source, age, maturity and alteration characteristics of oil reservoirs using apgc ms/ms
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Source, age, maturity and alteration
characteristics of oil reservoirs using
APGC/MS/MS analysis of oil biomarkers
Douglas M. Stevens1, Chang S. Hsu2, Keith Hall3, Gareth Harriman4,
Peter Hancock1
Waters Corporation,
Florida State University, Dept of Chemical & Biomedical Engineering,
Hall Analytical Laboratories Ltd,
GHGeochem Ltd
2
Overview
Petroleum biomarkers background
Analytical approach
– APGC MS and MS/MS data examples
Biomarkers of source
– C30 steranes
Biomarkers of age
– C26 nordiacholestanes
Biomarkers of maturity
– Methylphenanthrenes
Conclusion
3
Petroleum biomarker analysis provides valuable geological information and enables oil quality to be assessed during exploration
Steranes and hopanes are among the common biomarkers analyzed by GC/MS/MS
Vacuum source techniques like EI,
CI, and FI have been widely applied
in MS analysis of petroleum
samples
More recently ESI, APCI and APPI
have been applied to the analysis of
heavy petroleum fractions
Petroleum Biomarkers
4
• Retain basic carbon skeleton of biological origins • Useful molecules for exploration/production in upstream • Provide geochemical information on source, age, maturity and alteration • Used for oil-oil and oil-source rock correlation • Used for environmental forensics for source identification
Analytical Advances for Hydrocarbon Research, Ch9, Biomarker Analysis for Petroleum Exploration, C. S. Hsu (Ed.). Kluwer Academic/Plenum Publishers: New York, 2003
Characteristics of Petroleum Biomarkers
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Analytical Advances for Hydrocarbon Research, Ch9, Biomarker Analysis for Petroleum Exploration, C. S. Hsu (Ed) Kluwer Academic/Plenum Publishers: NY, 2003
Typical Biomarkers and Their Origin
Ni, V
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Instrument Photo Source Diagram
Combined APGC and LC/MS/MS System
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APGC Charge Exchange Spectrum Compared with EI Spectrum
Journal of Applied Sciences in Environmental Sanitation, Vol 7, Number 2: 75-86, June, 2012
M.+
M.+
412
412
APGC spectrum
EI spectrum
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APGC MS and MS/MS Spectra
APGC MS/MS product ion spectrum
APGC MS spectrum
9
SR-1: Concurrent MRM and Full Scan Data Acquisition
Concurrently acquired full scan data
Biomarker MRM trace
RADAR 3.35e7
2.23e6
SFE extract
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Biomarkers Source
Oil-Oil and oil-source correlation studies are an important
part of unravelling the sourcing of oils and their geohistory
(maturation, migration) within a petroliferous basin
Quadrupole EI SIR GC-MS is traditional method of detection,
however, co-elution of hydrocarbon species means MS/MS is
often required to answer specific geochemical questions
C30 steranes ubiquitous in marine sourced oils are absent
from non-marine oils. Their low abundance and the fact that
they co-elute with 4-methyl steranes mean that they can only
be detected and accurately quantified with MS/MS
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EI GC/MS/MS of a Marine Oil
C30 Steranes
C29 Steranes
C28 Steranes
C27 Steranes
Marine *
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EI GC/MS/MS of a Terrigenous Oil
C30 Steranes
C29 Steranes
C28 Steranes
C27 Steranes
Terrigenous
No biomarkers
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APGC MS/MS Marine Source Whole Oil
C30 Steranes Marine
*
C26 Steranes
C27 Steranes
C28 Steranes
C29 Steranes
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APGC MS/MS Lacustrine Source Rock
No C30 Steranes Lacustrine
C27 Steranes
C28 Steranes
C29 Steranes
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C28 steranes evolve and diversify through geological time.
Consequently, C28/C29 sterane ratio can be used to define the
age of an oil or source rock extract
Similarly, C26 nordiacholestanes present in oils along with co-
eluting C27 diasteranes are related to the appearance and
proliferation of diatoms and can be used to age date oils
EI SIR GC-MS C28/C29 sterane ratios can result in inaccuracies
whereas MS/MS provides accurate quantitation
C26 steranes are almost impossible to identify in EI SIR GCMS
but are readily detected and quantified by MS/MS
Biomarkers Age
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Analytical Advances for Hydrocarbon Research, Ch9, Biomarker Analysis for Petroleum Exploration, C. S. Hsu (Ed) Kluwer Academic/Plenum Publishers: NY, 2003
C28/C29 Sterane Ratio as Age Indicator for Marine Source Rock
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APGC MS/MS Data Age Determination
1
2
3
4
NDR ratio = 0.2 (1+2/1+2+3+4) = Jurassic
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Relatively abundant C27-C29 steranes provides information on
source and maturity
Ratios of methylphenanthrenes measured in GC/MS data can
be used to gauge maturity as well
Biomarkers – Maturity Methylphenanthrene Ratios
Journal of Petroleum Science and Engineering 61 (2008) 99–107
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EI GC/MS Nigerian Crude
m/z 178 Phenanthrene
m/z 192 Methylphenanthrenes
Journal of Petroleum Science and Engineering 61 (2008) 99–107
MPI-1=1.5(2MP+3MP)/(P+1MP+9MP) MPI-2=3(2MP)/(P+1MP+9MP)
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APGC GC/MS Nigerian Crude
m/z 178 Phenanthrene
m/z 192 Methylphenanthrenes
3MP
9MP
1MP
P
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APGC MS and MS/MS Nigerian Crude
Full scan data
MRM data
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APGC MS and MS/MS Source Rock Extract
Full scan data
MRM data
3.35e7
2.23e6
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Conclusions
APGC charge exchange ionization generates the same m/z for
MS/MS analysis as used with EI GC/MS/MS but with higher
response for the molecular ion
– Facilitates comparison of historic, archival EI GC/MS/MS data from
many sources to the data generated by this new technique
Concurrent acquisition of MS and MS/MS data allows the
investigation of abundant and trace level biomarkers
SFE shows promise as an extraction technique for preparation
of rock oil biomarkers
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