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12.158 Lecture 5
• Hopanoids and other cyclic terpenoids
– Structures, biosynthesis, diagenesis – Hopanoid hydrocarbons;
stereochemistry vs maturity
– Hopanoids as process and
environment indicators
1
Hopanoids
• First recognised as a class of
C30 pentacyclic triterpenes
found in ferns, mosses and
dammar resins
• �Hopane� named after the
Dipterocarp plant genus Hopea,
itself after botanist John Hope
• Biosynthetic kinship to sterols,
tetrahymanol & oleanoids, via
squalene recognised in 60�s
© Gaines, Eglinton & Rullkötter
These images have been removed due to copyright restrictions.
2
Evolution of Hopane & Sterol Bioynthesis
BHP
Squalene Diploptene
Squalene epoxide
o2
O
BACTERIA
HO HO C24 substitution by algaeLanosterol Cholesterol
some bacteria - Methylococcus Mycobacteria, Myxobacteria
EUCARYA o2
3
Structure and Function of a Squalene Cyclase K. Ulrich Wendt, Karl Poralla, Georg E. Schulz *
The crystal structure of squalene-hopene cyclase from Alicyclobacillus acidocaldarius was determined at 2.9 angstrom resolution. The mechanism and sequence of this cyclase are closely related to those of 2,3-oxidosqualene cyclases that catalyze the cyclization step in cholesterol biosynthesis. The structure reveals a membrane protein with membrane-binding characteristics similar to those of prostaglandin-H2 synthase, the only other reported protein of this type. The active site of the enzyme is located in a large central cavity that is of suitable size to bind squalene in its required conformation and that is lined by aromatic residues. The structure supports a mechanism in which the acid starting the reaction by protonating a carbon-carbon double bond is an aspartate that is coupled to a histidine. Numerous surface helices are connected by characteristic QW-motifs (Q is glutamine and W is tryptophan) that tighten the protein structure, possibly for absorbing the reaction energy without structural damage.
4
SQUALENE
3
HOPENE
B1:H B2
22
29
1
The proposed reaction steps in squalene-hopene cyclases involving carbocationic intermediates. The general acid B1:H protonates (H) squalene at C3, whereas the general base B2 deprotonates at C29 of the hopenyl cation. In a side reaction, the cation is hydroxylated forming hopan-22-ol (i.e. diplopterol)
Image by MIT OpenCourseWare.
5
This image has been removed due to copyright restrictions.
Figure 5. The color-coded surface representations (30) with nonpolar (yellow), positive (blue), and negative (red) areas. (A) View similar to Fig. 2 but rotated around a vertical axis and sliced. The cutting plane (checked) opens the large internal cavity with the bound inhibitor LDAO. The nonpolar channel runs to the left, opening into a nonpolar plateau. The channel constriction (C) appears closed, but it is mobile enough to be readily opened. At the upper left, hopane (two views) is shown at scale. (B) View similar to Fig. 2 directly onto the 1600 Å2 nonpolar plateau with the channel entrance (E) at its center and two nonpolar side chains pointing to the outside. This is the only large nonpolar region on the surface
6
Discovery of Geohopanoids
• Hopane identified in Green River Shale by Burlingame, Haug, Belksky &
Calvin, PNAS, 1965.
• C27-C31 Triterpanes in optically active petroleum distillates, Hills &
Whitehead, Nature 1966
• Homohopane in Green River, Ensminger Maxwell (Bristol & Strasbourg,
�72)
• Extended hopane series to C35 ubiquitous in the geosphere incl. petroleum,
soils and diverse sediments
Ensminger, van Dorsselaer, Spyckerelle, Albrecht, Ourisson (Strasbourg) and
Eglinton, Maxwell, Kimble, Philp & Brooks (Bristol) 1973-4
Hills & Whitehead (BP) speculated there was a C35 precursor 7
Hopanoids in Bacteria & Rocks?
• Diploptene (C30) identified in bacteria & cyanonbacteria, de Rosa (1971)
incl. Methylococcus capsulatus , Bird et al., (1971)
•ββ-hopane and ββ-homohopane in Bacillus acidocaldarius, de Rosa 1973
• Fossil hopanoids exhibit αβ, βα and ββ stereochemistry with 22S+R; ββ
and βα recognized as less stable than αβ
• C30 C-3 oxygenated triterpane alcohols and ketones in Messel, but not
equivalent C30 hydrocarbons suggest many hopane hydrocarbons entered
as 3-desoxy components
• Mystery ‘almost’ solved when Forster, Biemann et al characterized a C35 tetrahydroxy triterpenoid in Acetobacter xylinum (1973)
8
Hopanoids
Biochem. J. (1973) 135, 133-143
Printed in Great Britain 133
The Structure of Novel C35 Pentacyclic Terpenes from Acetobacter xylinum
By HANS J FRRSTER * and KLAUS BEIMANN Department of Chemistry, Massachusetts Institute of Technology,
Cambridge, Mass. 02139, U.S.A.
And W.GEOFFREY HAIGH Biomedical Research Laboratory, Dow Corning Corporation, Midland,
Mich, 48640, U.S.A.
And NEIL. H.TATTRIE and J.ROSS COLVIN, Division of Biological Sciences, National Research Council of Canada,
Ottawa K1A OR6, Canada
(Received 14 February 1973)
9
Patterns of Geohopanoids in GC-MS
Geochemists figured that the absence of C28 homologue and pairs of peaks from
C31-C35 are informative about side-chain structure
10
Hopanoids
Courtesy Elsevier, Inc., http://www.sciencedirect.com. Used with permission.
11
http://www.sciencedirect.com
Hopanoids
Courtesy Elsevier, Inc., http://www.sciencedirect.com. Used with permission.
12
http://www.sciencedirect.com
Hopanoids
Biochem J. (1973) 135, 133–143 133 Printed in Great Britain
The Structure of novel C35 pentacyclic terpenes from Acetobacter xylinum
By HANS J. FÖRSTER* and KLAUS BIEMANN Department of Chemistry, Massachusetts Institute of Technology,
Cambridge, Mass. 02139, U.S.A.
and W. GEOFFREY HAIGH
Biomedical Research Laboratory, Dow Corning Corporation, Midland,
Mich. 48640, U.S.A.
and NEIL H. TATTRIE and J. ROSS COLVIN
Division of Biological Sciences, National Research Council of Canada,
Ottawa K1A OR6, Canada
(Received 14 February 1973)
A novel C35 terpene and its monounsaturated analogue were isolated from cultures of Acetobacter xylinum, together with traces of their C36 homologues. These substances were found to be hopane derivatives substituted by a five-carbon chain bearing four vicinal hydroxyl groups. For the parent hydrocarbon the term bacteriohopane is proposed. The elucidation of the structures utilized high-resolution mass spectrometry of the terpenes, degradation to C32 hydrocarbons and detailed mass-spectrometric comparison of these with C32 hydrocarbons synthesized from known pentacyclic triterpenes. High-resolution mass-spectral data of the terpenes are presented. N.m.r. data are in agreement with the proposed structures, which are further supported by the isolation from the same organism of 22-hydroxyhopane and derivative hopene(s).
13
Hopanoid quotes
• The formation of the more stable αβ hopane
epimers could constitute , in a given environment, a geochemical clock unless they happen to be still unrecognized constituents of living organisms
�.......... Ensminger et al., Advances in OG..1973
• The total amount of geohopanoids is estimated to be ~1012 tons and same order as total mass of organic carbon in all living organisms
�.......... Ourisson and Albrecht, Geohopanoids, the most abundant natural products on Earth, Acc Chem Res 1992
14
11 known ring systems
Ring Variations
2
3 Δ6
Δ11 C-2 Me CYANOBACTERIA
Summons et al., 2000 22R
C-3 Me METHANOTROPHS (Acetic Acid bacteria)
Δ6 and/or Δ11 ACETIC ACID BACTERIA (Methanotroph)
15
Side Chain Variations
OH OH
OH XY
Z
TETRA: X=OH, NH2, composite; Y = Z = H
Composite
HEXA: X = NH2; Y = Z = OH
30 31
PENTA: X = OH, NH2, composite; Y = OH, Z = H X = OH, Y = H, Z = OH
O NH2
OH
OHOHOH
NH
O
NH2 NH2
O
O
COOH
OH OH
OH
16
Analysis Of Bbiohopanoids
• Highly functionalised, amphiphillic • Not amenable to conventional GC-MS • Side chain cleavage (Rohmer et al., 1984)
– Periodic acid/sodium borohydride – Product structure directly related to number
and position of functional groups in side chain
• Specific nature of functional groups lost
17
Periodic Acid Oxidation
OH
TETRA O OH
OH OH
32 OO OOH H5IO6/NaBH4 32-hopanol OH H
OH
OH OH
OHOH 31
PENTA 31-hopanol H5IO6/NaBH4 OH
HEXA OH
OH OH OH H5IO6/NaBH4 30-hopanol30
OH OH NH2
18
Hopanoids
The effect of thermal stress on source-rock quality as measured by hopane stereochemistry
WOLFGANG K. SEIFERT, J. MICHAEL MOLDOWAN
Chevron Oil Field Research Company, P.O. Box 1627, Richmond, California 94802, U.S.A.
This image has been removed due to copyright restrictions.
In: A.G. Douglas and J.R. Maxwell, Editors, Advances in Organic Geochemistry, Pergamon Press, Oxford (1980), pp. 229–237
19
Hopanoids & Thermal Maturity
20
Structural Diversity of Hopanoids
Courtesy Elsevier, Inc., http://www.sciencedirect.com. Used with permission.
21
http://www.sciencedirect.com
Hopanoids and Physiology
Distribution of hopanoid triterpenes in prokaryotes
Rohmer, M. , Bouvier-Nave, P. , Ourisson, G. Ecole Nationale Superieure de Chimie de Mulhouse, Universite de Haute Alsace, 68093 Mulhouse Cedex, France
Present in 50% of some 100 strains across diverse taxa
In almost all cyanobacteria, obligate methylotrophs , purple non-sulfur bacteria and diverse chemoheterotrophs
Absent from purple sulfur bacteria, archaebacteria
Not detected in any anaerobe
Bacteriohopane tetrol most common
Journal of General Microbiology Volume 130, Issue 5, 1984 1137-1150 22
Functional Role of Hopanoids?
Proc. Natl. Acad. Sci. USA Vol. 76, No. 2, pp. 847-851, February 1979
Molecular evolution of biomembranes: Structural equivalents and phylogenetic precursors of sterols
(triterpenes/tetraterpenes/prokaryotes/pre-aerobic evolution)
MICHEL ROHMER, PIERRETTE BOUVIER, AND GUY OURISSON
Rohmer & Ourisson, 1976
Rohmer et al., 1979
Kannenberg & Poralla, 1980
Many lines of evidence show an association of
BHP with cellular membranes
Image courtesy of Michel Rohmer. Used with permission.
Evolution
23
First Report of 3-Methyl Hopanoids
Courtesy Elsevier, Inc., http://www.sciencedirect.com. Used with permission.
24
http://www.sciencedirect.com
Discovery of Methylated Hopanoids
Acetobacter BHP hypothesized to be 3
methylhopanoids on biosynthetic grounds
25
This image has been removed due to copyright restrictions.
Discovery of
Methylated Hopanoids
Proof of structure of 3-methyl BHT by
correlation with synthetic 3-methyl
bishomohopane
Stereochemistry at C3 not assigned
until 1985
3β by nmr &
comparison with 3β-methyldiplopterol
& 3β-methylhopan-29-01 synthesized
from 22-hydroxyhopan-3-one.
3β-methylhopanoid content of A.
pasteurianus ssp. pasteurianus could
be increased up to 60% of
the total hopanoid content by addition
of L-methionine, the actual methyl
donor, to the culture medium.
26
Discovery of 2β-Me Hopanoids
Prokaryotic triterpenoids 2.2ß-Methylhopanoidsfrom Methyfobacterium organophilum and Nostoc muscorum, a new series of prokaryotic triterpenoids
Philippe BISSERET, Magali ZUNDEL and Michel ROHMER
Ecole Nationale Suptrieure de Chimie de Mulhouse
Eur. J. Biochem. 150, 29-34 (1985)
©FEBS 1985
27
2β-Me Hopanoids
2β by nmr & direct comparison with 2β-methyldiplopterol
synthesized from 22
hydroxyhopan-3-one.
This image has been removed due to copyright restrictions.
28
2α-Me Hopanoids Tetrahedron Vol 47, No. 34, pp 7081-7090, 1991 ©1991 Pergamon Press pic Printed in Great Britain
2 Į -Methylhopanoids: First Recognition in the Bacterium Methylobacterium organophilum and Obtention via Sulfur Induced Isomerization of
2ß-Methylhopanoids. An account for their presence in sediments.
P Stampf. D Herrmann. P Bisseret. M Rohmer
c. 5% methyldiplopterols 2α by 13 C nmr & direct comparison with 2α-methyldiplopterol
synthesized from 22-hydroxyhopan-3-one.
Sloppy methylase? Any 2α-methyl in Nostoc or
Rhodopseudomonas?
29
Geological Occurrence of Methyl Hopanoids
• Fossil methyl hopanes reported in sedimentary
rocks and oils eg SEIFERT and MOLDOWAN, 1978;
ALEXANDER et al., 1984; MCEVOY and GIGER,
1986; SUMMONS and POWELL, 1987
• Tentatively but erroneously thought to be 3-methyl hopanes based on the reports of 3-methylhopanoids in methylotrophs
• Complex mixtures precluded any spectroscopic
analysis other than GC-MS
• Synthetic approaches already developed by
Rohmer but not applied to geo hopanoids
30
Geological Occurrence of Methyl Hopanoids
31
1 0 0
%
00 0 3 0 7 2 4 0 1 1 0 0
%
00 0 3 0 7 2 4 0 1 1 0 0
%
6 5 .1 9 00
0 3 0 7 2 4 0 1 1 0 0
%
6 3 .9 8 6 4 .8 3 6 3 9 8 6 4 .8 3 0
0 3 0 7 2 4 0 1 1 0 0
6 4 .0 9
%
6 3 .9 8 6 4 .2 5 6 0 .0 0 6 2 .8 1
0
0 3 0 7 2 4 0 1
6 3 .9 8 1 0 0
% 6 1 .7 6 6 2 .6 3
6 3 .7 4 6 4 .1 3
0
6 8 .4 6
7 1 .2 8 7 1 .7 7
6 6 .1 4 6 7 .0 2 6 9 .0 4 7 1 .0 9
7 2 .4 3 7 3 .2 9 7 4 .2 2454.452 > 205.194
6 7 .9 7 6 8 .3 8
6 6 .8 8 6 8 .9 6 7 0 .3 9
6 6 .2 2
6 6 .4 7
6 9 .1 6 6 9 .4 5 6 6 .9 6 6 8 .0 3
6 6 .1 2 6 6 .3 7
6 6 .8 8 6 7 .1 1 6 7 9 7 6 7 .9 7
6 6 .1 4 6 6 .3 9
6 6 .7 2
6 7 .9 9 6 8 .4 06 8 .4 0
6 6 1 26 6 .1 2 6 6 .3 9
7 0 .3 9
440.437 > 191.179
440.437 > 205.194
426.421 > 191.179
426.421 > 205.194
6 0 .0 0 6 2 .0 0 6 4 .0 0 6 6 .0 0 6 8 .0 0 7 0 .0 0
412.406 > 191.179
7 4 .0 0 7 6 .0 0 7 8 .0 07 2 .0 0
GC with MS-MS -> isomers of each individual homologue to be seen in
separate chromatograms
32
Geological Occurrence of Methyl Hopanoids
Compparison of 2α
methyl hopane and 3β
methyl hopane with
This image has been removedThis image has been removed fossil hydrocarbonsfossil hydrocarbons due to copyright restrictions.
Sample was an iimmatture OO drdoviiciian
sediment with two series of methyyl
hopanes
33
Geological Occurrence of Methyl Hopanoids
Relative retention timesRelative retention times used to assign identity
to C27-C35 series’
Sample s an immature
Ordovician kukersite
S di t th l h d i d f th l l f BHPSedimentary methyl hopanes derived from methyl analogues of BHP
34
O2-Diagnostic Bacteriohopanes ??O2 Diagnostic Bacteriohopanes ??
R
OH OH 21
32
19
35 22 diagenesis
1
R3 OH
32 17
R2 2
43
10
1125
29 14 16
35
R1
cyanobacteria
diagenesis maturation
cyanobacteria cyanobacteria δ13C -20 to -35 ‰
1
R3
OH
OH
OH 21
32 1711
19
25
29 14 16
35
OH
22
NH2
diagenesis maturation
12
43
10 29
methanotrophic bacteria methanotrophs δ13C -45 to -80 ‰
Jahnke et al., 1992, 1993; 1999; Summons & Jahnke, 1988, 1990; Summons et al., 1994, 1999
35
Isotopic Signature of 3-Methyl Hopanoids
pMMO sMMO
C-isotopic fractionation in biomass of M. capsulatus:
varies as a function of substrate, growth stage, MMO type
Summons et al., GCA, 1994 Courtesy Elsevier, Inc., http://www.sciencedirect.com. Used with permission. 36
http://www.sciencedirect.com
Isotopic Signature of 3-Methylhopanoids
Biomass-triterpenoids ε ~ 36‰Biomass triterpenoids ε 36‰
Distribution and C-isotopic fractionation in hopanoids of M.
capsulatus as function of growth stage
Summons et al., GCA, 1994 Courtesy Elsevier, Inc., http://www.sciencedirect.com. Used with permission. 37
http://www.sciencedirect.com
Geological Occurrence of 3-Methylhopanoids
Advances in Organic Geochemistry 1991 Org. Geochem. Vol. 19, Nos 1-3, pp. 265-276, 1992 Printed in Great Britain
An isotopic biogeochemical study of the Green River Oil shale
JAMES W. COLLISTER, ROGER E. SUMMONS, ERIC LICHTFOUSE, and J. M. HAYES Biogeochemical Laboratories, Department of Geological Sciences and Chemistry Geology Building, Indiana University, Bloomington, IN 47405, U.S.A. and Bureau of Mineral Resources, G.P.O Box 378,
Canberra, A.C.T 2601, Australia
This image has been removed due to copyright restrictions. Please see Figure 7 in the above article.
38
Hamersley Basin biomarker & isotopic records
Courtesy of National Academy of Sciences, U. S. A. Used with permission. Source: Eigenbrode et al (2008) National Academy of Sciences, USA. Eigenbrode et al, PNA S Copyright (c) 2008, National Academy of Sciences, U.S.A. 2008 39
Cyyanobacterial Lippids 9
COOH OH phytol11
C 16-18 fattyy acid and PUFA16 18
n-heptadecane
7
7- & 8
methylheptadecane
88 OHOH
7 11
COOH
β tβ-carotene
R
7 11 dimeth lh tadecane7,11-di thylhept d hopanoids & 2-methylhopanols
40
Are 2-methylhopanes biomarkers for
cyanobacteria and O photosynthesis?cyanobacteria and O2-photosynthesis?
• Sppecificityy of 2-MeBHP for Cb? ~30% of Cb surveyyed ((Talbot et al, OG 2008))
– Methylobacterium, N-fixing soil bacteria (Rhizobiales) – Rhodopseudomonas palustris (Rashby et al., 2007) – Commonly present in heterocystous cyanobacteria – Relatively abundant in a Baltic Sea strain ofRelatively abundant in a Baltic Sea strain of NodulariaNodularia
• What are the environmental occurrences? – Very abundant in hot spring mats; low levels in marine hypersaline Cb mats
• What are the biological functions of BHP & methylated BHP? – Membrane-associated in P luridum and Mc Bath; pCO2 control in Phormidium?
• Geological occurrences? Secular in shales; Always at OAEsGeological occurrences? Secular in shales; Always at OAEs
• What is the biosynthetic pathway? – No unsaturated precursors; Radical SAM? See Paula’s talk
• Are biosynthetic pathways conserved over geological time? Does a
biomarker found today mean the same thing as one 500Myr old?
41
2-MeHopanes vs Lithology & Paleogeography
0 25
0.30
Carbonate
Marl
Distal Shale
0.20
0.25
x
Distal Shale
0.15
ylho
pane
Inde
x
0.10
2-M
ethy
0.05
0.00 -90 -70 -50 -30 -10 10 30 50 70 90
Paleolatitude 42
2-Me BHP - Biomarkers for Cyanobacterial Photosynthesis ?
0 30
2-M
ethy
lhop
aane
Inde
xx
0.30
0.20
0.10
Carbonate
Marl
Distal Shale
200 400 600 800 1000 1200 1400 1600 1800 Sediment Age MYA
43
2-Me BHP - Biomarkers for Cyanobacterial Photosynthesis ? Frasnian-Famennian
Toarcian OAEOAE
Permian-Triassic Cretaceous OAEs
0.30
x
Carbonate
Marl
Distal Shale
0.20 ane
Inde
xet
hylh
opa
0.10
2-M
e
0 100 200 300 400 500
Sediment Age MYA
600
44
2-Methylhopane Index for Sediments/Oils
Barney Creek Fm #1698Barney Creek Fm #1698
αβ-hopane
412 ->191
2α(Me)-αβ-hopane2α(Me) αβ hopane
426 >205
2α-MeH Index
2 (M )/2 (M ) β 426 ->205= 2α(Me)/2α(Me)+αβ
1:00:00 1:04:00 Time
45
2α-Methylhopane index 2.72-2.56 Ga samples from
the Hamersleyy Province
Courtesy of National Academy of Sciences, U. S. A. Used with permission.
Source: Eigenbrode et al (2008) National Academy of Sciences, USA. Eigenbrode et al, PNAS
Copyright (c) 2008, National Academy of Sciences, U.S.A. 2008 46
Meishan Drilling Project 2004 c.120 samples Late Permian-Mid Triassic for bulk geochemistry: 87Sr/86Sr, TOC, 13δ carb, 13δorg, 15δorg and detailed lipid biomarkers
Meishan-1 core
drilled near GSSP
Jan 2004Jan 2004
This image has been removed This image has been removed due to copyright restrictions. due to copyright restrictions.
Multiple radiometric ages constrain pace; Ash in bed 25 = 251.4 s 0.3 Ma, Bowring et al, 1998; Revised 252.6 s 0.2 Ma Mundil, 2004; & 252.25 s 0.06 Crowley, Bowring 2008
47
δ15N of Meishan Organic Matter
ve +ve
-90
-85 -4 -2 0 2 4
-ve +ve
-95
90
35-1 35-2
36-3
37-2
-100
dept
h/m
34-12
-105
26-2
34-3 34-1
b24
30-1
-110 22-3
23-4
b24
-115
δ15N kerogen
z P itiPositive l (+3 t +2) i l tvalues (+3 to +2) in late
Permian Beds 6 -24
z Trend to zero or neggative values of δ15N in latest Permian reflects depletion of nitrate/nitrite pool driven by euxinic conditions
z Large swings in E. Triassic may reflect waxing and waning of euxinia
z Predominantly cyanobacterial primary N fixation
Peaks in 2Peaks in 2-MeHI >15%MeHI >15%
Peaks of aryl isoprenoids
48
EARTHRISE Certified Pesticide
FREE
SPIRULINA
Blue-Green Algae Rich in Beta Carotene
Essential Vitamins & Phytonutrients Biologically Grown in the USA
100 TABLETS Net Wt. 50 grams
49
Meishan-1 Isotope Geochemistry
This image has been removed due to copyright restrictions.
50
Meishan-1 Euxinia/Redox
This image has been removed due to copyright restrictions.
51
Meishan-1 Microbial Physiologies
This image has been removed due to copyright restrictions.
52
Hopanoids
The effect of thermal stress on source-rock quality as measured
by hopane stereochemistry
WOLFGANG K. SEIFERT and J.MICHAEL MOLDOWAN
Chevron Oil Field Research Company, P.O. Box 1627, Richmond,
California 94802, U.S.A.
This image has been removed due to copyright restrictions.
In: A.G. Douglas and J.R. Maxwell, Editors, Advances in Organic Geochemistry, Pergamon Press, Oxford (1980), pp. 229–237
53
Meishan-1 Maturity Parameters
This image has been removed due to copyright restrictions.
54
Sample with high moretanes, 2-methylmoretanes and 3-methylmoretanes
ms-1-core 36-3 alis 08 June 28 07 2: MRM 25 Channels EI+
69.45 69.85 454.452 > 205.194 100
70.87 72.86 72.06
72.96 73.44 2.71e5 65.64 66.52% 67.78 68.90 74.86
0
74.65 67.09
08 June 28 07 2: MRM 25 Channels EI+ 67.63 440.437 > 205.194 100
66.52 65.64
67.90 68.78 70.83 68.93
69.64
9.96e5 72.15 %
74.01 72.73 73.59 0
08 June 28 07 2: MRM 25 Channels EI+ 68.90 426.421 > 205.194 100 67.78
65.54 70.03 71.08 66.42 69.64
6.65e6
%
0 08 June 28 07 2: MRM 25 Channels EI+
67.78 426.421 > 191.179 100
65.64
68.05 68.90
3.02e7
%
0 08 June 28 07 2: MRM 25 Channels EI+
65.64 412.406 > 191.179 100 1.01e8 66.52 %
0 Time 66.00 68.00 70.00 72.00 74.00
55
Sample with low moretanes, 2-methylmoretanes and 3-methylmoretanes
ms05-2b sats 0.7mg 08 June 28 04 2: MRM 25 Channels EI+
69.87
72.42 71.39 70.93
72.96 454.452 > 205.194 100 5.07e5 69.47 73.44
% 65.64 66.54 67.84 68.40 74.70
0 08 June 28 04 2: MRM 25 Channels EI+
70.83 440.437 > 205.194 100 67.63 71.14 8.78e5 67.90
%
67.00 66.52 72.10
72.73 68.53 69.45 70.35 73.44 0
08 June 28 04 2: MRM 25 Channels EI+ 67.78 426.421 > 205.194 100
68.05
68.93
1.52e6 65.54
% 69.62 65.91 66.86 70.83
0
08 June 28 04 2: MRM 25 Channels EI+
67.78 426.421 > 191.179 100 68.05 1.05e7
%
0 66.37 68.67 69.62
08 June 28 04 2: MRM 25 Channels EI+ 65.64 412.406 > 191.179 100 2.22e7
% 66.04
67.78 0 Time
66.00 68.00 70.00 72.00 74.00
56
0
100
%
4.03e6
65.64 66.52 68.90 67.78
69.85
70.87 72.96 71.20
73.46 74.68
Sample with high moretanes and 2-methylmoretanes
ms-1-core 35-1 alis 08 June 28 09 2: MRM 25 Channels EI+
69.45 454.452 > 205.194
08 June 28 09 2: MRM 25 Channels EI+ 67.65 440.437 > 205.194 100
66.54
67.90 68.76
70.83 69.64 71.1472.15
1.88e7
%
0
08 June 28 09 2: MRM 25 Channels EI+
67.78
66.44 69.62 70.03 71.08
65.56 68.93 426.421 > 205.194 100 2.92e7
%
0 08 June 28 09 2: MRM 25 Channels EI+
67.78 426.421 > 191.179 100
66.42 65.54
68.05 68.90
1.32e8
%
0 08 June 28 09 2: MRM 25 Channels EI+
65.64 412.406 > 191.179 100 4.20e8 66.52 %
0 Time 66.00 68.00 70.00 72.00 74.00
57
Information from Molecular Fossils
A marker for aerobic methanotrophy
2
3
17 21
29
R
3-methylhopane
Collister et al., Organic Geochemistry, 1992
Courtesy Elsevier, Inc., http://www.sciencUsed with permission.
edirect.com.
Summons et al., GCA, 2004
58
http://www.sciencedirect.com
Life’s History on Earth Cloud, Holland, Walker Paradigm Prokaryote
World
1
Multi-cell Life
0.1 Humans
(atm
) 0.01 First Eukaryotes (algae)
First InvertebratesGOE
P O
2 (
0.001
0.0001 Oldest ‘compelling’ fossil, stromatolite and C-isotopic evidence for life
0.00001 4.5 4 3.5 3 2.5 2 1.5 1 0.5 0
Time before Present (Ga) 59
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12.158 Molecular Biogeochemistry Fall 2011
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