Petroleum Biomarkers for Downstream and Environmental Applications C. S. Hsu Future Fuels Institute Florida State University 242 nd ACS National Meeting August 28 – September 1, 2011 Denver, Colorado
Petroleum Biomarkers for Downstream
and Environmental Applications
C. S. Hsu
Future Fuels InstituteFlorida State University
242nd ACS National MeetingAugust 28 – September 1, 2011
Denver, Colorado
Differences in upstream and downstream analytical focuses
• Samples are different :
• Upstream – source rocks and oils from wells (localized).
mostly in native states, molecules stay intact (with possible
“contamination” from production chemicals)
• Downstream –blended crude oils from refineries. molecules
most likely altered in upgrading process streams and products.
• Bulk analyses and molecular speciation emphasis are different.
• Upstream:
Bulk analysis – TOC, isotope ratio, vitrinite reflectance, etc.
Molecular speciation - isomer specific for critical molecules
of geological significance.
• Downstream (also exploitation geochemistry in upstream):
Bulk analysis - SimDist, total sulfur, API gravity, etc.
Molecular speciation - molecules grouped into compound
types and carbon numbers. Unknown identification in
processes and products.
• retain basic carbon skeleton of biological origins.
• useful molecules for exploration/production in upstream.
• provide information on source, age, maturity and alteration.
• used for oil-oil and oil-source rock correlation.
• rarely applied in downstream processes
• used as source identification of petroleum-related pollution
Characteristics of petroleum biomarkers
Typical biomarkers and their origins
171816
1514131211
1098
7
65
4
19 20
21 2223 24
25262728293031323334
35363738
39 40
pristane phytane cyclic biomarkers
● isoprenoid hydrocarbons
Typical biomarker distributions in crude oils
20 30 40 50 60 70 80 90
27
28
29
28
29
30
31
32
33
34
35
Ts
Tm
23
24
2526
28
2930
222120
19
20
21
Normal Steranes
Diasteranes
Homohopanes
Hopanes
Tricyclic Terpanes
m/z 191 ion chromatogram
m/z 217 ion chromatogram
R
R R
191
217
259
hopanes steranes diasteranes
R
R R
191
217
259
hopanes steranes diasteranes
Hopanes and steranes provide most geochemical information
(Characteristic ions of:
Monoaromatic steranes at 253 Da
Triaromatic steranes at 231 Da)
Steranes resolved by GC/MS/MS
C26
C27
C28
C29
C30
M+ 368
M+ 372
M+ 386
M+ 400
M+ 414
A
B
C
D E
F
G
H
Hsu, C. S. Analytical Advances for Hydrocarbon Research, Chapter 9,
Kluwer Academic/Plenum Publishers, 2003.
G. H. Isaksen, Oil & Gas J., 3/18/91; pp. 130.
Gulf of Suez, Egypt; Miocene
Kupferschiefer, North Sea; Permian
Hopane / Sterane
Umiat Mt. Alaska; MesozoicParis Basin; Toarcian
North Sea; KimmeridgianHaltenbanken, Norway; U. Jurassic
Yemen Arab Republic; U. JurassicMonterey, California; Miocene
Marine
Denver Basin; L. CretaceousHaltenbanken, Norway; L. Jurassic
Mahakam Delta; TertiaryNiger Basin
Lake Chad; Santonian & EoceneGreen River Fm; Eocene
Doseo Basin, Chad; L. Cret. South Sumatra; L. Miocene
Lake Chad; Coniacian
Colombia; Aptian-Albian
Salinity
Paralic Lacustrine/Terrigenous
1 2 4 6 8 10 20 302515 35
Use of Hopane/Sterane Ratio as Source Facies Indicator
Use of C28/C29 Sterane Ratio as Age Indicator for marine source rocks
Simplified refining processes
Red: straight-run products containing biomarkers
Blue: processed products
VPS
APS
VPS
hy
jet fuel
diesel
gas oil
VGO
resid
gas
naphtha
hydrocrackerhydrocracking
product
hydrofiner hydrofining
product
FCC FCC product
coker coker oils
Lube Unit lube oils
distillates
Fate of biomarkers in refining processes
• Most of biomarkers survive the straight run processes.
Their presence in products depends on volatility.
• Commonly used biomarkers, steranes and hopanes,
concentrated in gas oils.
• Metalloporphyrins are concentrated in resids and heavy oils.
• Catalytic cracking processes destroy or alter most of the biomarkers.
Biomarker applications in downstream
• differentiation of straight run versus processed intermediates/products
• as measurement of severity of processes
• as fingerprints to distinguish from naturally occurring pollutants
Waters GCT (GC/Time-of-Flight) with a FI Source
Blend 10-7-03
2.50 5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00 37.50 40.00Time0
100
%
T31212015 TOF MS TIC
3.00e4
Blend 10-7-03
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300m/z0
100
%
T31212015 579 (15.464) Cm (3:1398-(1398:1621+2:3)) TOF MS 3.75e5201.96
156.09
142.07134.11
120.09
106.08
92.06 98.11 112.12
132.09
148.12
170.10
160.12
184.12
182.11
176.06 196.12
203.96
206.11
210.13220.12
240.28 254.30 268.32
• GC separates components
• Time correlates to b.p. on a
nonpolar column
• FI produces only molecular ions
• Reflectron TOF allows accurate
mass measurement
Time scale Mass scale
• Configuration
• Key features
Reflectron
GC MS
GCMS
Heidrun 150N 11/20/03 5dl
20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460 480 500 520 540 560 580 600m/z0
100
%
T40217009 877 (42.882) Cm (497:1053-(1084:1349+2:492)) TOF MS 1.15e5372.382
362.395
348.379
346.364
334.363
332.348
320.348
318.332
316.317
306.332
302.301
43.056
29.041
292.317
290.301
286.270
386.398
400.414
404.444
418.460
420.474
432.477
434.491
446.493
448.508
460.509
474.527
478.557
Field Ionization yields molecular ion profile
mass
inte
nsity
fragment ions from
isoparaffins
0
1
2
3
10 15 20 25 30 35 40 45 50
Carbon Number
wt%
2 0 -2 -4 -6 -8 -10
Biomarker fingerprint shown in lubricant oil basestock
steranes
hopanes
1-ring cycloparaffins
paraffins
2-ring cycloparaffins
3-ring cycloparaffins
5-ring cycloparaffins
4-ring cycloparaffins
Environmental applications
• Biomarkers as fingerprint for contamination source identifications
• seeps from oil spills
• ship cargo leaks versus refined products
• tar ball identification
• Doping of biodegradation resistant biomarkers, such as steranes and
hopanes, can be used for measurement of efficiency of remediation
of environmental contamination.
• Diamondoids resist biodegredatation and even catalytic processes,
could be good candidates as tracers in refining and environmental
applications.
Relative extent of biodegradation for various biomarker classes
• General trend: n-
paraffins>isoparaffins>
cycloparaffins>aromatics
• Hopane can be used as
an internal marker for oil
depletion determination.
Determination of oil depletion by hopane Content
Hopane Conc. (in ppm)
Calculated Oil Depleted
Gravimetrically Measured Depletion
Crude oil 255 0% 0%
521 F Plus (a) 366, 355, 373 30 1% 30%
600 F Plus (b) 418, 440 41 1% 40%
(a) after topping at 521F
(b) after topping at 600 F
• Hopane analysis provides numerical values for the efficacy of
remediation
19
Provided by Robert Nelson and Chris Reddy of Woods Hole Oceanographic Institutition
Rtx-1, 60 m x 0.25 mm x 0.25 µm
GCxGC biomarker fingerprints
GCxGC 191 Da and 217 Daromatograms (provided by LECO)
Summary - Petroleum Biomarkers
• important class of compounds for upstream geochemical information
• little used in downstream process controls and monitoring
• widely used in environmental area as fingerprints for contamination
source identification, mainly by GC-MS.
• biodegradation resistant biomarkers - good internal standards for oil
spill damage and remediation assessment.
Contact information:
CSH – [email protected]
FFI – research.fsu.edu/ffi