projects

CURRENT
PROJECTS

UREY/ESA Pasteur/ExoMars


 

COMPLETED
PROJECTS

ASTEP 2004
ASTID 2003
MSL Proposal
PIDDP 2002

CURRENT PROJECTS

UREY: 

Mars Organic and Oxidant Detector
Searching for Signs of Life on Mars
ESA Pasteur/ExoMars Mission

Science Team Members:

Jeffrey L. Bada, PI, Scripps Institution of Oceanography, U. C. San Diego
Ron Amundson, University of California, Berkeley
Laurence Barron, University of Glasgow, UK
Diana L. Blaney, Jet Propulsion Laboratory, Cal Tech
Oliver Botta, International Space Science Institute, Bern, Switzerland
Benton Clark, Lockheed Martin, Denver
Max Coleman, Jet Propulsion Laboratory, Cal Tech
Pascale Ehrenfreund, Astrobiology, Leiden University, The Netherlands
Daniel Glavin, NASA Goddard Space Flight Center
Frank Grunthaner, Jet Propulsion Laboratory, Cal Tech
Beda Hoffman, Natural History Museum, Bern
Jean-Luc Josset, Space Exploration Institute, Switzerland
Richard A. Mathies, University of California, Berkeley
Richard Quinn, SETI Institute
Petra Rettberg, German Aerospace Center, Koln, Germany
Francois Robert, Natural Museum of History, Paris
Mark Sephton, Imperial College, London
Albert Yen, Jet Propulsion Laboratory, Cal Tech
Aaron Zent, NASA Ames Research Center

On Monday, Jan. 8, 2007, NASA announced its decision to fund the Urey instrument at an initial level of $750,000 for a technology development study. Urey was judged as having the best science value among 26 proposals submitted to NASA in August 2006 in response to an open announcement of opportunity.

NASA selected UREY for technology development studies to enhance its capabilities as a contribution to the ESA ExoMars Mission.  Urey has already been selected by ESA as a component of the ExoMars Mission scheduled for 2013.  This receipt of funds for additional technical development from NASA is an important step toward the development of a flight instrument.  The Urey instrument would investigate organics and oxidant materials on Mars using three complementary detection systems. 

"These mission selections represent unprecedented future research that will lead to further advancing our knowledge and understanding of the Red Planet's climate, and atmospheric composition," said Mary Cleave, associate administrator for NASA's Science Mission Directorate, NASA Headquarters, Washington.

ABSTRACT

The UREY Instrument is designed to carry out a series of in situ experiments on Mars as a part of the rover package on the ESA ExoMars-Pasteur Mission which is scheduled for launch in 2013.  The instrument suite is named for Professor Urey in recognition of the landmark Miller-Urey experiment that first showed amino acids could be made via abiotic processes as well as Urey’s insights into the origin of the solar system.   UREY consists of four components:  a subcritical water extractor (SCWE) and a sublimation apparatus called the Mars Organic Detector (MOD) for isolation and concentration of organic biomarkers; a novel lab-on-a-chip microcapillary electrophoresis (CE) system for composition and chirality analysis; and the Mars Oxidant Instrument (MOI).  The SCWE is used to extract the target compounds from samples.  MOD next uses sublimation to purify and concentrate the target organic compounds.  The presence of the target organic compounds is determined by measuring the fluorescence on a MOD sublimation capture cold finger.  In the case of amino acids, amines and nucleobases, fluorescence is generated by their reaction with the fluorogenic dye fluorescamine.  Sublimed PAH’s are naturally fluorescent and can be detected directly and analyzed with a fluorescence spectrograph.  When an amine/amino acid signal is detected, the microchip based CE separation device with integrated reaction chambers, pumps, and a capillary sipper is used to gather the sublimate from the fluorescamine coated portion of the cold finger and determine amino acid composition and chirality in order to evaluate their origin. The observation of nonracemic amino acids would suggest the presence of life based on peptide polymers.  The combined system has been field tested in the Atacama Desert, Chile and shown to provide part-per-billion to part-per-trillion sensitivity for amino acids, amines and nucleobases.  The SCWE/MOD/CE suite is combined with the MOI component that is used to determine oxidative characteristics of the samples in order to provide data on the role of oxidation reactions on the survival of organic compounds in the Martian regolith.  UREY is a powerful suite of instruments designed to sensitively look for the presence of extinct or extant life on Mars.

UREY IN MORE DETAIL

The UREY Instrument is designed to carry out a series of in situ experiments on Mars as a part of the rover package on the ESA ExoMars-Pasteur Mission which is scheduled for launch in 2013. The instrument suite is named for Professor Urey in recognition of the landmark Miller-Urey experiment that first showed amino acids could be made via abiotic processes as well as Urey’s insights into the origin of the solar system. UREY consists of four components: a subcritical water extractor (SCWE) and a sublimation apparatus called the Mars Organic Detector (MOD) for isolation and concentration of organic biomarkers; a novel lab-on-a-chip microcapillary electrophoresis (CE) system for composition and chirality analysis; and the Mars Oxidant Instrument (MOI). The SCWE is used to extract the target compounds from samples. MOD next uses sublimation to purify and concentrate the target organic compounds. The presence of the target organic compounds is determined by measuring the fluorescence on a MOD sublimation capture cold finger. In the case of amino acids, amines and nucleobases, fluorescence is generated by their reaction with the fluorogenic dye fluorescamine. Sublimed PAH’s are naturally fluorescent and can be detected directly and analyzed with a fluorescence spectrograph. When an amine/amino acid signal is detected, the microchip based CE separation device with integrated reaction chambers, pumps, and a capillary sipper is used to gather the sublimate from the fluorescamine coated portion of the cold finger and determine amino acid composition and chirality in order to evaluate their origin. The observation of nonracemic amino acids would suggest the presence of life based on peptide polymers. The combined system has been field tested in the Atacama Desert, Chile and shown to provide part-per-billion to part-per-trillion sensitivity for amino acids, amines and nucleobases. The SCWE/MOD/CE suite is combined with the MOI component that is used to determine oxidative characteristics of the samples in order to provide data on the role of oxidation reactions on the survival of organic compounds in the Martian regolith. UREY is a powerful suite of instruments designed to sensitively look for the presence of extinct or extant life on Mars.

Science Investigation

Urey: Mars Organic and Oxidant Detector, has been selected for the Pasteur payload in the European Space Agency’s (ESA’s) ExoMars rover mission and is considered a fundamental instrument to achieve the mission’s scientific objectives. 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 insitu organic detection systems. Urey will perform the first insitu 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 orgin and will evaluate the survival potential of organic compounds in the environment using state-of-the-art chemoresistor oxidant sensors.

Overview
The National Research Council (NRC) report, New Frontiers in the Solar System: An Integrated Exploration Strategy, states that the three key questions “for a paradigm-altering discovery” are:

• Does life currently exist on Mars?
• Did life ever exist there?
• How hospitable was and is Mars to life?

These questions form the basis for the primary goal of the Pasteur Instrument payload on
ESA’s ExoMars mission: “To search for signs of past and present life.”

Urey addresses each of the NRC report questions, as well as the Pasteur instrument payload’s primary goal, in a robust and comprehensive manner. Specifically, Urey
investigates the following hypotheses:

• Are organic compounds with a primary amino group (amino acids, amines, nucleobases, amino sugars) and polycyclic aromatic hydrocarbons (PAHs)—our target compounds—derived from either extinct or extant life and/or abiotic sources, detectable in the regolith of Mars?

• Using compositional and chirality characteristics of detected amino acids, can we determine whether they are of biotic or abiotic origin?

• Are organic compounds degraded in near-surface environments on Mars via an array of photolytic and heterogeneous chemical processes, and are these processes a central factor in determining the abundance and type of our target compounds in the Mars regolith?

To test these hypotheses, Urey carries out two complementary experiments:

1. Urey uses a Sub-Critical Water Extractor (SCWE), the Mars Organic Detector (MOD), and a Micro-Capillary Electrophoresis (μCE) analyzer to investigate the target organic compounds in samples collected during the ExoMars rover activities. Samples will be analyzed to detect the presence of organic compounds—and to determine their composition. If detected, amino acids are analyzed further to determine their chirality.

2. Urey uses a chemometric sensor array, the Mars Oxidant Instrument (MOI), to measure the reaction rates of films that have different sensitivities to particular types of oxidants expected to be present in the Mars surface environment. By controlling the temperature of these films and their exposure to dust, ultraviolet light and water vapor, Urey will evaluate organic degradation pathways that may take place at sampled localities on Mars. These data will provide important insights into the observed organic matter inventory and the potential for survival of various classes of organic compounds under Martian environmental conditions.

The Mars Organic and Oxidant Detector 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.  

Click to see full size PDFs


Hypotheses Linked to UREY Experiments


Schematic of the UREY Instrument

(Please be patient, this is a very large file)

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'New Stratgies to Detect Life on Mars' by Jeffrey Bada et al.

The quest to determine whether life exiseted, or still exists, on Mars continues with several missions planned for the red planet by both the European Space Agency (ESA) and the National Aeronautics and Space Administration (NASA) in the next few decades. One instrument designed for these missions is the Mars Organic Detector (MOD), which uses a new approach to achieve exceptionally high detection sensitivities and analysis capabilities for key bio-organic compounds. MOD is scheduled to fly in the ESA ExoMars mission early next decade and will attempt to answer the question of whether we are alone in the solar system. Here the MOD team explains why we have reason to be optimistic about uncovering the organic secrets of Mars. ...more

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Microfabricated Organic Analyzer for In Situ Exploration of Mars and Other Solar Bodies

A NASA Astrobiology Science and Technology for Exploring Planets (ASTEP) grant has been awarded to Prof. Mathies, Prof. Bada at Scripps and Dr. Grunthaner at JPL for a total of $1,820,400 to develop the Microfabricated Organic Analyzer for In Situ Exploration of Mars and Other Solar Bodies (2/15/04-2/14/07).

Briefly in collaboration with Dr. Jeffrey Bada (U.C. San Diego) and Dr. Frank Grunthaner (Jet Propulsion Laboratory) this is a proposal to integrate and field test the Microfabricated Organic Analyzer, designed to be deployed on Mars and other planets for the quantitation and characterization of amino acids in soil and other samples. The total budget includes $860,400 for work at JPL, $225,000 for work at UCSD and $735,000 at UCB over the three year period.

This multi-institutional proposal will integrate a portable version of the Microfabricated Organic Analyzer (MOA) and use it to test for key bio-organic marker compounds in terrestrial sites having chemical and environmental conditions that model the deployment of in situ Astrobiology instrumentation on planetary missions to the Martian surface. The goals of this project will be (i) to complete the brass-board development of a novel lab-on-a-chip device for the analysis of organic amines and for amino acid composition and chirality analysis, (ii) to couple this microchip analyzer with the previously developed Mars Organic Detector (MOD) which will function as the sample acquisition and preparation unit, and (iii) to perform a series of field campaigns in the Mojave and in three unique Atacama Desert sites, with strikingly different water abundances and organic content, to test and improve this brass-board analysis system. This project is based on the mature MOD platform that uses sublimation to purify PAH's, organic amines and amino acids from soil and other samples. The presence and concentration of these targets is indicated by their reaction with a dye, fluorescamine, on a capture cold-finger followed by fluorescence detection. A microfabricated capillary electrophoresis (CE) separation device with reaction chambers, pumps and capillary sipper sample input is then used to gather the sublimed and labeled sample from the cold finger followed by CE analysis to determine the amine composition and amino acid composition and chirality. This project combines a complementary suite of in situ instruments with state-of-the-art organic compound detection to perform organic biomarker compound characterization. The success of this project will establish the feasibility of the MOA for Mars exploration and for the study of other solar system targets such as Europa. Our specific objectives are to:

  • Document the maturation, integration and field operation of two in situ MIDP- PIDDP- and ASTID-derived instruments. (technology thrust).
  • Deploy the integrated Microfabricated Organic Analyzer in Field Campaigns to the Mojave and to the Atacama Desert with experiments conducted under flight-like remote operation conditions to enhance the TRL of the MOA for possible flight opportunities such as the MSL.
  • Increase our understanding of the limits and constraints of life in extreme environments by comparing Atacama sites that range from sterile to viable and to develop a better under-standing of the identity and sensitivity of potential chemical biomarkers (science thrust).

Design of the portable capillary electrohoresis (CE) analysis device together with capillary sipper that will be used for analysis of
amino acids in field sites

Note that in this multilayer structure, red channels are within the electrophoresis layer, blue channels are between the electrophoresis layer and the PDMS membrane, and green channels are in the pneumatic layer. The instrument will be 4 x 10 x 8" and the chip is a 100 mm diameter wafer.

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A Microfabricated Bio-organic Laboratory for In Situ Extraterrestrial Exploration

A NASA Astrobiology Science Technology Instrument Development (ASTID) grant has been awarded to Prof. Mathies for the period 12/01/03-11/30/06 for the amount of $569,441 to develop A Microfabricated Bio-organic Laboratory for In Situ Extraterrestrial Exploration

Briefly the goal of this research is to develop novel capture matrix-based concentration and labeling methods and apparatus for automated in situ analysis of a broad range of bio-organic molecules. A more detailed statement of our activities is given below:

Recent advances in the development of microfabricated lab-on-a-chip analysis systems have enhanced the feasibility and capabilities of in situ chemical and biochemical analyzers. While a wide variety of bio-organic molecules can be probed with such systems, we focused our initial studies on the development of an amino acid analyzer with the hypothesis that extraterrestrial life would be based on homochiral amino acid polymers. We developed an electrophoresis chip, detection system and analysis method where the hydrolyzed amino acids were fluorescently labeled and then analyzed in minutes via a capillary zone electrophoresis separation in the presence of g-cyclodextrin as the chiral recognition agent. We now propose the development of a more general Microfabricated Bio-organic Laboratory (MBL) that will analyze samples for a more complete menu of bio-organics including but not limited to zwitterionic amino acids, nucleobases, sugars, organic acids and organic bases using novel capture matrix chemistries coupled with a second dimension of microchip CE analysis.

The MBL uses microfabricated pumps and sippers to sample from a source which can be an aqueous sample stream from a cryobot, an aqueous extract of solid samples, etc. The sample passes through microfluidic elements to adjust ionic strength and pH into acceptable ranges if needed and is then directed to a series of affinity capture chambers. These capture chambers contain a polymeric sol-gel modified with group-specific affinity reagents that will concentrate and purify the sample by chemical affinity. This process permits the concentration, purification and stratification of input molecules from potentially very dilute or dirty inputs. Following capture, the analytes are released, labeled with a group-specific reagent, and separated on-chip to produce a second "spectral" dimension of analysis that is used for further chemical identification.

The Microfabricated Bio-organic Laboratory proposed here has several benefits: it will provide multiparameter analysis for the presence of bio-organics in extraterrestrial environments thereby more generally testing for the presence of extant or extinct life. Second, the broadly based organic analysis capabilities of the device will make it advantageous for missions to other extraterrestrial bodies such as asteroids and Europa. Finally, the small size, low power requirements, and microfluidic elements of the MBL allow it to be integrated with a wide variety of exploration platforms and to operate in low g or low pressure environments.

Schematic Design of the Mars Bio-organic Laboratory

A two-stage analysis is performed: samples are first partitioned by the use of affinity capture matrices into five groups: amino acids, nucleobases, sugars, organic acids and organic bases. The second stage of analysis is performed by releasing the molecules, labeling them with a fluorescent dye and sending them to a microfabricated separation column for secondary molecular analysis.

Adapted from Skelley, A. M., Grunthaner, F. J., Bada, J. L., and Mathies, R. A. Mars Organic Detector III: A Versatile Instrument for Detection of Bio-organic Signature on Mars, SPIE - The International Society for Optical Engineering Proceedings, First Jet Propulsion Laboratory In Situ Instruments Workshop, June 11-13, 2002, Pasadena, CA, G. H. Bearman and P. M. Beauchamp, Editors, Volume 4878, p. 59-67 (2003). Link to PDF

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COMPLETED PROJECTS

Mars Astrobiology Probe (MAP): The Search for Indigenous Organic Compounds on Mars

Team Members:

Jeffrey L. Bada, Scripps Institutution of Oceanography, U.C. San Diego, PI
Frank Grunthaner, Jet Propulsion Laboratory, CoI
Richard A. Mathies, University of California, Berkeley, CoI
Benton Clark, Lockheed Martin Astronautics, CoI
Steven D’Hondt, University of Rhode Island, CoI
Pascale Ehrenfreund, Leiden Observatory, International Partner
Daniel Glavin, NASA Goddard Space Flight Center, CoI
Michael Hecht, Jet Propulsion Laboratory, CoI
Richard Quinn, NASA Ames Research Center, CoI
Aaron Zent, NASA Ames Research Center, CoI

Adjunct Members:
Sally Ride, UC San Diego, Educational Partner
Meenakshi Wadhwa, The Field Museum, Chicago

We propose to carry out a series of in situ experiments on Mars using the Mars Astrobiology Probe (MAP) that are designed to address in a robust and comprehensive manner one of the primary goals of the Mars Science Laboratory (MSL) mission, that is to “assess the biological potential of at least one target environment identified prior to MSL or discovered by MSL”. MAP consists of four separate major components: a subcritical water extractor (SCWE); the Mars Organic Detector (MOD); a novel lab-on-a-chip micro-capillary electrophoresis (CE) system; and the Mars Organic Reactor Suite (MORS). The SCWE is used to extract the target compounds from samples provided by the Mars Science Laboratory sample distribution system. MOD next uses sublimation at Mars ambient pressure to extract, purify and concentrate the target organic compounds from the SCWE extract. The presence of the target compounds is determined by measuring the fluorescent response on a MOD capture cold finger. In the case of amino acids, fluorescence is generated by their reaction with a dye, fluorescamine, which is highly specific for primary amines. PAHs are naturally highly fluorescent so they can be detected directly. To permit the simultaneous detection of both target compounds, half of the cold finger is coated with the fluorescamine reagent, while the other half is uncoated. With the MOD fluorescence analyzer, the target compounds can be readily detected at the sub-ppb level. If an amine/amino acid signal is detected in the MOD-based analyses, the microfabricated chip-based CE separation device with integrated reaction chambers, pumps, and capillary sipper is used to gather the sublimate from the fluorescamine-coated portion of the cold finger and determine amino acid composition and chirality in order to evaluate their origin. Of particular importance would be the finding that the amino acids are present as a non-racemic mixture (non-equal amounts of the D- and L-isomers) which could be suggestive of a biotic origin.

The SCWE/MOD/CE suite is combined with the MORS component that is used to determine the oxidative characteristics of the samples in order to provide data on the role of oxidation reactions in the survival of organic compounds in the Martian regolith. These oxidant data will be of particular significance if a negative result is obtained by the MOD/CE system.

MAP has the potential of performing the first successful detection of organic compounds on Mars. The finding of amino acids of possible biological origin would be a sensational result of interest to both the scientific community and the public. The MAP project also includes an aggressive education and public outreach effort in order to transmit the results on national and world wide bases.

Schematic representation of the Mars Astrobiology Probe or MAP. The system consists of a primary sample carousel which feeds samples to the Sub Critical Water Extractor (SCWE). Aqueous extracts are fed to the Mars Organic Detector or MOD where amino acids are sublimed away from salts and deposited on a cooled substrate for fluorescent fluorescence labeling. Labeled amino acids are then passed to the Micro CE system for composition analysis and chirality determination.

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NASA Research Grant NAG5-12139
Richard Mathies, PI, UCB; Jeffrey Bada, PI, UC San Diego
Dates of Project: 5/1/02 – 4/30/04

Integration of a Micro-chip Amino Acid Chirality Detector into the Mars Organic Detector

We have developed CE chips designed for fluorescence detection of amino acids for NASA's Planetary Instrument Device Development Project. The separation of fluorescamine-labeled amino acids was studied to determine the optimal conditions for resolution of a standard mixture. This work has been recently been described in publications by Hutt et al. (Anal. Chem. 71, 4000-4006, 1999) and by Skelley and Mathies (J. Chromatography A, 1021, 191-199, 2003). Soil samples were obtained from the Atacama Desert in Chile with the goal of demonstrating amino analysis on the best terrestrial surrogate for a Mars analysis. This research is now being continued under ASTID and ASTEP NASA awards described in ‘Active Projects’.

Established Separation and Microscope Detection System. Schematic of lab-based amino acid analysis system with a blow up of the glass microchip that we are employing. Also shown are a series of amino acid analyses of exterior and interior samples from the Murchison meteorite.

(Click on picture for larger image.)

© Copyright 2004, Richard A. Mathies

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