Mars Organic Molecule Analyzer (MOMA) - Harsh-Environment ...

MOMA: Mars Organic Molecule Analyzer
Luann Becker
Johns Hopkins Physics and Astronomy
Harsh Environment Mass Spectrometry Workshop
September 23rd 2009

Strategy for Future Missions to Mars
- Lessons learned from ‘Past’
Rover/Lander Missions: Emphasis
on Life Detection
- ‘Present’ Missions: Looking Ahead to
the Next Decade
- New Instrument Concepts in Search
for Life: MOMA
2

Mission Timeline
MSL
Lander
Discovery
Mid Rover
Mission
NASA
Joint Missions
NASA/ESA
ExoMars
3

Earth and Mars Today
4

Map of Mars showing H 2 O and Landing Sites
P
5

Previous Mass Spectrometry Concepts
• High mass range à complex organic analysis
• Drill to 2m; depth profiling
• Multiple sampling modes
6

Viking Missions: What Happened?
Viking (1976)
– GCMS: Surface soil
– No organics found by
GCMS
– Nutrient Experiment
Inconclusive
Conclusions:
Highly oxidizing soil, low pH
(acidic), ionizing radiation
produce non-volatile organic
salts resulting in more
refractory ‘labile’ organic
material
1 Benner et al., (2000) The Missing Organic Molecules on Mars? PNAS 2425-2430.
2 Kminek G and Bada JL (2006). The effect of ionizing radiation on the preservation of amino acids on Mars. Earth Planet. Sci. Lett., 245, 1−5.
1
2
7

Organics in Murchison Meteorite
Murchison Meteorite LDMS-TOF
242 252 278
228
300
178 202
314
328
342
Murchison ‘Kerogen’
Pendleton & Allamandola,
Ap. J. Sup. Ser. 138, 75 (2002)
8

Is there, or was there, life on Mars?
• ALH84001
– Martian meteorite
– Antarctica
– 1996: nanobacteria
fossils; amino acids,
PAHs found
1 Becker, L., Popp, B., Rust, T., Bada, EPSL., 167, 71-79 (1999); Becker, L. NRC Signs of Life Workshop, 161-173 (2000) .
2 Becker, L., Popp, B., Rust, T., Bada, J. Adv. Space Res., 24, 4, 477 (1999).
9

What is MOMA?
• AP MALDI = Atmospheric Pressure Matrix Assisted Laser
Desorption/Ionization (ASTEP)
– a pulsed laser is focused onto a solid sample in ambient environment
(Mars P = 5-10 Torr CO 2
; IR or UV laser Nd:YAG 266 nm)
– neutral and ionized molecules are produced
– molecules are drawn into a mass spectrometer for analysis
• ITMS = Ion Trap Mass Spectrometer
– ions are stored in stable orbits by a 3D quadrupolar RF electric field in
the presence of a rarified background gas (1-10 mTorr CO 2
works fine)
– ions are scanned out and detected by ramping the RF amplitude
– can be used to isolate individual ions for fragment analysis (MS/MS)
* The AP-MALDI was merged with a GCMS proposed by a German and
French team for the ExoMars mission; It is part of the MOMA suite
which also includes Pyr-GC-EI-MS
10

MOMA Science Requirements
What are our requirements?
1. the mass analyzer will need to be compatible with both
laser desorption and GCMS
2. laser desorption will be carried out in situ, on solid
samples presented at Mars atmospheric pressure
3. the mass range should encompass that expected for
establishing the existence of organic or potentially
biological relevant molecules (e.g. small peptides), ca
2,000 Da
4. the instrument will need to accommodate two ionization
sources (LD and electron ionization)
11

Why use an ion trap?
ION Trap Selection
1. most compatible with external (atmospheric) ionization
using laser desorption
a. TOFs (and others) require very high vacuum and a
means for sample introduction
b. orthogonal TOFs can be used with external ionization
but require very high pumping speed to achieve high
vacuum
2. has the possibility for doing MS/MS for structural
analysis
3. low power ion traps have been used successfully in
GCMS configurations
12

MOMA Instrument Concept Design
What are the specific challenges?
1. combining low voltage/low power with a
sufficiently high mass range
2. transferring ions formed in the Mars
environment into the vacuum chamber and
the ion trap
3. accommodating two sources of ions: those
generated externally by LD and those
generated by the GC either internally or
externally using electron ionization
13

MOMA LDMS Instrument Concept Design
Atmospheric pressure
laser desorption on
Earth
Pulsed UV laser
P=760 torr
Extended capillary
Atmospheric pressure
laser desorption on
Mars
Quadrupole, hexapole or octopole
ion guides
P=5-10 torr
Orifice
14

MOMA Instrument Concept Design
Accommodating low power/low voltage and high mass range
TABLE I. Quadrupole and Cylindrical Ion Trap Parameters
Param eter Finnigan Cooks Rosetta Cylindrical Mars
1
Fundamental _ /2¹ (MHz) 1.1 1.1 0.6 1.1 1.0 0.8
Maximum amplitude V max (0-p) 7.5 kV 7.5 300 V 7.5 kV 300 V 300 V
kV
Radius r 0 (cm) 1.0 0.5 0.8 1.0 0.5 0.5
Axis 2z 0 (cm) 1.0 0.5 1.13 1.79 0.5 0.5
Mass range (Da) in mass -selective instability 650 2,600 150 600 126 197
mode q eject = 0.908
Supplemental RF frequency (kHz) 69.9 NA NA 425 22.1 34.4
qeject 0.182 NA NA NA 0.057 0.089
Mass range (Da) in resonance ejection mode 3,250 NA NA NA 2,000 2,000
Mars
2
( m / z)
max
=
q
8V
max
2 2
( r 2z
)
2
eject
Ω
0
+
0
a
Kaiser RE, Jr., Cooks RG, Moss J, Hemberger
PH, Mass Range Extension in a Quadrupole
Ion-trap Mass Spectrometer, Rapid Commun.
Mass Spectrom. 3, (1989) 50-53
b
March RE, Todd JF, Quadrupole Ion Trap Mass
Spectrometry, John Wiley & Sons, Inc. Hoboken
NJ, 2005
15

Uniqueness of MOMA Design
What are the specific innovations?
1. combining low voltage/low power and a mass range up
to 2,000 Da using lower trap frequency and a
supplemental excitation with very low q eject value
2. accommodating LD and EI using internal electron
ionization with the electron source on the ring electrode
3. supplemental voltage frequency scanning of the mass
range
4. use of CO 2 as a bath gas in the LD mode
16

MOMA Prototype Design Concept
Low voltage/low power and high mass range using lower trap
frequency and supplemental excitation at very low q eject value
MOMA Ion Trap Parameters:
Fundamental _ /2¹
Maximum amplitude V
max
(0-p)
Radius r 0
Axis 2z 0
Mass range in mass-selective instability mode q eject
= 0.908
800 kHz
300 V
Mars 2
0.5 cm
0.5 cm
197 Da
Supplemental RF frequency
34.4 kHz
Supplemental RF voltage (axial modulation)
5-10 V
q eject
0.089
Mass range in resonance ejection mode
2,000 Da
Bath gas He or CO
2
Ionization:
Ion introduction:
laser desorption at Mars atmosphere (5 -10 Torr)
RF quadrupole ion guide
17

MOMA Instrument Concept
A novel internal EI
source with filament
mounted on the ring
electrode
Ions from laser
desorption/ionization
at Mars atmosphere
(5-10 Torr)
Internal EI for GCMS
+
- -
+
Filament
supply
Electron
energy
Fundamental RF
voltage generator
800 kHz, 300-
700V 0-p
Supplemental
RF generator
18

MOMA Mars Organic Molecule Analyzer
Protoype built by SESI
19

MOMA ITMS Operational Requirements
MOMA ITMS must be capable of:
1) Operating with CO 2
as a bath gas
2) Unit Mass Resolution
3) MS/MS capability
556.6
Leucine Enkephalin
MW 556.6
MH
YGGFL
Y=Tyr, G=Gly
F= Phe, L=Leu MS/MS
a 4
MH-H 2
0
530 540 550 560 570 580 590
m/z
CO 2 pressure
Peak width
1.2 x 10 -4 Torr 0.5 Da
10 -3 Torr 1.5 Da
100 200 300 400 500 600 700
m/z
V. Doroshenko, SESI
20

Leu-enkephalin
(YGGFL), m/z =
556.6
Bradykinin
fragment1-7
(RPPGFSP)
m/z = 757.4
Angiotensin II
(human) (DRVYI),
m/z = 1046.5
P 14
R
(polyproline)
(PPPPPPPPP
PPPPPR) m/z
= 1534
MOMA Prototype-1
4 peptide mixture; original
or ‘raw’ data
experimental conditions: V RF
= 700 V 0‐p
;
P = 0.7 mTorr (CO 2
) in the trap
Leu-enkephalin
(YGGFL), m/z =
556.6
Bradykinin
fragment1-7
(RPPGFSP)
m/z = 757.4
P 14
R (polyproline)
(PPPPPPPPPPPPPPR
) m/z = 1534
4 peptide mixture;
300 points smoothing
Angiotensin II
(human)
(DRVYI), m/z =
1046.5
experimental conditions: V RF
= 700 V 0‐p
;
P = 0.7 mTorr (CO 2
) in the trap
600 800 1000 1200 1400 1600
21

MS/MS MOMA Prototype‐1
2.0
1.5
P 14 R (polyproline)
Intensity
1.0
2P
(PPPPPPPPPPPPPPR)
m/z = 1534
experimental conditions: trap
RF 700 V 0‐p
0.7 mTorr CO 2
in
the trap
0.5
2P
2P
P
2P
P
2P
P
2P
P
0.0
400 600 800 1000 1200 1400 1600 1800 2000
m/z
22

MOMA GCMS Interface
Count
3000
2000
1000
0
1500
1000
500
0
INTERNAL IONIZATION w/ CO 2
237.5V, -60/+240V pulsing
EXTERNAL IONIZATION w/ CO 2
0 100 200 300 400 500 600 700 800
Mass
166.5V
237.5V
166.25V,
1200
1000
800
600
400
200
0
-60/+160V pulsing
JHU SOM
CO 2 as the bath gas
T. Evans-Nguyen
23

Gold Standard LD Ion Trap Mass Spectrometer
Thermo LD ITMS SESI Peru Desert
JHU PHA Gold Standard
336
644
834
1080
1250
1476
172
1665
1891
Jarosite
24

In Martian Analog Samples
KT boundary extra by CH3OH in He266nm_40 #1-88 RT: 0.00-1.99 AV: 88 NL: 5.92E-1
T: ITMS + p MALDI Full ms [100.00-1000.00]
262.25
100
256
266
95
246.17
90
256
85
80
242
75
356.08
70
65
276
232.25
60
228
302 270
55
288
50
274.25 370.17
288.25
45
326.25
224.17
RelativeAbundance
302.25
40
384.17
KT boundary Magic Layer
65 myr Extinction Event
35
30
25
20
15
10
5
398.33
202
412.25
452.17
428.17
464.25
178
470.25
210.08
628.17
504.25
606.00
588.33
662.33 710.33
518.25 730.42
198.25 540.42
776.50
648.42 704.50
899.08
581.17 834.75 760.50 854.75
782.33 813.42
870.33 907.42
911.50 949.58
135.17 188.33
993.67
106.83 177.92
396 452 500 600 700
0
100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
scan T extr by tolu in He 266nm_090724135822 #1-45 RT: 0.00-2.68 AV: 45 NL: 3.03
: ITMS + p MALDI Full ms [150.00-2000.00]
276.17
100
278
95
90
85
RelativeAbundance
80
75
70
65
60
55
50
45
40
35
30
25
20
15
202
202.17
252
228
216.17
230.17
252.17
266.17
300
290.17
300.17
318.25
326.17
350
350.17
374.17
400
m/z
Escanaba Trough Hydrothermal Vent
East Pacific Rise
10
340.17
364.25
5
392.25 424.08
723.50
448.25 682.33
668.08 699.42
625.33
487.00 639.33 766.08
590.42
470.17 741.50 777.50
515.17 557.17
192.17 575.25
178.08
0
150 200 250 300 350 400 450 500 550 600 650 700 750 800
m/z

PEG 600 with He and CO 2
P E G 6 0 0 w i th H e tu rb o # 1-102 R T : 0.00-2.00 AV: 102 N L : 3.04
T: ITM S + p M ALD I t Full m s [100.00-2000.00]
100
95
789.33
90
701.33
85
80
75
657.33
70
65
60
613.33
833.33
Peg 600 He
55
50
45
877.33
40
569.00
906.00
35
30
921.33
950.00
550.67 994.00
25
379.00
20
1038.00
1139.33
1183.33
15
10
5
190.00
503.00 1227.00
278.00 481.00
1248.67
1365.33
256.00 335.00
459.00
1408.67
411.33 1466.33
172.00
1584.00
234.00 1626.33
133.00 1758.67
1834.00 1947.67
0
100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000
m /z
PEG 600 + C H C A w ith C 02 turbo_090625110557 # 1-45 R T : 0.00-0.87 AV: 45 N L : 3.28
T: ITM S + p M ALD I t Full m s [150.00-2000.00]
100
95
849.33
937.00
90
808.00
85
80
979.33
75
739.67
70
65
651.67
709.33
1023.67
Peg 600 CO 2
60
55
1066.67
50
45
40
564.00
622.67
607.67
1110.67
1144.33
1160.33
35
517.33
1229.67
1274.67
30
1297.00
25
20
491.67
1341.33
1360.33
1426.67
1466.33
15
10
212.33
272.00
361.67
403.33
449.33
1557.33
1603.33
1654.67
1722.00
1770.67
1805.33
1930.33
5
0
200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000
m /z
26

Ultramark + CHCA_090619125632 # 1-45 RT: 0.00-1.30 AV: 45 NL: 7.38
T: ITMS + p MALDI Full ms [100.00-2000.00]
100
95
90
85
80
75
70
65
60
55
50
45
40
35
30
25
20
15
10
5
0
1319.5 1320.0 1320.5 1321.0 1321.5 1322.0 1322.5 1323.0 1323.5 1324.0 1324.5 1325.0 1325.5 1326.0 1326.5
Ultramark+CHCA with CO2 turbo_090622163636 # 1-26 RT: 0.00-0.98 AV: 26 NL: 2.28
T: ITMS + p MALDI E Full ms [100.00-2000.00]
100
95
90
85
80
75
70
65
60
55
50
45
40
35
30
25
20
15
10
5
0
1395.12
1398.72
1400.64
1322.00
1414.12
1413.44
1413.04
1411.32
1410.16
m/z
1415.12
1394 1396 1398 1400 1402 1404 1406 1408 1410 1412 1414 1416 1418 1420 1422 1424 1426 1428 1430 1432 1434 1436
m/z
1323.00
1416.24
1417.80
1418.56
1419.08
1419.60
1324.00
1426.12
1430.08 1436.
1428.44
Helium vs CO 2
T : p m s [ 1 5 0 . 0 0 2 0 0 0 . 0 0 ]
100
90
1522.1
1622.1
80
70
60
m/z-1416
Helium
1322.1
1422.1
1721.9
50
40
1222.1
1821.9
30
20
219.2
1319.42 1319.58 1320.25 1324.67 1325.00
1319.83 1320.67 1325.50
1326.00
1326.33
1122.1
1921.9
10
430.9
1022.2
365.1 446.7 669.4 806.4
0
500 1000 1500 2000
T : + p m s [ 1 5 0 . 0 0 2 0 0 0 . 0 0 ]
m /z
1518.7
100
1618.0
90
80
70
60
50
40
30
20
10
0
211.1
1401.60 1422.52 1431.36
1404.28 1433.08
1393.08 1396.28 1407.56 1424.40 1427.04
1435.60
1405.60
1421.16
1408.96
424.7
m/z-1416
CO 2
530.3 855.5 1074.8
809.7
1118.1
1218.8
1418.0
1716.9
1318.3 1817.0
1917.3
500 1000 1500 2000
m /z
27