Organic compounds in Saturn's E-ring and its compositional profile in the vicinity of Rhea

The general topic of this dissertation is the analysis of impact ionization time-of-flight mass spectra of ice grains in Saturn’s E ring sampled in-situ by the Cosmic Dust Analyzer (CDA) onboard the Cassini-Huygens spacecraft. The source of these E ring ice grains is the subsurface ocean of Saturn’s cryo-volcanically active icy moon Enceladus. The Chemical Analyzer subsystem of CDA generated mass spectra of cations that form when the ice grains impinge onto the instrument’s target plate with high speed. The first aim of this work is a detailed compositional analysis of the organic material in the ice grains ejected from subsurface Enceladus’ into the E ring. Many of these ice grains carry diverse organic material that is characterized in this work. A laser-based analogue laboratory experiment is used to simulate the impact ionization CDA spectra of ice grains enriched in organic material. This experiment allowed to understand the varying cationic fragmentation patterns from organic material in a water ice matrix. Despite the relatively low mass resolution of the CDA, results of the analogue experiment allow to identify characteristic finger prints of certain classes of organic compounds in many CDA mass spectra. Three main categories are classified: (i) Amine-, (ii) Carbonyl-, and (iii) Aromatic-type mass spectra. Furthermore, some aromatic-type CDA spectra show features that correspond to breakup-products of larger complex aromatic species with masses above 200u. On the whole, the analysis of E ring ice grains in this work gives first insights into the largely varying and complex organic chemistry inside the ocean of Enceladus. The second aim of this thesis is to infer the compositional profile of ice particles in the E ring in the vicinity of Saturn’s moon Rhea, from a series of spectra recorded on Cassini’s Rhea flyby (R4) in 2013. No striking change in the frequency of different compositional types is observed along the spacecraft trajectory. However, a varying size distribution of different compositional populations of ice grains is observed and discussed. Sodium salts and organic compounds are more frequent in relatively large ice grains, whereas pure water ice particles become more abundant in smaller E ring grains. A generally higher number density of ice grains is observed in the close vicinity of Rhea, which might indicate either the presence of an ejecta cloud from Rhea’s surface or a general confinement of particles near the equatorial plane of the E ring

Complementary Mass Spectral Analysis of Isomeric O-bearing Organic Compounds and Fragmentation Differences through Analog Techniques for Spaceborne Mass Spectrometers

Mass spectrometers on board spacecraft typically use either impact ionization or electron ionization (EI) as ion sources. Understanding the similarities and differences in the spectral signatures and fragmentation patterns produced by different techniques in mass spectrometry could elucidate the composition of organic compounds. Here we present a comparison between the mass spectra obtained through laser-induced liquid beam ion desorption (LILBID; proven to simulate the impact ionization mass spectra of ice grains) and EI mass spectra of pairs of low-mass, isomeric aldehydes and ketones. Our comparison confirms that EI produces more fragmentation of carbonyl compounds, particularly aldehydes, than LILBID. We find protonated molecular ions [M+H]+ in LILBID but molecular ions [M]+ in EI spectra. From the evaluated species, LILBID generally produces oxygen-carrying fragment ions (e.g., [CHO]+ and [C2H3O]+) in the mass ranges 26–30 and 39–44 u, while in EI, most ions in these ranges correspond to hydrocarbon fragments. The LILBID spectra additionally show mostly protonated oxygen-bearing fragments [CH3O]+ and [C2H5O]+ at m/z 31 and 45, less commonly observed in EI spectra. We observe a decrease in the relative intensities of cation fragment mass lines between m/z 26 and 33 and an increase between m/z 39 and 45, with an increasing carbon number for ketones and aldehydes with LILBID and EI, respectively. Our study provides a basis for complementary compositional analysis to identify the structural properties of organic species in a space environment using different spaceborne mass spectrometers (e.g., SUrface Dust Analyzer and MAss Spectrometer for Planetary EXploration) on board NASA’s future Europa Clipper space mission

Probing the Oxidation State of Ocean Worlds with SUDA: Fe (ii) and Fe (iii) in Ice Grains

Characterizing the geochemistry of Europa and Enceladus is a key step for astrobiology investigations looking for evidence of life in their subsurface oceans. Transition metals with several oxidation states, such as iron, may be tracers of the oxidation state of icy ocean moon interiors. Their detection, as well as the characterization of their oxidation states, on the moons' (plume) ice grains would bring valuable new information about the geochemistry of both the subsurface oceans and surface processes. Impact ionization mass spectrometers such as the SUDA instrument on board Europa Clipper can analyze ice grains ejected from icy moons' surfaces and detect ocean-derived salts therein. Here we record mass spectra analogs for SUDA using the Laser Induced Liquid Beam Ion Desorption technique for Fe2+ and Fe3+ salts (both sulfates and chlorides). We show that impact ionization mass spectrometers have the capability to detect and differentiate ferrous (Fe2+) from ferric (Fe3+) ions in both cation and anion modes owing to their tendency to form distinct ionic complexes with characteristic spectral features. Peaks bearing Fe3+, such as [Fe3+ (OH)2]+ and [Fe3+ (OH)a Clb]−, are particularly important to discriminate between the two oxidation states of iron in the sample. The recorded analog spectra may allow the characterization of the oxidation state of the oceans of Europa and Enceladus with implications for hydrothermal processes and potential metabolic pathways for life forms in their subsurface oceans

Radial compositional profile of Saturn's E ring indicates substantial space weathering effects

Saturn's large and diffuse E ring is populated by microscopic water ice dust particles, which originate from the Enceladus plume. Cassini’s Cosmic Dust Analyser sampled these ice grains, revealing three compositional particle types with different concentrations of salts and organics. Here, we present the analysis of CDA mass spectra from several orbital periods of Cassini, covering the region from interior to Enceladus’ orbit to outside the orbit of Rhea, to map the distribution of the different particle types throughout the radial extent of the E ring. This will provide a better understanding of the potential impact of space weathering effects on to these particles, as the ice grains experience an increasing exposure age during their radially outward migration. In this context, we report the discovery of a new ice particle type (Type 5), which produces spectra indicative of very high salt concentrations, and which we suggest to evolve from less-salty Enceladean ice grains by space weathering. The radial compositional profile, now encompassing four particle types, reveals distinct radial variations in the E ring. At the orbital distance of Enceladus our results are in good agreement with earlier compositional analyses of E ring ice grains in the moon's vicinity. With increasing radial distance to Saturn however, our analysis suggests a growing degree of space weathering and considerable changes to the spatial distribution of the particle types. We also find that the proportion of Type 5 grains – peaking near Rhea's orbit – probably reflects particle charging processes in the E ring

Cassini’s CDA observes a variety of dust populations just outside Saturn’s main rings

Before the end of its mission, the Cassini spacecraft orbited Saturn in a series of highly inclined elliptical ‘Ring-Grazing’ orbits (RGO). During the RGO, the spacecraft passed repeatedly through the ring plane outside the F ring, near the orbits of Janus and Epimetheus, at an average relative speed of ∼20 km s–1. For the first time, Cassini’s Cosmic Dust Analyser (CDA) directly sampled dust particles from this region. Here, we analyse the compositions of dust grains sampled within ±15 min relative to nine ring plane crossings of the RGO. The compositions of most analysed RGO grains are similar to those of E ring ice grains, implying that the E ring extends to within at least 2.45 Saturn radii (RS) of Saturn. The compositional distribution of these grains point at a similar average period (decades) since ejection from Enceladus as of particles in the outer E ring (beyond 8 RS). Higher fractions of larger grains are found near the orbits of Janus and Epimetheus, which probably represent ejecta from these moons. Most of these grains have compositions similar to the background E ring grains, indicating that E ring material is coating the surfaces of Janus and Epimetheus. We also report the detection of several types of mineral grains on prograde orbits, one of which, a water ice/silicate mixture, has never been observed by CDA elsewhere. These mineral grains appear to have a different origin from the E ring, and may arise from nearby moons, the F ring, or main rings

Detection of phosphates originating from Enceladus’s ocean

Saturn’s moon Enceladus harbours a global1 ice-covered water ocean2,3. The Cassini spacecraft investigated the composition of the ocean by analysis of material ejected into space by the moon’s cryovolcanic plume4,5,6,7,8,9. The analysis of salt-rich ice grains by Cassini’s Cosmic Dust Analyzer10 enabled inference of major solutes in the ocean water (Na+, K+, Cl–, HCO3–, CO32–) and its alkaline pH3,11. Phosphorus, the least abundant of the bio-essential elements12,13,14, has not yet been detected in an ocean beyond Earth. Earlier geochemical modelling studies suggest that phosphate might be scarce in the ocean of Enceladus and other icy ocean worlds15,16. However, more recent modelling of mineral solubilities in Enceladus’s ocean indicates that phosphate could be relatively abundant17. Here we present Cassini’s Cosmic Dust Analyzer mass spectra of ice grains emitted by Enceladus that show the presence of sodium phosphates. Our observational results, together with laboratory analogue experiments, suggest that phosphorus is readily available in Enceladus’s ocean in the form of orthophosphates, with phosphorus concentrations at least 100-fold higher in the moon’s plume-forming ocean waters than in Earth’s oceans. Furthermore, geochemical experiments and modelling demonstrate that such high phosphate abundances could be achieved in Enceladus and possibly in other icy ocean worlds beyond the primordial CO2 snowline, either at the cold seafloor or in hydrothermal environments with moderate temperatures. In both cases the main driver is probably the higher solubility of calcium phosphate minerals compared with calcium carbonate in moderately alkaline solutions rich in carbonate or bicarbonate ions

How to identify cell material in a single ice grain emitted from Enceladus or Europa

Icy moons like Enceladus, and perhaps Europa, emit material sourced from their subsurface oceans into space via plumes of ice grains and gas. Both moons are prime targets for astrobiology investigations. Cassini measurements revealed a large compositional diversity of emitted ice grains with only 1 to 4% of Enceladus’s plume ice grains containing organic material in high concentrations. Here, we report experiments simulating mass spectra of ice grains containing one bacterial cell, or fractions thereof, as encountered by advanced instruments on board future space missions to Enceladus or Europa, such as the SUrface Dust Analyzer onboard NASA’s upcoming Europa Clipper mission at flyby speeds of 4 to 6 kilometers per second. Mass spectral signals characteristic of the bacteria are shown to be clearly identifiable by future missions, even if an ice grain contains much less than one cell. Our results demonstrate the advantage of analyses of individual ice grains compared to a diluted bulk sample in a heterogeneous plume

Is There Such a Thing as a Biosignature?

The concept of a biosignature is widely used in astrobiology to suggest a link between some observation and a biological cause, given some context. The term itself has been defined and used in several ways in different parts of the scientific community involved in the search for past or present life on Earth and beyond. With the ongoing acceleration in the search for life in distant time and/or deep space, there is a need for clarity and accuracy in the formulation and reporting of claims. Here, we critically review the biosignature concept(s) and the associated nomenclature in light of several problems and ambiguities emphasized by recent works. One worry is that these terms and concepts may imply greater certainty than is usually justified by a rational interpretation of the data. A related worry is that terms such as “biosignature” may be inherently misleading, for example, because the divide between life and non-life—and their observable effects—is fuzzy. Another worry is that different parts of the multidisciplinary community may use non-equivalent or conflicting definitions and conceptions, leading to avoidable confusion. This review leads us to identify a number of pitfalls and to suggest how they can be circumvented. In general, we conclude that astrobiologists should exercise particular caution in deciding whether and how to use the concept of biosignature when thinking and communicating about habitability or life. Concepts and terms should be selected carefully and defined explicitly where appropriate. This would improve clarity and accuracy in the formulation of claims and subsequent technical and public communication about some of the most profound and important questions in science and society. With this objective in mind, we provide a checklist of questions that scientists and other interested parties should ask when assessing any reported detection of a “biosignature” to better understand exactly what is being claimed

Developing a Laser Induced Liquid Beam Ion Desorption Spectral Database as Reference for Spaceborne Mass Spectrometers

Spaceborne impact ionization mass spectrometers, such as the Cosmic Dust Analyzer on board the past Cassini spacecraft or the SUrface Dust Analyzer being built for NASA's upcoming Europa Clipper mission, are of crucial importance for the exploration of icy moons in the Solar System, such as Saturn's moon Enceladus or Jupiter's moon Europa. For the interpretation of data produced by these instruments, analogue experiments on Earth are essential. To date, thousands of laboratory mass spectra have been recorded with an analogue experiment for impact ionization mass spectrometers. Simulation of mass spectra of ice grains in space is achieved by a Laser Induced Liquid Beam Ion Desorption (LILBID) approach. The desorbed cations or anions are analyzed in a time-of-flight mass spectrometer. The amount of unstructured raw data is increasingly challenging to sort, process, interpret and compare with data from space. Thus far this has been achieved manually for individual mass spectra because no database containing the recorded reference spectra was available. Here we describe the development of a comprehensive, extendable database containing cation and anion mass spectra from the laboratory LILBID facility. The database is based on a Relational Database Management System with a web server interface and enables filtering of the laboratory data using a wide range of parameters. The mass spectra can be compared not only with data from past and future space missions but also mass spectral data generated by other, terrestrial, techniques. The validated and approved subset of the database is available for general public (https://lilbid-db.planet.fu-berlin.de)

Developing a Laser Induced Liquid Beam Ion Desorption Spectral Database as Reference for Spaceborne Mass Spectrometers

Spaceborne impact ionization mass spectrometers, such as the Cosmic Dust Analyzer on board the past Cassini spacecraft or the SUrface Dust Analyzer being built for NASA's upcoming Europa Clipper mission, are of crucial importance for the exploration of icy moons in the Solar System, such as Saturn's moon Enceladus or Jupiter's moon Europa. For the interpretation of data produced by these instruments, analogue experiments on Earth are essential. To date, thousands of laboratory mass spectra have been recorded with an analogue experiment for impact ionization mass spectrometers. Simulation of mass spectra of ice grains in space is achieved by a Laser Induced Liquid Beam Ion Desorption (LILBID) approach. The desorbed cations or anions are analyzed in a time-of-flight mass spectrometer. The amount of unstructured raw data is increasingly challenging to sort, process, interpret and compare with data from space. Thus far this has been achieved manually for individual mass spectra because no database containing the recorded reference spectra was available. Here we describe the development of a comprehensive, extendable database containing cation and anion mass spectra from the laboratory LILBID facility. The database is based on a Relational Database Management System with a web server interface and enables filtering of the laboratory data using a wide range of parameters. The mass spectra can be compared not only with data from past and future space missions but also mass spectral data generated by other, terrestrial, techniques. The validated and approved subset of the database is available for general public (https://lilbid-db.planet.fu-berlin.de)