of the instrument into space by the original calibration model, and adjusting for the gain change, the new model brings INMS densities into much closer agreement with the other Cassini systems. Accordingly, the INMS ion densities are revised upward by a constant detector sensitivity correction factor of 1.55±21 %, while the neutral sensitivities have a complex instrument pointing direction dependence, due (mostly) to the effect of the INMS vent and antechamber-to-closed source tube. In the special case of on-ram pointing the neutral densities are revised upward by a constant factor of 2.2±23 %. The corrected neutral and ion sensitivities given here are applicable to all previously published INMS results at Titan, Enceladus and elsewhere in the Saturn system. The new model gives reliable densities at high ram angles, in some cases above 90 degrees, thereby expanding the list of Titan flybys from which INMS densities may be extracted. We apply the model to obtain accurate densities from several off-ram Titan flybys which gave unusual neutral density vs. altitude profiles, or unreasonably high densities, with the original calibration.

During six encounters between 2008 and 2013, the Cassini Ion and Neutral Mass Spectrometer (INMS) made in situ measurements deep within the Enceladus plumes. Throughout each encounter, those measurements contained density variations that reflected the nature of the source, particularly of the high-velocity jets. Since the dominant constituent of the vapor, H2O, interacted with the walls of the INMS inlet, we track changes in the external vapor density by using more-volatile species that responded promptly to those changes. However, the most-abundant volatiles, at 28 u and 44 u, behaved differently from each other in the plume. At least a portion of their differences may be attributed to mass-dependent thermal velocity that affects Mach number in the high-velocity jets. Variations between volatiles place an emphasis on modeling as a means to construct overall plume density from the volatile densities and to investigate the velocity, gas temperature, and location of the jets. Ice grains, entering the INMS aperture add complexity and uncertainty to the physical interpretation of the data because the grains modified the INMS measurements. A comparison of data from the last three encounters, E14, E17, and E18, are consistent with the VIMS observation of variability in jet production and a slower, more diffuse gas flux from the four sulci or tiger stripes. We provide and describe the INMS data, its processing, and its uncertainty. (C) 2015 Elsevier Inc. All rights reserved.

Highly sensitive, high‐mass resolution mass spectrometry is an important in situ tool for the study of solar system bodies. In this talk we detail the science objectives, develop the rationale for the measurement requirements, and describe potential instrument/mission methodologies for studying the formation, evolution, and habitability of the Galilean satellites. We emphasize our studies of Ganymede and Europa as described in our instrument proposals for the recently selected JUICE mission and the proposed Europa Clipper mission.

In the similar to 6 years since the Cassini spacecraft went into orbit around Saturn in 2004, roughly a dozen Titan flybys have occurred for which the Ion Neutral Mass Spectrometer (INMS) measured that moon's ionospheric density and composition. For these, and for the majority of the similar to 60 close flybys probing to altitudes down to similar to 950 km, Langmuir Probe electron densities were also obtained. These were all complemented by Cassini magnetometer observations of the magnetic fields affected by the Titan plasma interaction. Titan's ionosphere was expected to differ from those of other unmagnetized planetary bodies because of significant contributions from particle impact due to its magnetospheric environment. However, previous analyses of these data clearly showed the dominance of the solar photon source, with the possible exception of the nightside. This paper describes the collected ionospheric data obtained in the period between Cassini's Saturn Orbit Insertion in 2004 and 2009, and examines some of their basic characteristics with the goal of searching for magnetospheric influences. These influences might include effects on the altitude profiles of impact ionization by magnetospheric particles at the Titan orbit location, or by locally produced pickup ions freshly created in Titan's upper atmosphere. The effects of forces on the ionosphere associated with both the draped and penetrating external magnetic fields might also be discernable. A number of challenges arise in such investigations given both the observed order of magnitude variations in the magnetospheric particle sources and the unsteadiness of the magnetospheric magnetic field and plasma flows at Titan's (similar to 20Rs (Saturn Radius)) orbit. Transterminator flow of ionospheric plasma from the dayside may also supply some of the nightside ionosphere, complicating determination of the magnetospheric contribution. Moreover, we are limited by the sparse sampling of the ionosphere during the mission as the Titan interaction also depends on Saturn Local Time as well as possible intrinsic asymmetries and variations of Titan's neutral atmosphere. We use organizations of the data by key coordinate systems of the plasma interaction with Titan's ionosphere to help interpret the observations. The present analysis does not find clear characteristics of the magnetosphere's role in defining Titan's ionosphere. The observations confirm the presence of an ionosphere produced mainly by sunlight, and an absence of expected ionospheric field signatures in the data. Further investigation of the latter, in particular, may benefit from numerical experiments on the inner boundary conditions of 3D models including the plasma interaction and features such as neutral winds. Published by Elsevier Inc.

We have re-evaluated the Cassini Ion Neutral Mass Spectrometer (INMS) C-12/C-13 ratios in the upper atmosphere of Titan based on new calibration sensitivities and an improved model for the NH3 background in the (CH4)-C-13 mass channel. The INMS measurements extrapolated to the surface give a C-12/C-13 in CH4 of 88.5 +/- 1.4. We compare the results to a revised ratio of 91.1 +/- 1.4 provided by the Huygens Gas Chromatograph Mass Spectrometer and 86.5 +/- 7.9 provided by the Cassini Infrared Spectrometer and determine implications of the revised ratios for the evolution of methane in Titan's atmosphere. Because the measured C-12/C-13 is within the probable range of primordial values, we can only determine an upper boundary for the length of time since methane began outgassing from the interior, assuming that outgassing of methane (e.g., cryovolcanic activity) has been continuous ever since. We find that three factors play a crucial role in this timescale: (1) the escape rate of methane, (2) the difference between the current and initial ratios and the rate of methane, and (3) production or resupply due to cryovolcanic activity. We estimate an upper limit for the outgassing timescale of 470 Myr. This duration can be extended to 940 Myr if production rates are large enough to counteract the fractionation due to escape and photochemistry. There is no lower limit to the timescale because the current ratios are within the range of possible primordial values.

Titan's upper atmosphere produces an ionosphere at high altitudes from photoionization and electron impact that exhibits complex chemical processes in which hydrocarbons and nitrogen-containing molecules are produced through ion-molecule reactions. The structure and composition of Titan's ionosphere has been extensively investigated by the Ion and Neutral Mass Spectrometer (INMS) onboard the Cassini spacecraft. We present a detailed study using linear correlation analysis, 1-D photochemical modeling, and empirical modeling of Titan's dayside ionosphere constrained by Cassini measurements. The 1-D photochemical model is found to reproduce the primary photoionization products of N-2 and CH4. The major ions, CH5+, C2H5+, and HCNH+ are studied extensively to determine the primary processes controlling their production and loss. To further investigate the chemistry of Titan's ionosphere we present an empirical model of the ion densities that calculates the ion densities using the production and loss rates derived from the INMS data. We find that the chemistry included in our model sufficiently reproduces the hydrocarbon species as observed by the INMS. However, we find that the chemistry from previous models appears insufficient to accurately reproduce the nitrogen-containing organic compound abundances observed by the INMS. The major ion, HCNH+, is found to be overproduced in both the empirical and 1-D photochemical models. We analyze the processes producing and consuming HCNH+ in order to determine the cause of this discrepancy. We find that a significant chemical loss process is needed. We suggest that the loss process must be with one of the major components, namely C2H2, C2H4, or H-2.

This investigation extends the work presented by Bell et al. (2010a, 2010b). Using the one-dimensional (1-D) configuration of the Titan Global Ionosphere-Thermosphere Model (T-GITM), we quantify the relative importance of the different dynamical and chemical mechanisms that determine the CH4 escape rates calculated by T-GITM. Moreover, we consider the implications of updated Huygens Gas Chromatograph Mass Spectrometer (GCMS) determinations of both the Ar-40 mixing ratios and N-15/N-14 isotopic ratios in work by Niemann et al. (2010). Combining the GCMS constraints in the lower atmosphere with the Ion Neutral Mass Spectrometer (INMS) measurements in work by Magee et al. (2009), our simulation results suggest that the optimal CH4 homopause altitude is located at 1000 km. Using this homopause altitude, we conclude that topside escape rates of 1.0 x 10(10) CH4 m(-2) s(-1) (referred to the surface) are sufficient to reproduce the INMS methane measurements in work by Magee et al. (2009). These escape rates of methane are consistent with the upper limits to methane escape (1.11 x 10(11) CH4 m(-2) s(-1)) established by both the Cassini Plasma Spectrometer (CAPS) and Magnetosphere Imaging Instrument (MIMI) measurements of Carbon-group ions in the near Titan magnetosphere.

The Cassini Ultraviolet Imaging Spectrograph (UVIS) observed an occultation of the Sun by the water vapor plume at the south polar region of Saturn's moon Enceladus. The Extreme Ultraviolet (EUV) spectrum is dominated by the spectral signature of H2O gas, with a nominal line-of-sight column density of 0.90 +/- 0.23 x 10(16) cm(-2) (upper limit of 1.0 x 10(16) cm(-2)). The upper limit for N-2 is 5 x 10(13) cm(-2), or <0.5% in the plume; the lack of N-2 has significant implications for models of the geochemistry in Enceladus' interior. The inferred rate of water vapor injection into Saturn's magnetosphere is similar to 200 kg/s. The calculated values of H2O flux from three occultations observed by UVIS have a standard deviation of 30 kg/s (15%), providing no evidence for substantial short-term variability. Collimated gas jets are detected in the plume with Mach numbers of 5-8, implying vertical gas velocities that exceed 1000 m/sec. Observations at higher altitudes with the Cassini Ion Neutral Mass Spectrometer indicate correlated structure in the plume. Our results support the subsurface liquid model, with gas escaping and being accelerated through nozzle-like channels to the surface, and are consistent with recent particle composition results from the Cassini Cosmic Dust Analyzer. Citation: Hansen, C. J., et al. (2011), The composition and structure of the Enceladus plume, Geophys. Res. Lett., 38, L11202, doi:10.1029/2011GL047415.