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D P Glavin

Publications and source records attributed to D P Glavin.

13 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS2024

Organic Matter and Nanoglobules in Bennu Samples Revealed By Coordinated UV Fluorescence, SEM-EDX, and Two-Step Laser Mass Spectrometry

Carbonaceous meteorites are derived from asteroids, although specific parent bodies are generally unknown. However, on September 24, 2023, NASA’s Origins, Spectral Interpretation, Resource Identification, and Security–Regolith Explorer (OSIRIS-REx) mission delivered regolith from the carbonaceous B-type asteroid (101955) Bennu, enabling coordinated laboratory analysis of pristine samples, with a well characterized geological context, from an asteroid of known provenance. One of primary mission goals [1] was the identification and characterization of primordial organic matter present in the returned samples. We report results from the coordinated analyses of Bennu samples using UV fluorescence, two-step laser mass spectrometry (μ-L2MS) and scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX).

Asteroid Bennu↗
NASA NTRS2016

Measurements of Oxychlorine species on Mars

Mars landed and orbiter missions have instrumentation capable of detecting oxychlorine phases (e.g. perchlorate, chlorate) on the surface. Perchlorate (~0.6 wt%) was first detected by the Wet Chemistry Laboratory in the surface material at the Phoenix Mars Landing site. Subsequent analyses by the Thermal Evolved Gas Analyser aboard the same lander detected an oxygen release (~465°C) consistent with the thermal decomposition of perchlorate. Recent thermal analysis by the Mars Science Laboratory’s Sample Analysis at Mars instrument has also indicated the presence of oxychlorine phases (up to 1.2 wt%) in Gale Crater materials. Despite being at detectable concentrations, the Chemistry and Mineralogy (CheMin) X-ray diffractometer has not detected oxychlorine phases. This suggests that Gale Crater oxychlorine may exist as poorly crystalline phases or that perchlorate/chlorate mixtures exist, so that individual oxychlorine concentrations are below CheMin detection limits (~1 wt%). Although not initially designed to detect oxychlorine phases, reinterpretation of Viking Gas Chromatography/Mass Spectrometer data also suggest that oxychlorine phases are present in the Viking surface materials. Remote near-infrared spectral analyses by the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) instrument indicate that at least some martian recurring slope lineae (RSL) have spectral signatures consistent with the presence of hydrated perchlorates or chlorates during the seasons when RSL are most extensive. Despite the thermal emission spectrometer, Thermal Emission Imaging System, Observatoire pour la Minéralogie, l’Eau, les Glaces et l’Activité and CRISM detection of hundreds of anhydrous chloride (~10–25 vol%) deposits, expected associated oxychlorine phases (>5–10 vol%) have not been detected. Total Cl and oxychlorine data sets from the Phoenix Lander and the Mars Science Laboratory missions could be used to develop oxychlorine versus total Cl correlations, which may constrain oxychlorine concentrations at other locations on Mars by using total Cl determined by other missions (e.g. Viking, Pathfinder, MER and Odyssey). Development of microfluidic or ‘lab-on-a-chip’ instrumentation has the potential to be the next generation analytical capability used to identify and quantify individual oxychlorine species on future landed robotic missions to Mars.

Perchlorate↗
NASA NTRSDate not supplied

The Comet Astrobiology Exploration Sample Return (CAESAR) Mission

The Comet Astrobiology Exploration Sample Return (CAESAR) mission will acquire and return to Earth for laboratory analysis a minimum of 80 grams of surface material from the nucleus of comet 67P/Chur-yumov-Gerasimenko (67P). CAESAR will characterize the surface region sampled, preserve the collected sample in a pristine state, and return evolved volatiles by capturing them in a separate gas reservoir. NASA Goddard Space Flight Center provides project management, systems engineering, safety and mission assurance, contamination control, mission operations, and many other important functions. Northrop Grumman Space Systems will build the spacecraft, based on Dawn mission heritage, which like CAESAR, uses solar electric propulsion. CAESAR was selected by for Phase A study in the New Frontiers 4 Competition and will be proposed to New Frontiers 5.Collection of a sample from the surface of comet 67P is facilitated by a set of cameras that together provide images to support sample site selection, perform optical navigation, and document the sample before, during, and after col-lection. The sample is collected at the end of an arm during a 5-second touch-and-go (TAG) maneuver with the Sample Acquisition System (SAS)designed by Honeybee Robotics for the surface properties of comet 67P observed by the Rosetta mission. After sample collection, and while the sample is still cold (< -80°C), the TAG Arm inserts the sample container into the Sample Containment System (SCS) mounted inside the Sample Return Capsule (SRC). The SCS is sealed, preventing the sample from escaping into space. The sample is slowly warmed inside the SCS to enable sublimation of volatiles, which are collected in the Gas Containment System (GCS), a passively cooled gas reservoir. Separating the volatiles from the solid sample protects the solid sample from alteration. Once all sublimated H2O is transferred to the GCS, the GCS is sealed to capture the volatile sit contains, and the SCS is vented to space to maintain the solid sample under vacuum. The SCS vent is closed before Earth entry to prevent atmospheric contamination. Detailed laboratory analyses of the sample from 67P will trace the history of volatile reservoirs, delineate the chemical pathways that led from simple interstellar species to complex molecules, constrain the evolution of the comet, and evaluate the role of comets in delivering water and prebiotic organics to the early Earth. CAESAR will achieve these goals by carrying out coordinated sample analyses that will link macroscopic properties of the comet with microscale mineralogy, chemistry, and isotopic studies of volatiles and solids. Most of the sample (≥75%) will be set aside for analyses by generations of scientists using continually advancing tools and methods, yielding an enduring scientific treasure that only sample return can provide. This presentation will review development conducted during NF4 Phase A and discuss the NF5 mission concept.

A G Hayes↗
NASA NTRSDate not supplied

Investigation of the Glen Torridon Clay-Bearing Unit and Overlying Greenheugh Pediment by the Sample Analysis at Mars Instrument Suite

Exploring the Glen Torridon (GT) clay-bearing unit in Gale crater has long been a prime goal for the Mars Science Laboratory (MSL) because of spectral signatures of smectite identified from orbit. Smectite clay minerals can indicate habitable environments [1,2] and possibly facilitate the preservation of organic compounds [e.g., 3-7].Also, sulfate-bearing layers overlie GT and this sequence may record a large-scale change in aqueous conditions overtime [8].The Sample Analysis at Mars (SAM) instrument suitehas been essential in understanding volatile-bearing phases in Gale crater materials. SAM EGA has detected H2O, CO2, O2, H2, SO2, H2S, HCl, NO, and other trace gases, including organic fragments, evolved from many samples on heating. The identity and evolution temperature of evolved gases can support mineral detection by CheMin instrument X-ray diffraction (XRD)and place constraints on trace volatile-bearing phases, clay mineral compositions, and X-ray amorphous materials. In GT, SAM analyzed the sample Kilmarie (KM) from the Jura member, Glen Etive (GE), Mary Anning (MA) and Groken (GR)from the Knockfarril Hill member (KHm), Glasgow (GG) and Hutton (HU) from the fractured Intermediate Unit (fIU), and Edinburgh (EB) from the Stimson formation rocks of the Greenheugh Pediment (GP). The Jura, KHm and fIU are all members of the Murray formation. HU was sampled near the basal Siccar Point group (SPg) unconformity between the fIU and GP, in an area that exhibits a brighter tone and differences in geochemistry compared to Murray materials down-section [9,10]. CheMin XRD of most samples (except for HU and EB)showed large abundances of smectite clay minerals (~25-35%) and all samples showed X-ray amorphous materials and relatively low amounts of well-crystalline hematite[11]. SAM evaluated mineralogy through evolved gas analysis mass spectrometry (EGA) while detailed organic chemistry of several samples was examined by pyrolysis gas chromatography mass spectrometry and wet chemistry experiments [12,13].Here we discuss data and interpretations from SAM EGA analyses.

Mars↗
NASA NTRSDate not supplied

Organic Matter in Itokawa Particles

The first Hayabusa mission returned samples from the near-Earth S-type asteroid 25143 Itokawa to Earth in 2010[1]. Although Itokawa has a lithology related to ordinary chondrites(OCs) that typically have low organic contents, several Itokawa particles were found to contain organic matter (OM)[2-5]. However, there was not an explicit conclusion to the origin of the observed OMin these early studies. We have extended our search for OM into other Itokawa grains. Here, we report extraterrestrial OM (macromolecular carbon and amino acids) observed in six Itokawa particles(including a category1 particle: RA-QD02-0162[#62; also nicknamed “Amazon”],and five category3 carbon-rich particles:RA-QD02-0012[#12], RA-QD02-0078[#78], RB-CV-0029[#29], RB-CV-0080 [#80] and RB-QD04-0052[#52]).All allocated Itokawa samples were initially analysed by spot and point-by-point mapping Raman spectroscopic analysis at the Open University, UK. Amazon was then transferred and mounted into indium on an aluminium stub, which was studied with a NanoSIMS 50L ion microprobe for its H,C,N isotopic compositions. The rest of the samples were mounted in sterile gold foils, and the amino acid contents of their acid hydrolysed hot water extracts were obtained with a liquid chromatography with tandem fluorescence and accurate mass detection at NASA Goddard Space Flight Center, USA. Based on the observation of the Raman parameters(e.g. the peak locations and widths of the defect (D) and graphite (G) bands)[6], a significant variety of carbonaceous materials has been observed in Amazon. The carbonaceous materials include primitive and unaltered OM that shares similarity with the IOM in primitive (CI,CM,CR) carbonaceous chondrites, as well as OM that has been heavily graphitised. The organic structure of the heated material is best represented by nanocrystalline graphite, comparable to that observed for metamorphosed meteorites (e.g., L3–6 Inman, Tieschitz and New Concord,CV3 Allende, and EH4 Indarch),suggesting peak metamorphic temperatures (PMT) of >~600°C. The thermal history recorded in the graphitic OM agrees with PMT estimates for returned Itokawa regolith grains (600–800°C)[7].We have obtained the H,C,N isotopic compositions for the primitive OM in Amazon, which exhibits unambiguously extraterrestrial isotopic signatures (δD = +4868±2288‰; δ13C = −24±5‰; δ15N = +344±20‰), contrasting to the typically negative isotopic values obtained for terrestrial organic matter[8]. The δD and δ13C values of the organic material in Amazon are comparable to OCs, however, the δ15N value is higher than that typically observed for OCs (δ15N = −47 to +36‰), and is similar to that of CRs (δ15N = +153 to +309‰)[9].Our data suggest a genetic link between the primitive organic material observed in Itokawa to CRs and IDPs for they share similar D, 13C and 15N enrichments[10].The high carbon contents of the five category 3 Itokawa particles suggest potentially higher OM abundances, hence we extracted and analysed amino acids in these samples. Although terrestrial contamination was observed primarily as L-protein amino acids, several terrestrially uncommon non-protein amino acids were also observed at low abundances, such as β-aminoisobutyric acid (β-AIB),β-amino-n-butyric acid (β-ABA), and β-alanine. Itokawa amino acid content observed here was dissimilar to thermally altered OCs, but preliminarily analogous to more aqueously altered CR2s.Continued evolution of Itokawa is evident by the in fall of primitive organic material derived from CRs/IDPs, accounting for a complex interplay between the remnant Itokawa silicates with exogenous organics. The results reported here are the first evidence of extraterrestrial OM in asteroid material from a sample-return mission, showcasing a working protocol for analysing samples returned by the Hayabusa2 and OSIRIS-REx missions

Q. H. S. Chan↗
NASA NTRSDate not supplied

Extraterrestrial Amino Acids in the C2 Ungrouped Carbonaceous Chondrite Tarda: A Unique Distribution

Introduction: Meteorites provide a record of the chemical processes that occurred in the early solar sys-tem. The delivery of organic matter by carbonaceous chondrites to the early Earth could have been an im-portant source of amino acids and other prebiotic or-ganic molecules required for the emergence of life [1]. To date, 96 amino acids have been named in meteor-ites, most of which are rare or absent in the biosphere [2]. The variability in amino acid concentrations and isomer distributions measured in carbonaceous chon-drites can be explained by differences in parent body chemistry and alteration conditions [3]. In addition, aqueous alteration was likely important in the amplifi-cation of some left-handed amino acids over their right-handed forms (L-excesses up to ~60%) in the Tagish Lake meteorite [3], suggesting that the origin of life on Earth and possibly elsewhere in the solar sys-tem was biased towards L-amino acids. On August 25, 2020, a fireball was witnessed in southern Morocco and the first pieces of the meteorite fall were recovered the following day near the town of Tarda [4]. Thousands of individual fragments were recovered from the strewn field totaling ~4 kg [4]. Based on petrographic observations, bulk mineralogy, and chemical and O-isotopic analyses, Tarda has been classified as a C2 ungrouped carbonaceous chondrite with similarities to Tagish Lake (though more primi-tive), as well as CI, CY, and CR chondrites [4,5]. The fall and rapid recovery of the Tarda stones provide an important opportunity to investigate a C-rich meteorite using the state-of-the-art techniques that will also be used to study the samples returned from asteroids Ryugu and Bennu by the Hayabusa2 and OSIRIS-REx missions, respectively. Here, we report the first amino acid analyses of the Tarda meteorite. The total concentrations, enantio-meric ratios and relative distributions of amino acids were determined using ultrahigh performance liquid chromatography with UV fluorescence and time-of-flight mass spectrometry (LC-FD/ToF-MS) at NASA GSFC. This analytical technique was employed on extracts from two different pre-rain Tarda meteorite fragments and a sample of sand collected from the Tarda fall site for the purpose of assessing potential terrestrial contamination. Bulk H, C, and N elemental and isotopic analyses were also conducted at the Car-negie Institution for Science (CIS) to assist with petro-logic type classification using elemental analysis iso-tope ratio mass spectrometry (EA-IRMS).

D P Glavin↗
NASA NTRSDate not supplied

The Search for Chiral Asymmetry as a Potential Biosignature in Samples from Mars

The search for evidence of extraterrestrial life in our solar system has been guided by our under-standing of terrestrial biology and its associated biosignatures. The observed homochirality in all life on Earth, that is, the predominance of “left-handed” or L-amino acids and “right-handed” or D-sugars, is a unique property of life that is crucial for molecular recognition, enzymatic function, information storage and structure, and is thought to be a prerequisite for the origin or early evolution of life. Therefore, the detection of L- or D-excesses of chiral amino acids or sugars could be a powerful indicator of extant or extinct life on Mars or other habitable environments in our solar system. However, studies of primitive meteorites have revealed that they contain extraterrestrial amino acids and sugar acids with large enantiomeric excesses (60% and higher) that resulted from non-biological processes [1], complicating the use of chiral asymmetry by itself as a definitive biosignature. The exploration of habitable environments on Mars, including an assessment of the preservation potential for complex organics of either abiotic or biological origin, is an objective of both current and future Mars missions. Now with the unambiguous detection of indigenous organic matter in sedimentary rocks by the Sample Analysis at Mars (SAM) instrument suite on Mars [2-5], NASA’s Curiosity rover has found evidence of the preservation of potential chemical biosignatures in the martian near surface. Although amino acids have not yet been identified by in situ measurements on Mars [5], indigenous achiral amino acids have been identified in one martian meteorite [6]. It is expected that amino acid racemization would be very slow and any chiral or isotopic signatures from an extinct martian biota could be preserved for billions of years, given the extremely cold and dry surface conditions [7]. The ESA/Roscosmos ExoMars mission scheduled for launch next year includes the Rosalind Franklin rover designed to acquire samples from a depth of ~2 m and deliver them to a suite of instruments, including the Mars Organic Molecule Analyzer (MOMA). The MOMA instrument contains a wet chemistry experiment designed specifically for the detection of amino acids and measurement of their enantiomeric compositions [8]. The complexity and limited duration of spaceflight operations, and the known analytical challenges associated with in situ extraction and characterization of trace reduced organic com-pounds in ancient rocks, make it challenging to determine the origins of martian organic matter found to date. Coordinated state-of-the-art laboratory measurements of returned samples from Mars that include spatially resolved chemical, mineralogical, bulk and molecule-specific isotopic, and enantiomeric measurements will be required to firmly establish whether the complex organic matter detected on Mars derives from bio-tic or abiotic processes. Ultimately, Mars Sample Return of rock cores collected by NASA’s Perseverance rover may be our best chance of identifying chemical biosignatures, including any chiral amino acid asymmetry resulting from a past or present martian biota, if one ever existed on Mars. Here we review our current knowledge of the distributions, and enantiomeric and isotopic com-positions of amino acids found in meteorites compared to terrestrial biochemistry. We also propose a set of measurement criteria that should be used to help establish the sources of any amino acids detected in samples returned from Mars using state-of-the-art gas and liquid chromatography mass spectrometry techniques [1].

D P Glavin↗
NASA NTRSDate not supplied

Coordinated Analysis of Isotopically Anomalous Nanoglobules and Insoluble Organic Matter in Quick-Look Samples From Asteroid Bennu

Spectral characterization of B-type asteroid Bennu by the Origins, Spectral Interpretation, Resource Identification, and Security–Regolith Explorer (OSIRIS-REx) spacecraft indicated abundant organic matter with similarities to insoluble organic matter (IOM) in meteorites. IOM in chondritic samples occurs in multiple forms, including a fluffy morphology and submicron-sized rounded nanoglobules. Isotopic anomalies in H, C, and N have been observed in both morphologies and are postulated to result from low-temperature chemical reactions in the molecular cloud or outer protoplanetary disk [e.g., 2,3]. We tested the hypothesis that Bennu also contains such isotopically anomalous organic matter by conducting coordinated in situ analysis of “quick-look” samples collected from the avionics deck of the OSIRIS-REx sample canister. This study expands our understanding of the fundamental nature of Bennu and its pre-accretionary environment by investigating the morphologies and isotopic distribution of presolar organic matter in Bennu.

A N Nguyen↗
NASA NTRSDate not supplied

The Mars Sample Return Analogue Collection

The Mars 2020 Perseverance rover touched down in Jezero crater on February 18th, 2021, and sealed the first sample for Mars Sample Return (MSR) later that summer. As of sol 1088, 23 rock cores have been collected across a diverse set of lithologies that span rock types from sedimentary to igneous. As the cache on Perseverance continues to grow, the overall portfolio of MSR expands, creating long lasting implications for a wide net in the scientific community as well as supporting detailed analyses for generations to come. To best prepare for these precious samples to return to Earth one day, NASA and ESA are jointly planning to create a MSR Analogue Collection that will be available to the community in the near future.

M T Thorpe↗