GAS CHROMATOGRAPHY

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

GC SATURATES AROMATICS NSO

Biomarker
MOLECULAR THIN LAYER
distribution SIEVING CHROMATOGRAPHY

BRANCHED & DI & TRI

CYCLIC NUCLEAR
FRACTIONS FRACTIONS

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

Phytane b. Crude oil

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)

Compound Biological origin Environment Authors

nC15, C17, C19 Algae Lacustrine, Tissot and Welte
marine (1984)

nC27, C29, C31 Higher plants As above

Terrestrial
Pristane/Phytane Phototrophs. Fu et al. (1986,
(low) Archaebacteria Reducing to 1990)
anoxic, high
Botryococcane Green algae salinity Moldowan and
(Botryococcus Seifert (1980)
braunii) Lacustrine/bracki
sh
Cooper (1990)
(Tissot and Welte, 1984)
Response_

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:

1. The occurrence of bbhopanes

2. Ratio: C31 22S/22R ~ 150% or 22S/(22S+22R) ~

60%

3. Ratio: moretane/hopane for C30 ~ 0.1 or 10%

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)

INJECTION PORT COLUMN SOURCE TIME

(SEPARATION)
RECORDER

DETECTOR
QUADRUPOLE
ANALYSER (ION
SELECTION)

ION PRODUCER

Schematic diagram of a combination between gas chromatography

and mass spectrometry (GC-MS) (modified from Waples, 1985).
Steranes:

1. aa(H),17a(H)-sterane or
normal steranes
2. ab(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)

 High diasteranes/steranes ratios are typical of

petroleum derived from source rocks
containing abundant clays.
 High diasteranes/steranes ratios in some
petroleums appear to result from:
 High thermal maturity
 Heavy biodegradation
High diasteranes
 m/z 217 Steranes
Low diasteranes

C27 C28

C29

20R 20R
20S bb
20S
aa
 Biological configuration in sediments

Catalyst
Geological configuration in sediments
immature

mature
The use of steranes:

1. Maturity: C29 20S/20R ~ 1.1 or

20S/(20S+20R) ~ 0.55 (50%)

2. Maturity: bb/aa ~ 3 (300%) or

bb/(bb+aa) ~ 0.75 (75%)

3. Depositional environment: C27, C28, and

C29