Linear Ion Trap Mass Spectrometer (LITMS) Instrument Field and Laboratory Tests as Part of the ARADS Field Campaigns.

The highly compact Linear Ion Trap Mass Spectrometer (LITMS), developed at NASA Goddard Space Flight Center, combines Mars-ambient laser desorption-mass spectrometry (LD-MS) and pyrolysis-gas chromatography-mass spectrometry (GC-MS) through a single, miniaturized linear ion trap mass analyzer. The LITMS instrument is based on the Mars Organic Molecule Analyser (MOMA) investigation developed for the European Space Agency's ExoMars Rover Mission with further enhanced analytical features such as dual polarity ion detection and a dual frequency RF (radio frequency) power supply allowing for an increased mass range. The LITMS brassboard prototype underwent an extensive repackaging effort to produce a highly compact system for terrestrial field testing, allowing for molecular sample analysis in rugged planetary analog environments outside the laboratory. The LITMS instrument was successfully field tested in the Mars analog environment of the Atacama Desert in 2019 as part of the Atacama Rover Astrobiology Drilling Studies (ARADS) project, providing the first in situ planetary analog analysis for a high-fidelity, flight-like ion trap mass spectrometer. LITMS continued to serve as a laboratory tool for continued analysis of natural Atacama samples provided by the subsequent 2019 ARADS final field campaign.

ExoMars Mars Organic Molecule Analyzer (MOMA) Laser Desorption/Ionization Mass Spectrometry (LDI-MS) Analysis of Phototrophic Communities from a Silica-Depositing Hot Spring in Yellowstone National Park, USA.

The Mars Organic Molecule Analyzer (MOMA) is a key scientific instrument on the ExoMars Rover mission. MOMA is designed to detect and characterize organic compounds, over a wide range of volatility and molecular weight, in samples obtained from up to 2 m below the martian surface. Thorough analog sample studies are required to best prepare to interpret MOMA data collected on Mars. We present here the MOMA characterization of Mars analog samples, microbial streamer communities composed primarily of oxygenic and anoxygenic phototrophs, collected from an alkaline silica-depositing hot spring in Yellowstone National Park, Wyoming, USA. Samples of partly mineralized microbial streamers and their total lipid extract (TLE) were measured on a MOMA Engineering Test Unit (ETU) instrument by using its laser desorption/ionization mass spectrometry (LDI-MS) mode. MOMA LDI-MS detected a variety of lipids and pigments such as chlorophyll a, monogalactosyldiacylglycerol, digalactosyldiacylglycerol, diacylglycerols, and ß-carotene in the TLE sample. Only chlorophyll a was detected in the untreated streamer samples when using mass isolation, which was likely due to the higher background signal of this sample and the relative high ionization potential of the chlorophyll a compared with other compounds in unextracted samples. The results add to the LDI-MS sample characterization database and demonstrate the benefit of using mass isolation on the MOMA instrument to reveal the presence of complex organics and potential biomarkers preserved in a natural sample. This will also provide guidance to in situ analysis of surface samples during Mars operations.

Unique capabilities of AC frequency scanning and its implementation on a Mars Organic Molecule Analyzer linear ion trap.

A limitation of conventional quadrupole ion trap scan modes which use rf amplitude control for mass scanning is that, in order to detect a subset of an ion population, the rest of the ion population must also be interrogated. That is, ions cannot be detected out of order; they must be detected in order of either increasing or decreasing mass-to-charge (m/z). However, an ion trap operated in the ac frequency scan mode, where the rf amplitude is kept constant and instead the ac frequency is used for mass-selective operations, has no such limitation because any variation in the ac frequency affects only the subset of ions whose secular frequencies match the perturbation frequency. Hence, an ion trap operated in the ac frequency scan mode can perform any arbitrary mass scan, as well as a sequence of scans, using a single ion injection; we demonstrate both capabilities here. Combining these two capabilities, we demonstrate the acquisition of a full mass spectrum, a product ion spectrum, and a second generation product ion spectrum using a single ion injection event. We further demonstrate a "segmented scan" in which different mass ranges are interrogated at different rf amplitudes in order to improve resolution over a portion of the mass range, and a "periodic scan" in which ions are continuously introduced into the ion trap to achieve a nearly 100% duty cycle. These unique scan modes, along with other characteristics of ac frequency scanning, are particularly appropriate for miniature ion trap mass spectrometers. Hence, implementation of ac frequency scanning on a prototype of the Mars Organic Molecule Analyzer mass spectrometer is also described.

The Mars Organic Molecule Analyzer (MOMA) Instrument: Characterization of Organic Material in Martian Sediments.

The Mars Organic Molecule Analyzer (MOMA) instrument onboard the ESA/Roscosmos ExoMars rover (to launch in July, 2020) will analyze volatile and refractory organic compounds in martian surface and subsurface sediments. In this study, we describe the design, current status of development, and analytical capabilities of the instrument. Data acquired on preliminary MOMA flight-like hardware and experimental setups are also presented, illustrating their contribution to the overall science return of the mission. Key Words: Mars-Mass spectrometry-Life detection-Planetary instrumentation. Astrobiology 17, 655-685.

Mars Organic Molecule Analyzer (MOMA) laser desorption/ionization source design and performance characterization.

The Mars Organic Molecule Analyzer (MOMA), a dual-source, ion trap-based instrument capable of both pyrolysis-gas chromatography mass spectrometry (pyr/GC-MS) and laser desorption/ionization mass spectrometry (LDI-MS), is the core astrobiology investigation on the ExoMars rover. The MOMA instrument will be the first spaceflight mass analyzer to exploit the LDI technique to detect refractory organic compounds and characterize host mineralogy; this mode of analysis will be conducted at Mars ambient conditions. In order to achieve high performance in the Martian environment while keeping the instrument compact and low power, a number of innovative designs and components have been implemented for MOMA. These include a miniaturized linear ion trap (LIT), a fast actuating aperture valve with ion inlet tube. and a Microelectromechanical System (MEMS) Pirani sensor. Advanced analytical capabilities like Stored Waveform Inverse Fourier Transform (SWIFT) for selected ion ejection and tandem mass spectrometry (MS/MS) are realized in LDI-MS mode, and enable the isolation and enhancement of specific mass ranges and structural analysis, respectively. We report here the technical details of these instrument components as well as system-level analytical capabilities, and we review the applications of this technology to Mars and other high-priority targets of planetary exploration.

Detection of trace organics in Mars analog samples containing perchlorate by laser desorption/ionization mass spectrometry.

Evidence from recent Mars missions indicates the presence of perchlorate salts up to 1 wt % level in the near-surface materials. Mixed perchlorates and other oxychlorine species may complicate the detection of organic molecules in bulk martian samples when using pyrolysis techniques. To address this analytical challenge, we report here results of laboratory measurements with laser desorption mass spectrometry, including analyses performed on both commercial and Mars Organic Molecule Analyzer (MOMA) breadboard instruments. We demonstrate that the detection of nonvolatile organics in selected spiked mineral-matrix materials by laser desorption/ionization (LDI) mass spectrometry is not inhibited by the presence of up to 1 wt % perchlorate salt. The organics in the sample are not significantly degraded or combusted in the LDI process, and the parent molecular ion is retained in the mass spectrum. The LDI technique provides distinct potential benefits for the detection of organics in situ on the martian surface and has the potential to aid in the search for signs of life on Mars.

A novel planar ion funnel design for miniature ion optics.

The novel planar ion funnel (PIF) design presented in this article emphasizes simple fabrication, assembly, and operation, making it amenable to extreme miniaturization. Simulations performed in SIMION 8.0 indicate that ion focusing can be achieved by using a gradient of electrostatic potentials on concentric metal rings in a plane. A prototype was fabricated on a 35 × 35 mm custom-designed printed circuit board (PCB) with a center hole for ions to pass through and a series of concentric circular metal rings of increasing diameter on the front side of the PCB. Metal vias on the PCB electrically connected each metal ring to a resistive potential divider that was soldered on the back of the PCB. The PIF was tested at 5.5 × 10(-6) Torr in a vacuum test setup that was equipped with a broad-beam ion source on the front and a micro channel plate (MCP) ion detector on the back of the PIF. The ion current recorded on the MCP anode during testing indicated a 23× increase in the ion transmission through the PIF when electric potentials were applied to the rings. These preliminary results demonstrate the functionality of a 2D ion funnel design with a much smaller footprint and simpler driving electronics than conventional 3D ion funnels. Future directions to improve the design and a possible micromachining approach to fabrication are discussed in the conclusions.

High-speed digital frequency scanning ion trap mass spectrometry.

A novel means of simultaneous ion injection and mass scanning has been studied. Classic injection methods for ion trap mass spectrometry proceed by loading the trap and scanning out in mutually exclusive time segments. This mode implicitly imparts a duty cycle and acquisition rate limit to ion trap mass analysis. Using digital frequency scanning methods without the use of discrete injection phases, we demonstrate continuous injection and acquisition rates up to 1000 Hz (averaging 400,000 Th/s) in a 3D ion trap configuration showing an alternatively faster control of ions over the classic voltage ramping mass-selective instability scanning method. The digital frequency scanning method may accommodate current advances in high-speed separation [e.g., ultraperformance liquid chromatography (UPLC), two-dimensional gas chromatography (GC×GC), ion mobility spectrometry (IMS), and capillary electrophoresis (CE)] and ion transfer efficiency (e.g., ion funnels). These ion sources may comprise high ion currents with compositions that change quickly and require high-speed mass analysis. Though resolution is compromised with higher acquisition rates, the frequency scanning mode permits a more flexible platform to accomplish the optimal trade-off of speed and mass spectral quality.

Calibration of an in situ membrane inlet mass spectrometer for measurements of dissolved gases and volatile organics in seawater.

Use of membrane inlet mass spectrometers (MIMS) for quantitative measurements of dissolved gases and volatile organics over a wide range of ocean depths requires characterization of the influence of hydrostatic pressure on the permeability of MIMS inlet systems. To simulate measurement conditions in the field, a laboratory apparatus was constructed for control of sample flow rate, temperature, pressure, and the concentrations of a variety of dissolved gases and volatile organic compounds. MIMS data generated with this apparatus demonstrated thatthe permeability of polydimethylsiloxane (PDMS) membranes is strongly dependent on hydrostatic pressure. For the range of pressures encountered between the surface and 2000 m ocean depths, the pressure dependent behavior of PDMS membranes could not be satisfactorily described using previously published theoretical models of membrane behavior. The observed influence of hydrostatic pressure on signal intensity could, nonetheless, be quantitatively modeled using a relatively simple semiempirical relationship between permeability and hydrostatic pressure. The semiempirical MIMS calibration developed in this study was applied to in situ underwater mass spectrometer (UMS) data to generate high-resolution, vertical profiles of dissolved gases in the Gulf of Mexico. These measurements constitute the first quantitative observations of dissolved gas profiles in the oceans obtained by in situ membrane inlet mass spectrometry. Alternative techniques used to produce dissolved gas profiles were in good accord with UMS measurements.