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2008
Botta, O, Martins Z, Emmenegger C, Dworkin JP, Glavin DP, Harvey RP, Zenobi R, Bada JL, Ehrenfreund P.  2008.  Polycyclic aromatic hydrocarbons and amino acids in meteorites and ice samples from LaPaz Icefield, Antarctica. Meteoritics & Planetary Science. 43:1465-1480. AbstractWebsite

We have analyzed ice samples and meteorites from the LaPaz region of Antarctica to investigate the composition of polycyclic aromatic hydrocarbons (PAHs) and amino acids with the goal to understand whether or not there is a compositional relationship between the two reservoirs. Four LL5 ordinary chondrites (OCs) and one CK carbonaceous chondrite were collected as part of the 2003/2004 ANSMET season. Ice samples collected from directly underneath the meteorites were extracted. In addition, exhaust particles from the snowmobiles used during the expedition were collected to investigate possible contributions from this source. The meteorite samples, the particulate matter and solid-state extracts of the ice samples and the exhaust filters were subjected to two-step laser mass spectrometry (L2MS) to investigate the PAH composition. For amino acids analysis, the meteorites were extracted with water and acid hydrolyzed, and the extracts were analyzed with offline OPA/NAC derivatization combined with liquid chromatography with UV fluorescence detection and time of flight mass spectrometry (LC-FC/ToF-MS). PAHs in the particulate matter of the ice were found to be qualitatively similar to the meteorite samples, indicating that micron-sized grains of the meteorite may be embedded in the ice samples. The concentration levels of dissolved PAHs in all the ice samples were found to be below the detection limit of the L2MS. The PAH composition of the snowmobile exhaust is significantly different to the one in particulate matter, making it an unlikely Source of contamination for Antarctic meteorites. The amino acids glycine, beta-alanine and gamma-amino-n-butyric acid that were detected at concentrations of 3 to 19 parts per billion (ppb) are probably indigenous to the Antarctic meteorites. Some of the LaPaz ice samples were also found to contain amino acids at concentration levels of 1 to 33 parts per trillion (ppt), in particular alpha-aminoisobutyric acid (AIB), an abundant non-protein amino acid of extraterrestrial Origin found in some carbonaceous chondrites. We hypothesize that this amino acid could have been extracted from Antarctic micrometeorites and the particulate matter of the meteorites during the concentration procedure of the ice samples.

Botta, O, Bada JL, Gomez-Elvira J, Javaux E, Selsis F, Summons R.  2008.  "Strategies of life detection": Summary and outlook. Space Science Reviews. 135:371-380.   10.1007/s11214-008-9357-9   Website
Bada, JL, Ehrenfreund P, Grunthaner F, Blaney D, Coleman M, Farrington A, Yen A, Mathies R, Amudson R, Quinn R, Zent A, Ride S, Barron L, Botta O, Clark B, Glavin D, Hofmann B, Josset JL, Rettberg P, Robert F, Sephton M.  2008.  Urey: Mars Organic and Oxidant Detector. Space Science Reviews. 135:269-279.   10.1007/s11214-007-9213-3   AbstractWebsite

One of the fundamental challenges facing the scientific community as we enter this new century of Mars research is to understand, in a rigorous manner, the biotic potential both past and present of this outermost terrestrial-like planet in our solar system. Urey: Mars Organic and Oxidant Detector has been selected for the Pasteur payload of the European Space Agency's (ESA's) ExoMars rover mission and is considered a fundamental instrument to achieve the mission's scientific objectives. The instrument is named Urey in recognition of Harold Clayton Urey's seminal contributions to cosmochemistry, geochemistry, and the study of the origin of life. The overall goal of Urey is to search for organic compounds directly in the regolith of Mars and to assess their origin. Urey will perform a groundbreaking investigation of the Martian environment that will involve searching for organic compounds indicative of life and prebiotic chemistry at a sensitivity many orders of magnitude greater than Viking or other in situ organic detection systems. Urey will perform the first in situ search for key classes of organic molecules using state-of-the-art analytical methods that provide part-per-trillion sensitivity. It will ascertain whether any of these molecules are abiotic or biotic in origin and will evaluate the survival potential of organic compounds in the environment using state-of-the-art chemoresistor oxidant sensors.

2007
Skelley, AM, Aubrey AD, Willis PA, Amashukeli X, Ehrenfreund P, Bada JL, Grunthaner FJ, Mathies RA.  2007.  Organic amine biomarker detection in the Yungay region of the Atacama Desert with the Urey instrument. Journal of Geophysical Research-Biogeosciences. 112   10.1029/2006jg000329   AbstractWebsite

The Urey in situ organic compound analysis instrument, consisting of a subcritical water extractor ( SCWE) and a portable microchip capillary electrophoresis instrument called the Mars Organic Analyzer ( MOA), was field tested in the Atacama Desert, Chile, in June 2005. Soil samples from the most arid Yungay region were collected, biomarkers were extracted by the SCWE, and organic amine composition and amino acid chirality analysis was performed by the MOA. Samples collected from the top 1 cm of duracrust soil but shielded from the ambient environment by rocks were compared to the exposed duracrust. The shielded duracrust yielded amines and amino acids ranging from 50 to 100 ppb, while amino acid signals from the exposed duracrust were below blank levels. Samples from buried gypsum deposits located directly above a water flow channel contained amino acids ranging from 13 to 90 ppb. Chiral analysis revealed D/L ratios of 0.39 +/- 0.08 and 0.34 +/- 0.07 for alanine/serine and 0.78 +/- 0.06 for aspartic acid, indicating significant racemization of biologically produced amino acids. On the basis of the D/L ratios, we estimate sample ages ranging from 10(3) to 10(5) years. These results demonstrate the successful field testing of the Urey instrument, as well as the detection of biomarkers from past terrestrial life in one of the most arid and Mars-like regions on Earth.

2005
Skelley, AM, Scherer JR, Aubrey AD, Grover WH, Ivester RHC, Ehrenfreund P, Grunthaner FJ, Bada JL, Mathies RA.  2005.  Development and evaluation of a microdevice for amino acid biomarker detection and analysis on Mars. Proceedings of the National Academy of Sciences of the United States of America. 102:1041-1046.   10.1073/pnas.0406798102   AbstractWebsite

The Mars Organic Analyzer (MOA), a microfabricated capillary electrophoresis (CE) instrument for sensitive amino acid biomarker analysis, has been developed and evaluated. The microdevice consists of a four-wafer sandwich combining glass CE separation channels, microfabricated pneumatic membrane valves and pumps, and a nanoliter fluidic network. The portable MOA instrument integrates high voltage CE power supplies, pneumatic controls, and fluorescence detection optics necessary for field operation. The amino acid concentration sensitivities range from micromolar to 0.1 nM, corresponding to part-per-trillion sensitivity. The MOA was first used in the lab to analyze soil extracts from the Atacama Desert, Chile, detecting amino acids ranging from 10-600 parts per billion. Field tests of the MOA in the Panoche Valley, CA, successfully detected amino acids at 70 parts per trillion to 100 parts per billion in jarosite, a sulfate-rich mineral associated with liquid water that was recently detected on Mars. These results demonstrate the feasibility of using the MOA to perform sensitive in situ amino acid biomarker analysis on soil samples representative of a Mars-like environment.

2001
Glavin, DP, Schubert M, Botta O, Kminek G, Bada JL.  2001.  Detecting pyrolysis products from bacteria on Mars. Earth and Planetary Science Letters. 185:1-5.   10.1016/s0012-821x(00)00370-8   AbstractWebsite

A pyrolysis/sublimation technique was developed to isolate volatile amine compounds from a Mars soil analogue inoculated with similar to 10 billion Escherichia coli cells. In this technique, the inoculated soil is heated to 500 degreesC for several seconds at Martian ambient pressure and the sublimate, collected by a cold finger, then analyzed using high performance liquid chromatography. Methylamine and ethylamine, produced from glycine and alanine decarboxylation, were the most abundant amine compounds detected after pyrolysis of the cells. A heating cycle similar to that utilized in our experiment was also used to release organic compounds from the Martian soil in the 1976 Viking gas chromatography/mass spectrometry (GC/MS) pyrolysis experiment. The Viking GC/MS did not detect any organic compounds of Martian origin above a level of a few parts per billion in the Martian surface soil. Although the Viking GC/MS instruments were not specifically designed to search for the presence of living cells on Mars, our experimental results indicate that at the part per billion level, the degradation products generated from several million bacterial cells per gram of Martian soil would not have been detected. (C) 2001 Elsevier Science B.V. All rights reserved.

2000
Kminek, G, Bada JL, Botta O, Glavin DP, Grunthaner F.  2000.  MOD: an organic detector for the future robotic exploration of Mars. Planetary and Space Science. 48:1087-1091.   10.1016/s0032-0633(00)00082-9   AbstractWebsite

Searching for extinct or extant life on Mars is part of the future NASA surveyor class missions. Looking for key organic compounds that are essential for biochemistry as we know it or indicative of extraterrestrial organic influx is the primary goal of the Mars Organic Detector (MOD). MOD is able to detect amino acids, amines and PAHs with at least 100 times higher sensitivity than the Viking GCMS experiment. MOD is not capable of identifying specific organic molecules but can assess the organic inventory of amines and PAHs on the planet. MOD can also quantify adsorbed and chemisorbed water and evolved carbon dioxide in a stepped heating cycle to determine specific carbon-bearing minerals. All that comes with no sample preparation and no wet chemistry. The organics can be isolated from the carrier matrix by heating the sample and recovering the volatile organics on a cold finger. This sublimation technique can be used for extracting amino acids, amines and PAHs under Mars ambient conditions. The detection of amino acids, amines and PAHs is based on a fluorescence detection scheme. The MOD concept has functioned as a laboratory breadboard since 1998. A number of natural samples including shells, clays, bones, lambda -DNA and E.-coli bacteria have been used and organic molecules have been extracted successfully in each case. The first prototype of MOD is operational as of early fall of 1999. MOD has been selected for the definition phase of the NASA-MSR 2003 mission. (C) 2000 Elsevier Science Ltd. All rights reserved.

1999
Becker, L, Popp B, Rust T, Bada JL.  1999.  The origin of organic matter in the Martian meteorite ALH84001. Earth and Planetary Science Letters. 167:71-79.   10.1016/s0012-821x(99)00014-x   AbstractWebsite

Stable carbon isotope measurements of the organic matter associated with the carbonate globules and the bulk matrix material in the ALH84001 Martian meteorite indicate that two distinct sources are present in the sample. The delta(13)C values for the organic matter associated with the carbonate globules averaged -26 parts per thousand and is attributed to terrestrial contamination, In contrast, the delta(13)C values for the organic matter associated with the bulk matrix material yielded a value of -15 parts per thousand. The only common sources of carbon on the Earth that yield similar delta(13)C values, other then some diagenetically altered marine carbonates, are C(4) plants. A delta(13)C value of -15 parts per thousand, on the other hand, is consistent with a kerogen-like component, the most ubiquitous form of organic matter found in carbonaceous chondrites such as the Murchison meteorite. Examination of the carbonate globules and bulk matrix material using laser desorption mass spectrometry (LDMS) indicates the presence of a high molecular weight organic component which appears to be extraterrestrial in origin, possibly derived from the exogenous delivery of meteoritic or cometary debris to the surface of Mars. (C) 1999 Published by Elsevier Science B.V. All rights reserved.

Glavin, DP, Bada JL, Brinton KLF, McDonald GD.  1999.  Amino acids in the Martian meteorite Nakhla. Proceedings of the National Academy of Sciences of the United States of America. 96:8835-8838.   10.1073/pnas.96.16.8835   AbstractWebsite

A suite of protein and nonprotein amino acids were detected with high-performance liquid chromatography in the water- and acid-soluble components of an interior fragment of the Martian meteorite Nakhla, which fell in Egypt in 1911. Aspartic and glutamic acids, glycine, alanine, beta-alanine, and gamma-amino-n-butyric acid (gamma-ABA) were the most abundant amino acids detected and were found primarily in the 6 M HCl-hydrolyzed, hot water extract, The concentrations ranged from 20 to 330 parts per billion of bulk meteorite. The amino acid distribution in Nakhla, including the D/L ratios (values range from <0.1 to 0.5), is similar to what is found in bacterially degraded organic matter. The amino acids in Nakhla appear to be derived from terrestrial organic matter that infiltrated the meteorite soon after its fall to Earth, although it is possible that some of the amino acids are endogenous to the meteorite. The rapid amino acid contamination of Martian meteorites after direct exposure to the terrestrial environment has important implications for Mars sample-return missions and the curation of the samples from the time of their delivery to Earth.

Becker, L, Popp B, Rust T, Bada JL.  1999.  The origin of organic matter in the Martian meteorite ALH84001. Life Sciences: New Insights into Complex Organics in Space. 24( Ehrenfreund P, Robert F, Eds.).:477-488., Oxford: Pergamon Press Ltd   10.1016/s0273-1177(99)00090-3   Abstract

Stable carbon isotope measurements of the organic matter associated with the carbonate globules and the bulk matrix material in the ALH84001 Martian meteorite indicate that two distinct sources are present in the sample. The delta(13) C values for the organic matter associated with the carbonate globules averaged -26 parts per thousand and is attributed to terrestrial contamination. In contrast, the delta(13)C values for the organic matter associated with the bulk matrix material yielded a value of -15 parts per thousand. The only common carbon sources on the Earth that yield similar delta(13) values, other then some diagenetically altered marine carbonates, are C(4) plants. A delta(13)C value of -15 parts per thousand, on the other hand, is consistent with a kerogen-like component, the most ubiquitous form of organic matter found in carbonaceous chondrites such as the Murchison meteorite. Examination of the carbonate globules and bull; matrix material using laser desorption mass spectrometry (LDMS) indicates the presence of a high molecular weight organic component which appears to be extraterrestrial in origin, possibly derived from the exogenous delivery of meteoritic or cometary debris to the surface of Mars. (C) 1999 COSPAR. Published by Elsevier Science Ltd.