1

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

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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