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05 06 07 Biomarker
05 06 07 Biomarker
BIOMARKER - ALKANES
LECO TOC
ROCKS
ROCK-EVAL * Maturity
* Richness
* Type of OM
EXTRACTION OPTIC
(DICHLOROMETHANE) - VR
- TAI * Maturity
- SCI
- Etc.
OIL BITUMEN
REMAIN
GAS COLUMN
Biomarker
CHROMATOGRAPHY PY-GC
distribution
Biomarker
MOLECULAR THIN LAYER
distribution SIEVING CHROMATOGRAPHY
GC / GC-MS
Biomarker distribution
Schematic diagram of gas chromatography (GC)
ISOPRENOIDS
C15
Farnesane
C16-2,6,10-Tri-
methyltridecane
(TMTD)
C18
Norpristane
C19
Pristane
C20
Phytane
a. Bitumen
Pristane
Retention time
25
30
Ph
20
Pr
15
Acyclic biomarkers as indicators of biological input or depositional
environment (assumes high concentrations of component)
(Peters and Moldowan, 1993)
Signal: ATIYYAU2.D\FID1A.CH
14000
13000
12000
11000
10000
9000
nC13
nC27
nC28
nC14
nC15
8000
nC12
nC25
nC26
nC29
Pr
nC24
nC16
nC23
nC22
nC11
nC17
nC21
nC19
nC18
7000
nC20
nC30
nC31
nC10
6000
nC32
nC9
5000
nC33
nC34
nC8
nC35
4000
nC36
nC37
nC7
3000
Ph
2000
2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00
Time
n-Alkane
Peak Label Compound Name Peak Ht Norm % Isoprenoids
n C6 Normal Alkane C6 - -
n C7 Normal Alkane C7 715 0.71
n C8 Normal Alkane C8 1370 1.35
n C9 Normal Alkane C9 2244 2.22
n C10 Normal Alkane C10 3156 3.12
n C11 Normal Alkane C11 4201 4.15
n C12 Normal Alkane C12 4740 4.68
n C13 Normal Alkane C13 5358 5.29
n C14 Normal Alkane C14 4884 4.82
n C15 Normal Alkane C15 4934 4.87
n C16 Normal Alkane C16 4295 4.24 Pristane: 5313
n C17 Normal Alkane C17 4181 4.13 Phytane: 688
n C18 Normal Alkane C18 3893 3.84 Pristane/Phytane: 7.72
n C19 Normal Alkane C19 3874 3.83 Pristane/nC17: 1.24
n C20 Normal Alkane C20 3805 3.76 Phytane/nC18: 0.16
n C21 Normal Alkane C21 4010 3.96
n C22 Normal Alkane C22 4188 4.14 n-Alkanes:
n C23 Normal Alkane C23 4203 4.15 A. Total C25-C33 Odd: 18.01
n C24 Normal Alkane C24 4429 4.37 B. Total C24-C32 Even: 20.16
n C25 Normal Alkane C25 4487 4.43 C. Total C26-C34 Even: 17.31
n C26 Normal Alkane C26 4451 4.40 CPI* : 0.97
n C27 Normal Alkane C27 4977 4.91
n C28 Normal Alkane C28 4707 4.65 D. Total C23-C27 Odd: 12.90
n C29 Normal Alkane C29 4132 4.08 E. Total C25-C29 Odd: 13.42
n C30 Normal Alkane C30 3000 2.96 F. Total C24-C28 Even: 13.50
n C31 Normal Alkane C31 2614 2.58 CPI2* : 0.98
n C32 Normal Alkane C32 1652 1.63
n C33 Normal Alkane C33 1324 1.31
n C34 Normal Alkane C34 592 0.58
n C35 Normal Alkane C35 428 0.42
n C36 Normal Alkane C36 253 0.25
n C37 Normal Alkane C37 171 0.17
101268
* CPI= 0.5*((A/B) + (A/C)), after Bray and Evans, 1961
CPI2= (D+E)/;(2*F), after Marzi et al, 1993
Pristane/nC17 vs
Phytane/nC18
East Jawa Oil Samples – Satyana, 2003
GAS CHROMATOGRAPHY
BIOMARKER - TRITERPANES
Hopanoids:
1. 17b(H),21b(H)-hopanes or bb-hopanes
2. 17b(H),21a(H)-hopanes or moretanes
3. 17a(H),21b(H)-hopanes
Non-hopanes:
1. Oleananes
2. Gammacerane
OL: oleananes
No. Name
1 C27-18a(H)-22,29,30-trisnorneohopane (Ts)
2 C27-17a(H)-22,29,30-trisnorhopane (Tm)
3 C29-17a(H), 21b(H)-30-norhopane
4 C29-17b(H), 21a(H)-30-normoretane
5 C30-17a(H), 21b(H)-hopane
6 C30-17b(H), 21a(H)-moretane
7 C31(22S+22R)-17a(H)-29-homohopane
8 C30 gammacerane
9 C32(22S+22R)-17a(H)-29,30-bishomohopane
10 C33(22S+22R)-17a(H)-29,30,31-trishomohopane
11 C34(22S+22R)-17a(H)-29,30,31,32-tetrakishomohopane
12 C35(22S+22R)-17a(H)-29,30,31,32,33-pentakishomohopane
OZ
Marine shelf
17a(H)-hopane (C30)
17a(H)-homohopanes
Gammacerane
Greece
Carbonate
anoxic
Maturity based on hopanoids:
4. Ratio: Ts/Tm
Ts: 18a(H),21b(H)-22,29,30-trisnorneohopane
Tm: 17a(H),21b(H)-22,29,30-trisnorhopane
5. Ratio: oleananes
bb Steranes
Adapted from Mackenzie, 1984
Biomarker maturity (%)
20S Steranes
Moretanes
22S Hopanes
bb Hopanes
GAS CHROMATOGRAPHY
BIOMARKER - STERANES
MASS SPECTROMETRY
GAS CHROMATOGRAPHY (MS)
(GC)
DETECTOR
QUADRUPOLE
ANALYSER (ION
SELECTION)
ION PRODUCER
1. aa(H),17a(H)-sterane or
normal steranes
2. ab(H),17b(H)-sterane or
isosteranes
T im e -->
5 2 .0 0 5 4 .0 0 5 6 .0 0 5 8 .0 0 6 0 .0 0 6 2 .0 0 6 4 .0 0
I o n 2 1 7 . 1 0 (2 1 6 . 8 0 t o 2 1 7 . 8 0 ): S A T -K W 1 1 . D
Abundance
5 Sediment sample
5000
KW-11
4500 15
E,2,3
4000
A 1
3500
11
3000
B
2500 F 10 12,13
2000
4
14
7,8
1500 C
D
9
6
1000
500
0
T im e -->
5 4 .0 0 5 6 .0 0 5 8 .0 0 6 0 .0 0 6 2 .0 0 6 4 .0 0
Peak No. Carbon No. Identification
A 27 13b(H),17a(H)-Diacholestane (20S)
B 27 13b(H),17a(H)-Diacholestane (20R)
C 28 24-Methyl-13b(H),17a(H)-Diacholestane (20S)
D 28 24-Methyl-13b(H),17a(H)-Diacholestane (20R)
E 29 24-Ethyl-13b(H),17a(H)-Diacholestane (20S)**
¹F 29 24-Ethyl-13b(H),17a(H)-Diacholestane (20R)
a 27 13a(H),17b(H)-Diacholestane (20S)
b 27 13a(H),17b(H)-Diacholestane (20R)
c 28 24-Methyl-13a(H),17b(H)-Diacholestane (20S)
d 28 24-Methyl-13a(H),17b(H)-Diacholestane (20R)
e 29 24-Ethyl-13a(H),17b(H)-Diacholestane (20S)
f 29 24-Ethyl-13a(H),17b(H)-Diacholestane (20R)
1 27 5a(H),14a(H),17a(H)-Cholestane (20S)
¹2 27 5b(H),14a(H),17a(H)-Cholestane (20R)
¹3 27 5a(H),14b(H),17b(H)-Cholestane (20R)
4 27 5a(H),14b(H),17b(H)-Cholestane (20S)
5 27 5a(H),14a(H),17a(H)-Cholestane (20R)**
6 28 24-Methyl-5a(H),14a(H),17a(H)-Cholestane (20S)**
²7 28 24-Methyl-5b(H),14a(H),17a(H)-Cholestane (20R)**
²8 28 24-Methyl-5a(H),14b(H),17b(H)-Cholestane (20R)**
9 28 24-Methyl-5a(H),14b(H),17b(H)-Cholestane (20S)
10 28 24-Methyl-5a(H),14a(H),17a(H)-Cholestane (20R)
11 29 24-Ethyl-5a(H),14a(H),17a(H)-Cholestane (20S)
12 29 24-Ethyl-5a(H),14b (H),17b (H)-Cholestane (20R)
13 29 24-Ethyl-5b (H),14b(H),17b(H)-Cholestane (20S)
14 29 24-Ethyl-5a(H),14b(H),17b(H)-Cholestane (20S)
15 29 24-Ethyl-5a(H),14a(H),17a(H)-Cholestane (20R)
m/z 217 Steranes
C27 C28
C29
20R 20R
20S bb
20S
aa
(Huang dan Meinschein, 1979)
DIASTERANES (Peters and Moldowan, 1993)
Diasteranes/steranes ratios are commonly used
to distinguish petroleum from carbonate versus
clastic source rocks (e.g. Mello et al., 1988).
Low diasteranes/steranes ratios (m/z 217) in
oils indicate anoxic, clay-poor, carbonate
source rock. During diagenesis of these
carbonate sediments, bicarbonate and
ammonium ions are provided by bacterial
activity resulting in increased water alkalinity.
Under these conditions of low Eh and high pH,
calcite tends to precipitate and organic matter
preservation is improved.
DIASTERANES (Peters and Moldowan, 1993)
C27 C28
C29
20R 20R
20S bb
20S
aa
Biological configuration in sediments
Catalyst
Geological configuration in sediments
immature
mature
The use of steranes: