The origin of amino acids in lunar regolith samples

We analyzed the amino acid content of seven lunar regolith samples returned by the Apollo 16 and Apollo 17 missions and stored under NASA curation since collection using ultrahigh-performance liquid chromatography with fluorescence detection and time-of-flight mass spectrometry. Consistent with results from initial analyses shortly after collection in the 1970s, we observed amino acids at low concentrations in all of the curated samples, ranging from 0.2 parts-per-billion (ppb) to 42.7 ppb in hot-water extracts and 14.5-651.1 ppb in 6 M HCl acid-vapor-hydrolyzed, hot-water extracts. Amino acids identified in the Apollo soil extracts include glycine, D-and L-alanine, D-and L-aspartic acid, D-and L-glutamic acid, D-and L-serine, L-threonine, and L-valine, all of which had previously been detected in lunar samples, as well as several compounds not previously identified in lunar regoliths: alpha-aminoisobutyric acid (AIB), D-and L-b-amino-n-butyric acid (beta-ABA), DL-alpha-amino-n-butyric acid, gamma-amino-n-butyric acid, beta-alanine, and epsilon-amino-n-caproic acid. We observed an excess of the L enantiomer in most of the detected proteinogenic amino acids, but racemic alanine and racemic beta-ABA were present in some samples. We also examined seven samples from Apollo 15, 16, and 17 that had been previously allocated to a non-curation laboratory, as well as two samples of terrestrial dunite from studies of lunar module engine exhaust that had been stored in the same laboratory. The amino acid content of these samples suggested that contamination had occurred during non-curatorial storage. We measured the compound-specific carbon isotopic ratios of glycine, beta-alanine, and L-alanine in Apollo regolith sample 70011 and found values of -21% to -33%. These values are consistent with those seen in terrestrial biology and, together with the enantiomeric compositions of the proteinogenic amino acids, suggest that terrestrial biological contamination is a primary source of the amino acids in these samples. However, the presence of the non-proteinogenic amino acids such as AIB and b-ABA suggests the possibility of some contribution from exogenous sources. We did not observe a correlation of amino acid content with proximity to the Apollo 17 lunar module, implying that lunar module exhaust was not a primary source of amino acid precursors. Solar-wind-implanted precursors such as HCN also appear to be at most a minor contributor, given a lack of correlation between amino acid content and soil maturity (as measured by I-s/FeO ratio) and the differences between the delta C-13 values of the amino acids and the solar wind. Published by Elsevier Ltd.