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Minerals and Primitive Life DetectionMinerals and Primitive Life Detection
Mark van ZuilenGeobiology groupGeobiology group
Institut Physique du Globe Paris (IPGP)
Earth history Early Life
GreatWorldwide Red beds GreatOxidationEvent
Lomagundi‐Jatuli event
Huronian Glaciation
Giant meteorite impacts
FirstLate Heavy Bombardment
Giant meteorite impacts
habitableconditionsFormation of the Moon
First Oceans
Earth history Early Life Molecular Biomarkers
GreatWorldwide Red beds GreatOxidationEvent
Lomagundi‐Jatuli event
Huronian Glaciation
FirstLate Heavy Bombardment
habitableconditionsFormation of the Moon
First Oceans
Earth history Early Life Stable Isotopes
GreatWorldwide Red beds GreatOxidationEvent
Lomagundi‐Jatuli event
Huronian Glaciation
FirstLate Heavy Bombardment
habitableconditionsFormation of the Moon
First Oceans
Carbon isotope record
after Schidlowski (2001) Precam.Res 106, 117‐134
Earth history Early Life Stromatolites
GreatWorldwide Red beds GreatOxidationEvent
Lomagundi‐Jatuli event
Huronian Glaciation
FirstLate Heavy Bombardment
habitableconditionsFormation of the Moon
First Oceans
Earth history Early Life Microfossils
10 µm
GreatWorldwide Red beds GreatOxidationEvent
Lomagundi‐Jatuli event
Huronian Glaciation
FirstLate Heavy Bombardment
habitableconditionsFormation of the Moon
First Oceans
Metamorphism
Organic material:
- loss of morphology- loss of H, N, O, P, S- isotope exchange- carbonizationcarbonization- graphitization
ght
10 µm
tacking he
ig
P,T P,T
Crystal domain size
St
kerogen graphite
Fundamental obstacles for tracing ancient life:
‐Morphology: Limited diversity in microbial shapes (filaments, spheres)
‐Metamorphism: ‐ Carbonization and graphitization of biologic materials‐ Recrystallizing mineral assemblages‐ Abiologic formation of graphite‐Migration of organic compounds
‐ Habitat: ‐ Abiotic hydrocarbon formation in hydrothermal settings‐ Chemolithoautotrophs in hydrothermal settingsChemolithoautotrophs in hydrothermal settings
Raman spectrum of carbonaceous material:
first order
second order
Qtz
cm-1
500 1000 1500 2000 2500 3000 3500 4000
First order Raman spectrum of carbonaceous material:
Isua 550°CTumbiana < 200°C Barberton 350°C
800 1000 1200 1400 1600 1800 2000800 1000 1200 1400 1600 1800 2000800 1000 1200 1400 1600 1800 2000
cm-1
800 1000 1200 1400 1600 1800 2000
cm-1
800 1000 1200 1400 1600 1800 2000
cm-1
800 1000 1200 1400 1600 1800 2000
g he
ight
P,T P,T
Stacking
, ,
kerogen graphiteCrystal domain size
kerogen graphite
First order Raman spectrum of carbonaceous material:
Isua 550°CTumbiana < 200°C Barberton 350°C
DG G G
D
D
cm-1
800 1000 1200 1400 1600 1800 2000
cm-1
800 1000 1200 1400 1600 1800 2000
cm-1
800 1000 1200 1400 1600 1800 2000
Peak width (FWHM): Dw and Gw2 0
Peak positions Dp and Gp
Peak‐intensity ratio ID/IGPeak‐area ratio AD/(AD+AG)
IG
1.5
2.0
Used to classify: ‐ kerogens, coals‐ carbonaceous chondrites
ID/I
0.5
1.0
Bonal et al. (2006), Pasteris and Wopenka (1993), Quirico et al. (2009), Olcutt‐Marshall et al. (2011).
Dw
20 40 60 80 100 120 1400.0
First order Raman spectrum of carbonaceous material:
2.0
Carbonization:
Ch i l ll i h
1.5
Chemical process allowing theformation of a pure sp2 carbonmaterial.
ID/IG
1.0
Graphitization:
Physical process correspondinglli h f
0.5
to crystalline growth of purecarbon
Rouzaud et al. (2015) C.R. Geosc. 347, 124‐
20 40 60 80 100 120 1400.0
ght
133
Dw
20 40 60 80 100 120 140
tacking he
ig
Crystal domain size
St
First order Raman spectrum of carbonaceous material:
D
Isua 550°CTumbiana < 200°C Barberton 350°C
G G G
D
D
cm-1
800 1000 1200 1400 1600 1800 2000
cm-1
800 1000 1200 1400 1600 1800 2000
cm-1
800 1000 1200 1400 1600 1800 2000
1 6
1.8
2.0
Nanocrystalline carbonAmorphous carbon1) Number of ordered sp2-rings
D1/
G- h
eigh
t)
0.8
1.0
1.2
1.4
1.6
ID/IG
R1
(D
0.0
0.2
0.4
0.6
Tuinstra&Koenig (1970) J.Chem.Phys.53, 1126
2
2) Domain size of graphite crystallites
1
La (Å)
1 10 100 1000 10000
Crystal domain size (La)Ferrari and Robertson (2000)Phys.Rev.B, 61, 14095‐14107
First order Raman spectrum of carbonaceous material:
D1
Isua 550°CTumbiana < 200°C Barberton 350°C
G G G
D1
D1D3
D4 D4D2
D2D2D3
cm-1
800 1000 1200 1400 1600 1800 2000
cm-1
800 1000 1200 1400 1600 1800 2000
cm-1
800 1000 1200 1400 1600 1800 2000
R1 = D1/G intenistyR2 = D1/(D1+D2+G) area
RA1 = (D1+D4)/(D1+D2+D3+D4+G) areaRA2 = (D1+D4)/(D2+D3+G) area
Used for calculating peak metamorphic temperature
Beyssac et al. (2002)Lahfid et al., 2010)Aoya et al., 2010)
Aoya et al. (2010) J.Met.Geol. 28, 895‐914
First order Raman spectrum of carbonaceous material:
2.0350°C
Carbonization:
Ch i l ll i h
1.5
350°C
300°C
Chemical process allowing theformation of a pure sp2 carbonmaterial.
ID/IG
1.0 400°C
250°C
200°C
Graphitization:
Physical process correspondinglli h f
0.5 450°C
200 Cto crystalline growth of purecarbon
Rouzaud et al. (2015) C.R. Geosc. 347, 124‐
20 40 60 80 100 120 1400.0
ght
600°C500°C133
Dw
20 40 60 80 100 120 140
tacking he
ig
Crystal domain size
St
In situ analytical techniques Raman spectroscopy
50 μm
Siderite Ankerite
cm-1
500 1000 1500 2000
Rividi et al (2010) Astrobiology 10 293‐309
carbonate kerogen50 μm
Rividi et al. (2010) Astrobiology, 10, 293‐309
Sforna et al. (2014) GCA, 124, 18‐33
3.9 Ga Akilia Association, Southern West Greenland
Mojzsis et al. (1996) Nature 384, 55‐59
FirstLate Heavy Bombardment
habitableconditionsFormation of the Moon
First Oceans
Sample G91‐26, Akilia Island3.9 Ga Akilia Association, Southern West Greenland
B
Main event: ‐ Granulite facies (700°C, >6 kbar)Retrograde event: ‐ Amphibolite facies (550°C, 5 kbar)
B
D
C
G91‐26‐G
E
FF
G
H
Lepland et al. (2011) Geobiology 9, 2‐9
3.9 Ga Akilia Association, Southern West Greenland
CO2
CO2
GCO2
CO2CO2
Fluid inclusion trails
1200 1300 1400 1500 1600 1700 1800
D
1200 1300 1400 1500 1600 1700 1800
cm-1
1200 1300 1400 1500 1600 1700 1800
GCO
cm-1
G
G
CO2
CO2
D D
cm-1
1200 1300 1400 1500 1600 1700 1800
cm-1
1200 1300 1400 1500 1600 1700 1800
3.9 Ga Akilia Association, Southern West Greenland
2.0CO2
IG
1.5
G
CO2
ID/
0.5
1.0D
Dw
20 40 60 80 100 120 140 1600.0
cm-1
1200 1300 1400 1500 1600 1700 1800600°C
Dw
Lepland et al. (2011) Geobiology 9, 2‐9
M i G li f i (700°C 6 kb )Main event: ‐ Granulite facies (700°C, >6 kbar)Retrograde event: ‐ Amphibolite facies (550°C, 5 kbar)
3.9 Ga Akilia Association, Southern West Greenland
Graphitization from carbonic fluid:
T t d f lit t hib lit f i‐ Temperature decrease from granulite to amphibolite facies‐ Selective water diffusion e.g. during granulite facies‐ Changes in fluid composition e.g. during calcite breakdown
C
0.9
1.00.0
0.1
C
0.9
1.00.0
0.1
C C
0.6
0.7
0.80.2
0.3
0.4
500 C
0.6
0.7
0.80.2
0.3
0.4
500 C800 C
0.3
0.4
0.50.5
0.6
0.7
0 8 b0.3
0.4
0.50.5
0.6
0.7
0 8
graphite+ fluid graphite+ fluidCO2CO2
CH4 CH4
H0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.00.0
0.1
0.2
O
0.8
0.9
1.0
ab
c
H0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.00.0
0.1
0.2
O
0.8
0.9
1.0
a
bfluidfluid
fluidfluid
O H HOH OH O
CO2 + CH4 = 2H2O + 2C
H2OH2O
Lepland et al. (2011) Geobiology 9, 2‐9
3.9 Ga Akilia Association, Southern West Greenland
Apatite
Apatite‐graphite association
cm-1
800 1000 1200 1400 1600 1800
trails10 μm
G
clusters
ApatiteD
800 1000 1200 1400 1600 180040 μmcm-1
Lepland et al. (2011) Geobiology 9, 2‐9
4.1 Ga Zircon crystals, Jack Hills, Western Australia
Bell et al. (2015) PNAS 112, 14518‐14521
FirstLate Heavy Bombardment
habitableconditionsFormation of the Moon
First Oceans
4.1 Ga Zircon crystals, Jack Hills, Western Australia
D‐peak width (FWHM) = 180 cm‐1P k i t it ti ID/IG 0 562 0
Bell et al. (2015) PNAS 112, 14518‐14521
Peak‐intensity ratio ID/IG = 0.56
IG
1.5
2.0
ID/I
0.5
1.0
?
Dw
20 40 60 80 100 120 1400.0
3.8 Ga Isua Supracrustal Belt, Southern West Greenland
Mojzsis et al. (1996) Nature 384, 55‐59
FirstLate Heavy Bombardment
habitableconditionsFormation of the Moon
First Oceans
3.8 Ga Isua Supracrustal Belt, Southern West Greenland
Isua 550°C
Amphibolite facies (550°C, 5 kbar)
1.5
2.0
G
ID/IG
1.0D
20 40 60 80 100 120 1400.0
0.5
600°Ccm-1
800 1000 1200 1400 1600 1800 2000
Dw
20 40 60 80 100 120 140
3.8 Ga Isua Supracrustal Belt, Southern West Greenland
High‐P,T disproportionation of carbonate veins (T = 550°C, P = 5 kbar)
6 FeCO3 = 2 Fe3O4 + 5CO2 + C
siderite magnetite graphite
graphite
siderite
apatite
magnetite
graphite
50 m50 μm
Van Zuilen et al. (2002) Nature 418, 627‐630
Fundamental obstacles for tracing ancient life:
‐Morphology: Limited diversity in microbial shapes (filaments, spheres)
‐Metamorphism: ‐ Carbonization and graphitization of biologic materials‐ Recrystallizing mineral assemblages‐ Abiologic formation of graphite‐Migration of organic compounds
‐ Habitat: ‐ Abiotic hydrocarbon formation in hydrothermal settings‐ Chemolithoautotrophs in hydrothermal settingsChemolithoautotrophs in hydrothermal settings
3.2‐3.4 Ga Barberton Greenstone Belt, South Africa
FirstLate Heavy Bombardment
habitableconditionsFormation of the Moon
First Oceans
Barberton Greenstone Belt, South Africa 3.4‐3.2 Ga
Greenschist facies (300‐400 °C, 2 kbar)
1 5
2.0300°C
410°C300°C GD
ID/IG
1.0
1.5 GD
0.5
Dw
20 40 60 80 100 120 1400.0
cm-1
800 1000 1200 1400 1600 1800 2000
3.2‐3.4 Ga Barberton Greenstone Belt, South Africa
0.008HooggenoegFootbridgeBuck Reef
Footbridge Chert
o (m
olar
)
0 004
0.006 Isua
N/C
-rat
io
0.002
0.004
Buck Reef Chert
-40 -30 -20 -10 00.000
δ13C (per mil, PDB)
0 30 0 0 0
Hooggenoeg H5c Isua graphite
van Zuilen et al. (2007)GCA 71, 655‐669
3.2‐3.4 Ga Barberton Greenstone Belt, South Africa
3.3 Ga Footbridge Chert, South Africa
-35.336 8 34 9
-37.8-32.6
-36.8 -34.9
Z il t l (2007) GCA 71 655 669van Zuilen et al. (2007) GCA 71, 655‐669
Fundamental obstacles for tracing ancient life:
‐Morphology: Limited diversity in microbial shapes (filaments, spheres)
‐Metamorphism: ‐ Carbonization and graphitization of biologic materials‐ Recrystallizing mineral assemblages‐ Abiologic formation of graphite‐Migration of organic compounds
‐ Habitat: ‐ Abiotic hydrocarbon formation in hydrothermal settings‐ Chemolithoautotrophs in hydrothermal settingsChemolithoautotrophs in hydrothermal settings
3.5 Ga Apex chert, Pilbara, Australia
FirstLate Heavy Bombardment
habitableconditionsFormation of the Moon
First Oceans
3.5 Ga Pilbara granitoid-greenstone belt Greenschist facies
Brasier et al. (2002) Nature 416, 76‐81 Schopf et al. (2002) Nature 416, 73‐76
10 µm10 µm
3.5 Ga Pilbara granitoid-greenstone belt Greenschist facies
2.0
Hydrothermal
ID/IG
1.0
1.5 Stratiform
0.5
Dw
20 40 60 80 100 120 1400.0
Sforna et al. (2014) GCA 124, 18‐33
Abiologic processes: Serpentinization and Fischer-Tropsch synthesis
Olivine + H2O = Serpentine + Brucite + Magnetite + H2
nCO + (2n+1)H2 = CnH2n+2 + nH2O
McCollom (2003) GCA 67, 311‐317 McCollom and Seewald (2006) EPSL 243, 74‐84McCollom (2003) GCA 67, 311 317 McCollom and Seewald (2006) EPSL 243, 74 84
Abiologic processes: Serpentinization and Fischer-Tropsch synthesis
Olivine + H2O = Serpentine + Brucite + Magnetite + H2
nCO + (2n+1)H2 = CnH2n+2 + nH2O
50 µm50 µ
Garcia-Ruiz et al (2003) Science 302 1194-1197Brasier et al (2005) Prec Res 140 55-102 Garcia-Ruiz et al. (2003) Science 302, 1194-1197 Brasier et al. (2005) Prec.Res. 140, 55-102
Fundamental obstacles for tracing ancient life:
‐Morphology: Limited diversity in microbial shapes (filaments, spheres)
‐Metamorphism: ‐ Carbonization and graphitization of biologic materials‐ Recrystallizing mineral assemblages‐ Abiologic formation of graphite‐Migration of organic compounds
‐ Habitat: ‐ Abiotic hydrocarbon formation in hydrothermal settings‐ Chemolithoautotrophs in hydrothermal settingsChemolithoautotrophs in hydrothermal settings
Nano scale structure of silica-carbonate biomorphs:
50 µm
Garcia-Ruiz et al. (2003) Science 302, 1194-1197
Focused Ion Beam Scanning Electron Microscopy (FIB-SEM)
2 µm
Wirth (2009) Chem.Geol.,261, 217‐229
Transmission Electron Microscopy (TEM)
Graphite
Quartz orgCorgCQuartz
2 µm
100 nm
Mineral-templated graphitization
van Zuilen et al. (2012) GCA, 83, 252‐262
Transmission Electron Microscopy (TEM)
Quartz graphite orgC
100 nm
quartz orgC
5 nm
quartz orgC
van Zuilen et al. (2012) GCA, 83, 252‐2622 µm
Earth history Early Life Mars
GreatGreatOxidationEvent
Firsthabitableconditions