minerals and primitive life detection - inaoe - p · minerals and primitive life detection mark van...

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



Huronian Glaciation



First Oceans

Earth history Early Life Stable Isotopes



Huronian Glaciation



First Oceans

Carbon isotope record

after Schidlowski (2001) Precam.Res 106, 117‐134

Earth history Early Life Stromatolites



Huronian Glaciation



First Oceans

Earth history Early Life Microfossils

10 µm



Huronian Glaciation



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



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


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


D


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


D1


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


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



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


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


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


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)


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



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


4.1 Ga Zircon crystals, Jack Hills, Western Australia

Bell et al. (2015) PNAS 112, 14518‐14521



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



First Oceans


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


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

3.2‐3.4 Ga Barberton Greenstone Belt, South Africa



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


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


3.3 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

3.5 Ga Apex chert, Pilbara, Australia



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

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

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