Source, age, maturity and alteration characteristics of oil reservoirs using APGC MS/MS
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APGC is a soft ionization technique which produces lower levels of fragmentation compared to traditional EI. Working in dry conditions, APGC typically produces spectra with strong radical cation molecular ions that facilitates the direct comparison of historic, archival EI data from many different sources. The abundant nature of these ions makes it possible to generate specific and sensitive MRM transitions for petroleum biomarkers which provide information on the biological source of the oil, the environment in which the parent organic matter was deposited, and the thermal history of the buried organic matter. Knowledge of these properties is especially useful in upstream applications and is ultimately linked to the economic productivity from a particular geological location. The universal ionization source offered on all Waters instrumentation facilitates the quick and simple coupling of APGC, UPLC or UPC2 on a single MS platform. Coupled with Xevo TQ-S, APGC enables low-level quantification of petroleum biomarkers that have proved challenging to analyze using GC-MS systems, allowing unambiguous confirmation of the deposition environment from which the oil originates.
Source, age, maturity and alteration characteristics of oil reservoirs using APGC MS/MS
- 1. 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. 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. 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. 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
- 5. 5 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
- 6. 6 Instrument Photo Source Diagram Combined APGC and LC/MS/MS System
- 7. 7 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
- 8. 8 APGC MS and MS/MS Spectra APGC MS/MS product ion spectrum APGC MS spectrum
- 9. 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
- 10. 10 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
- 11. 11 EI GC/MS/MS of a Marine Oil C30 Steranes C29 Steranes C28 Steranes C27 Steranes Marine *
- 12. 12 EI GC/MS/MS of a Terrigenous Oil C30 Steranes C29 Steranes C28 Steranes C27 Steranes Terrigenous No biomarkers
- 13. 13 APGC MS/MS Marine Source Whole Oil C30 Steranes Marine * C26 Steranes C27 Steranes C28 Steranes C29 Steranes
- 14. 14 APGC MS/MS Lacustrine Source Rock No C30 Steranes Lacustrine C27 Steranes C28 Steranes C29 Steranes
- 15. 15 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
- 16. 16 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
- 17. 17 APGC MS/MS Data Age Determination 1 2 3 4 NDR ratio = 0.2 (1+2/1+2+3+4) = Jurassic
- 18. 18 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) 99107
- 19. 19 EI GC/MS Nigerian Crude m/z 178 Phenanthrene m/z 192 Methylphenanthrenes Journal of Petroleum Science and Engineering 61 (2008) 99107 MPI-1=1.5(2MP+3MP)/(P+1MP+9MP) MPI-2=3(2MP)/(P+1MP+9MP)
- 20. 20 APGC GC/MS Nigerian Crude m/z 178 Phenanthrene m/z 192 Methylphenanthrenes 3MP 9MP 1MP P
- 21. 21 APGC MS and MS/MS Nigerian Crude Full scan data MRM data
- 22. 22 APGC MS and MS/MS Source Rock Extract Full scan data MRM data 3.35e7 2.23e6
- 23. 23 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