P31A-1883: Planetary In Situ Sample Analysis with Tandem Two-Step Laser Mass Spectrometry

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Authors: William B Brinckerhoff1, Stephanie A Getty1, Timothy J Cornish2, Scott A Ecelberger2, Xiang Li3, 1, Melissa A Merrill Floyd1, Ricardo Arevalo1, Jamie Elsila1, Michael P Callahan1

Author Institutions: 1. Goddard Space Flight Center, NASA, Greenbelt, MD, USA; 2. C & E Research, Inc., Columbia, MD, USA; 3. University of Maryland, Baltimore County, Baltimore, MD, USA

Future surface missions to comets and outer solar system satellites such as Europa, Enceladus, and Titan will benefit strongly from investigations that can detect a wide range of organics in complex sample mixtures and ices, as well as determine the structure of selected molecules, to provide insight into their origin and evolution. At the same time, such missions are likely to be among the most highly constrained in mass and power resources, particularly those flown within the tightly focused Discovery and New Frontiers programs. Techniques requiring minimal or no sample manipulation or preparation may be needed to reduce complexity. Pulsed laser-based mass spectrometry may satisfy such requirements, with total instrument masses potentially less than 5 kg, particularly where analysis of higher-molecular weight, nonvolatile species is a priority objective. Prototype flight-compatible mass spectrometers under active development in our lab are based on direct ultraviolet Nd:YAG laser desorption and ionization (LDI) of solid samples under high vacuum. Prompt ions from a single few ns-duration laser pulse are accelerated into a compact time-of-flight mass spectrometer (TOF-MS). Both inorganic species including elements and oxides such as M_xO_y (M = Mg, Al, Cl, Ca, Fe; x, y = 1-4) from the mineral matrix as well as organics with molecular weights up to several kDa are readily detected over a range of laser intensities. To improve our ability to distinguish among peaks and patterns in the often-complex LDI spectra obtained from natural samples, we have recently begun systematically testing several critical instrument enhancements. First, by moving the common voltage bias of the ion flight tube and detector to a common negative potential, we are able to switch between positive and negative ion detection modes with only electrostatic switching. Inter-comparison of cation and anion spectra can provide highly diagnostic information on both inorganic (e.g., Na+ and K+ vs. Cl-) and organic moieties. Second, by focusing a separate “post-ionization”ù laser pulse just above the sample surface, we can achieve two-step laser mass spectrometry, or L2MS, in the same highly-miniaturized TOF-MS. L2MS enables selective analysis of aromatic organics even in the presence of a complex mineral matrix. Finally, by introducing an ion optical gate in the flight path, we are able to take advantage of the broad focusing capabilities of the “curved field”ù reflectron at the core of the TOF-MS to achieve pseudo-tandem structural analysis of selected organics. The high-speed gate is used to admit only the molecular ion/s of interest into the reflectron. Diagnostic fragments of the ion/s obtained through metastable decay or active collision-induced dissociation (CID) remain in focus despite having widely variable velocities and masses. As such even molecular isomers with differing fragmentation pathways may be distinguished through a series of pseudo-tandem mass spectra that could be obtained in an automatic process during a mission. The “real-world”ù benefits of these enhancements are being fully characterized using a set of synthetic and natural standard samples as well as several planetary analogs and meteorites.

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