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Analysis of natural and synthetic extraterrestrial material Jason Dworkin. Meteorites. Returned Samples. Ice Simulations. Grain Simulations. http://astrobiology.gsfc.nasa.gov/dworkin/. Observations & Simulations. Lab Analysis. Simulations.

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Analysis of natural and synthetic extraterrestrial material

Jason Dworkin

Meteorites

Returned

Samples

Ice

Simulations

Grain

Simulations

http://astrobiology.gsfc.nasa.gov/dworkin/


Observations

& Simulations

Lab Analysis

Simulations



Russian botanist Mikhail Tsvet

invented chromatography in 1901

during his research on chlorophyll.


Chromatographic Tools

Liquid Chromatography

Mass Spectrometry

LC/MS

Gas Chromatography

Mass Spectrometry

GC/MS

HPLC & Detectors

MS

MS

GC

nanoLC

LIF Detector


(NAI)

(NAI)

(NAI)

(NAI)

(NAI)


Dworkin co authored abscicon presentations
Dworkin Co-Authored AbSciCon Presentations

  • Investigation of isovaline enantiomeric excesses in CM meteorites using liquid chromatography time of flight mass spectrometry. Glavin & Dworkin

  • Reassessing the organic content of antarctic ice and meteorites. Botta et al.

  • Icy prebiotic chemistry of nitriles and other molecules. Hudson, Moore & Dworkin

  • Studies of amino acid formation by photolysis of interstellar ice analogs. Elsila, Bernstein & Dworkin

  • A possible pathway for organic synthesis and implications for protostellar systems. Johnson et al.

  • Prebiotic phosphorylation through phosphorus radicals. Pasek, Dworkin & Lauretta

  • MALDI-MS analysis of hetero-trimer fractions formed by montmorillonite catalysis in the reaction of binary monomer mixtures. Hazen (Ertem) et al.

  • The astrobiology in secondary classroom (ASC) project. Walter, et al.

• STARDUST amino acid analysis • Hydrazine thruster contamination

• Amino acids in CM & CR meteorites • SAM GC/MS

• Nucleobases in CM meteorites • Asteroid sample return mission


Dworkin co authored abscicon presentations1
Dworkin Co-Authored AbSciCon Presentations

  • Investigation of isovaline enantiomeric excesses in CM meteorites using liquid chromatography time of flight mass spectrometry. Glavin & Dworkin

  • Reassessing the organic content of antarctic ice and meteorites. Botta et al.

  • Icy prebiotic chemistry of nitriles and other molecules. Hudson, Moore & Dworkin

  • Studies of amino acid formation by photolysis of interstellar ice analogs. Elsila, Bernstein & Dworkin

  • A possible pathway for organic synthesis and implications for protostellar systems. Johnson et al.

  • Prebiotic phosphorylation through phosphorus radicals. Pasek, Dworkin & Lauretta

  • MALDI-MS analysis of hetero-trimer fractions formed by montmorillonite catalysis in the reaction of binary monomer mixtures. Hazen (Ertem) et al.

  • The astrobiology in secondary classroom (ASC) project. Walter, et al.

• STARDUST amino acid analysis • Hydrazine thruster contamination

• Amino acids in CM & CR meteorites • SAM GC/MS

• Nucleobases in CM meteorites • Asteroid sample return mission


Synergies amino acids

gly

gABA

AIB

bala

ala

bABA

Synergies: Amino Acids

Collaborations with Glavin and Botta have focused research on amino acids and meteorites.

While I am fond of saying, “There is more to life than amino acids,” these compounds are relevant, popular, and (with our method of analysis) easy to generate extraordinary data.

1/2 of the AbSciCon abstracts from this lab are based on amino acid data from meteorites or lab simulations.

Lab facilities have been used to help characterize SAM derivitization agent


Amino acid protocol
Amino Acid Protocol

Sample

Water extraction (100ºC 24 h)

50%

Acid hydrolysis (6 M HCl 150ºC 3 h)

HPLC with UV fluorescence+ ToF-MS detection

Desalting of soils or meteorites (AG50W-X8 resin)

50%

Derivatization (OPA/NAC primary amines)


chirality

(non-super imposable mirror images)

With few exceptions, life is homochiral and abiotic chemistry is racemic

Using a chiral fluorescent label forms diastereomers with chiral amino acids (L,L and D,L) and allows for separation.


Studies of amino acid formation by photolysis of interstellar ice analogs. Elsila et al.

hn

10 K

H2O+CH3OH+HCN+NH3

Blank Fluorescence

Gly

Standard Fluorescence

b Ala

g ABA

Ala

D L

b ABA

D L

Sample Fluorescence


Studies of amino acid formation by photolysis of interstellar ice analogs. Elsila et al.

hn

10 K

H2O+CH3OH+HCN+NH3

Negative electrospray

OPA/NAC-Serine (-H+)

1 13C

2 13C

Positive electrospray

OPA/NAC-Serine (+H+)

1 13C

2 13C

m/z

Mass calibrate to internal or external standard


Studies of amino acid formation by photolysis of interstellar ice analogs. Elsila et al.

Alanine & b Alanine ESI+

Glycine ESI+

Serine ESI+

Fluorescence


Standards interstellar ice analogs.

C6

C5

C4

C3

C2

C3OH

C3COOH

C2COOH


Murchison Meteorite, CM2 interstellar ice analogs.

Danny Glavin’s Talk


Member of Organics Preliminary Examination Team interstellar ice analogs.

  • Analyze landing site mud for amine contamination

  • Arrange analysis of landing site and clean room air

  • Analyze heat shield and filters for amines

  • Analyze flight aerogel for amine contamination

  • Analyze comet-exposed aerogel for amines


Stardust evaluation of sources of 1 amine contamination r nh 2
STARDUST - Evaluation of Sources of 1° Amine Contamination (R-NH2)

Several flight quality aerogels and UTTR soil and standing water collected 2004 from near the Genesis recovery site were analyzed for amino acids. The results are compared to the Murchison (CM) and Orgueil (CI)meteorites.

Aerogel contamination should not be a problem for the STARDUST analyses. While, it is not anticipated that the samples were exposed to UTTR soil or water, some compounds (e.g. AIB) could still be determined.

*e-amino-n-caproic acid, from Nylon-6 degradation **a-amino-isobutyric acid


Analysis of air samples from the landing site and uttr clean room
Analysis of air samples from the landing site and UTTR clean room

  • Air samples were taken at the landing site near the heat shield and at the vents and in the UTTR clean room near the heat shield and the interior of the SRC.

  • Analyzed by GC and GC/MS at the NASA JSC Toxicology Laboratory.

  • Trace levels of volatile organic compounds were found at the heat shield and vents at the landing site.

  • Isopropanol and 1,1,1,2-tetrafluoroethane were found in the ppm range as well as trace levels of other volatile organic compounds at the heat shield and the interior of the SRC, after transfer to the Utah clean room.

1/2 L sampling bottle containing air from near the landing site vents analyzed at JSC.

  • The Sample Canister Filter has yet to be analyzed for any trapped gases.


Analytical techniques likely to be used for analysis of returned samples:

Analytical techniques to be used for analysis of returned samples

NanoSIMS Ion Microprobe): elemental and isotopic composition map

Inductively Coupled Plasma Mass Spectrometry (ICP-MS): elemental and isotopic composition

X-ray Absorption Near Edge Structure (XANES) Spectroscopy: general bonding of organics

Micro Laser Desorption Ionization Mass Spectrometry (µL2MS): polycyclic aromatic hydrocarbons (PAHs)

None will detect specific biomolecules!

Interplanetary Dust Particle (IDP)

Comet Wild 2


Can LC/MS techniques used in biotechnology be applied? returned samples:

Mass of single 10 µm grain: ~ 1 x 10-9 g

Concentration of AIB:

Murchison meteorite 3 ppm (µg/g)

Antarctic µmeteorite 0.2 ppm

Orgueil meteorite 0.04 ppm

Orgueil meteorite (b Ala) 2 ppm

Molecules AIB/grain (x 10-18 moles): 80 to 0.5

Detection limit (x 10-18 moles): ~10

Number 10 µm grains required: 1/4 to 20

Number 20 µm grains required: 1/32 to 2

Interplanetary Dust Particle (IDP)

Comet Wild 2


Stardust or IDP returned samples:

(10-20 µg)

ToF-MS

Water extraction (100ºC 24 h)

50%

LIF

Acid hydrolysis (6 M HCl 150ºC 3 h)

50%

Derivatization (OPA/NAC primary amines)

nLC

nLC with LIF

+ nanospray ToF-MS detection


Separation returned samples:

Column:

70µm x 100 mm

1.7µm resin


Fluorescence Detection returned samples:

Diode pulsed laser

70µm flow cell

PMT detector


Ionization returned samples:

Reference Sprayer

Baffle

MS Inlet

Sample Sprayer (20µm)


Detection of 10 amol of AIB by MS returned samples:

  • To do:

  • Reduce contamination (glass pipettes, pyrolyzed salts, clean room?)

  • Adapt HPLC separation technique to nLC


Adapt HPLC separation technique to nLC returned samples:

HPLC

4.6 mm, 5 µm resin

2 mm, 3 µm resin

1 mm, 3 µm resin

nLC

300 µm, 3 µm resin

100 µm, 3 µm resin

100 µm, 1.7 µm resin

70 µm, 1.7 µm resin

50 µm, 3 µm resin &

pre-column

70 µm, 1.7 µm resin

Goal

Phenylhexyl

XTerra C18

BEH C18


Ci meteorites a cometary origin
CI Meteorites: A Cometary Origin? returned samples:

CI CM

Orgueil (France, 1864)

AIB

b-alanine

glycine

  • CIs: fragments of extinct cometary nuclei(Lodders and Osborne, 1999)

  • Amino acid composition in CIs distinct from CMs

  • Amino acids consistent with volatiles detected in comets Hyakutake and Hale-Bopp (Crovisier and Bockelée-Morvan, 1999)

  • Direct analysis of comet or asteroid will help constrain the nature of meteorite parent bodies

Ehrenfreund et al. PNAS 98 (2001) 2138-2141


  • Ala returned samples:

  • Ala

    AIB

  • ABA

  • ABA

    g ABA


  • Ala returned samples:

  • Ala

    AIB

  • ABA

  • ABA

    g ABA