THE OSIRIS-REX MISSION IS EXPECTED TO RETURN TO EARTH 60 G OF MATERIAL SAMPLED FROM THE ASTEROID BENNU. THIS BODY HAS SPECTRAL PROPERTIES RESEMBLING THE INFERRED PARENT BODIES OF CLASSES OF METEORITES THAT ARE RICH IN VOLATILES INCLUDING ORGANIC COMPOUNDS. THIS MISSION WILL PROVIDE A RARE OPPORTUNITY TO EXPLORE THE ORGANIC CHEMISTRY OF A SOLAR SYSTEM BODY OUTSIDE THE EARTH WHERE THE SOURCE AND ENVIRONMENTAL CONTEXT OF THE SAMPLE IS WELL KNOWN TERRESTRIAL CONTAMINATION IS MINIMAL AND THERE IS RELATIVELY ABUNDANT MATERIAL FOR LABORATORY STUDY. STABLE ISOTOPE COMPOSITIONS (D 13C 15N 17 180 33 34 36S) OF METEORITIC NEBULAR AND INTERSTELLAR ORGANICS RECORD THEIR PRECURSORS AND FORMATION MECHANISMS; THEREFORE STABLE ISOTOPE MEASUREMENT TECHNOLOGIES APPROPRIATE FOR ORGANIC MOLECULES WILL BE KEY TO THE STUDY OF SAMPLES RETURNED BY OSIRIS-REX.WE PROPOSE TO DEVELOP TECHNOLOGY AND METHODS FOR THE ANALYSIS OF STABLE ISOTOPE DISTRIBUTIONS IN ORGANIC COMPOUNDS RETURNED FROM BENNU INCLUDING: (1) BULK STABLE ISOTOPE CONTENTS OF INDIVIDUAL MOLECULES (I.E. AVERAGED ACROSS ALL ATOMIC SITES IN THAT MOLECULE0; (2) POSITION-SPECIFIC DIFFERENCES IN ISOTOPIC CONTENT BETWEEN NON-EQUIVALENT ATOMIC SITES IN A GIVEN MOLECULE; AND (3) PROPORTIONS OF MULTIPLY-SUBSTITUTED ISOTOPOLOGUES (I.E. VERSIONS OF THE ANALYZED MOLECULE CONTAINING TWO OR MORE RARE ISOTOPES).WE WILL ACCOMPLISH THIS USING FOURIER-TRANSFORM MASS SPECTROMETRY (FTMS) WHICH HAS EXTRAORDINARY MASS RESOLUTION (M/AM 105-106) AND THE CAPACITY TO MAKE MEASUREMENTS ACROSS LARGE RANGES OF MASS ON MANY PEAKS PER COMPOUND. WE WILL ADAPT FOR THIS PURPOSE THE Q EXACTIVE GC (QEGC) AN INSTRUMENT PRODUCED BY THERMO FISHER SCIENTIFIC. THE QEGC HAS AN ELECTRON IMPACT GASION SOURCE QUADRUPOLE FOR MASS WINDOW SELECTION COLLISION CELL FOR MS-MS EXPERIMENTS AND MOST IMPORTANTLY CONTAINS AN ORBITRAP(COMPACT ELECTROSTATIC FTMS). THE CENTRAL IDEA BEHIND OUR APPROACH IS TO IONIZE EACH ORGANIC MOLECULE BY ELECTRON IMPACT PRODUCING A MASS SPECTRUM CONTAINING NUMEROUS PEAKS THAT EACH SUB-SAMPLE THE MOLECULAR STRUCTURE IN DIFFERENT WAYS (THUS ENCODING POSITIONS SPECIFIC ISOTOPIC INFORMATION). PORTIONS OF THAT MASS SPECTRUM THAT ARE KNOWN TO CONTAIN MOLECULAR SITES OF INTEREST (OR TO SAMPLE THE MOLECULE AS A WHOLE) WILL BE SELECTED USING THE QUADRUPOLE AND PASSED TO THE ORBITRAP FOR ISOTOPE RATIO ANALYSIS INCLUDING BOTH SINGLY AND MULTIPLY SUBSTITUTED SPECIES. WE PRESENT A PILOT STUDY DOCUMENTING THE ABILITY OF THIS MACHINE TO RETURN ISOTOPE RATIOS WITH PRECISIONS IN THE RANGE 0.2-1 PERCENT TO BE SIMILARLY ACCURATE WHEN APPROPRIATELY STANDARDIZED AND TO RECOVER KNOWN ISOTOPIC CONTENTS OF PORTIONS OF ORGANIC COMPOUNDS.OUR WORK ON THE QEGC WILL FOCUS ON: (1) FUNDAMENTAL CHARACTERIZATION OF ITS PERFORMANCE AS A MASS ANALYZER (E.G. LIMITS OF PRECISION AND SENSITIVITY); (2) DEVELOPMENT OF METHODS OF SAMPLE INTRODUCTION OPTIMIZED FOR ANALYSIS OF TRACE ORGANICS; AND (3) PROOF OF CONCEPT STUDIES OF ORGANICS EXTRACTED FROM THE MURCHISON METEORITE. WE WILL FOCUS ON THE AMINO ACIDS WHICH ARE IMPORTANT CONSTITUENTS OF EXTRA-TERRESTRIAL ORGANIC MATTER AND HAVE BEEN THE SUBJECT OF MANY PREVIOUS STUDIES. HOWEVER THE INSTRUMENTS AND METHODS SHOULD BE GENERALIZABLE TO OTHER CLASSES OF ORGANIC MOLECULES.THIS PROPOSAL IS A COLLABORATION BETWEEN TWO GROUPS WITH COMPLEMENTARY PRIOR EXPERIENCE: PI EILER WILL PROVIDE EXPERTISE AND INSTRUMENTATION FOR ANALYSIS OF ISOTOPIC STRUCTURES OF MOLCULES; CO-I ELSILA WILL PROVIDE EXPERTISE IN THE EXTRACTION PURIFICATION AND DERIVATIZATION OF AMINO ACIDS FROM METEORITES AND IN THE APPLICATION OF STABLE ISOTOPE GEOCHEMISTRY TO ORGANIC COSMOCHEMISTRY.
$306,000FY2017National Aeronautics and Space AdministrationNASA
California Institute Of Technology, Pasadena CA