University of Warwick crest Dr. Mark P. Barrow: Research in mass spectrometry

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Petroleomics

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FT-ICR mass spectrum of an oil extract

12 T solariX FTICR at the University of Warwick. Hover your cursor over the image for an magnified view.

APPI FT-ICR mass spectrum of oil sands process water

A broadband APPI FT-ICR mass spectrum of oil sands process water. Hover your cursor over the image for an magnified view.

Enlarged region of the APPI FT-ICR mass spectrum of oil sands process water

An enlarged region of the mass spectrum shown above, highlighting the ultra-high resolving power and mass accuracy associated with FT-ICR mass spectrometry. Hover your cursor over the image for an magnified view.

Plot of different naphthenic acid species in an oil extract

An example plot of the different naphthenic acid species present in a crude oil extract, shown as relative intensity versus carbon number. Hover your cursor over the image for an magnified view.

Petroleum

Petroleum-related samples, such as crude oils, are highly complex mixtures and typically contain thouands of components. Analysis of such mixtures using mass spectrometric methods has been termed "petroleomics," and can prove problematic. Any instrument employed for the task would require ultra-high resolving power and mass accuracy. The type of mass spectrometer most associated with such characteristics is the Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. For petroleum-related research at the University of Warwick, a 9.4 T Bruker BioAPEX II FT-ICR mass spectrometer and, more recently, a 12 T Bruker solariX instrument have been used.

A wide range of petroleum-related samples can be analyzed, including crude oils, crude oil extracts, and fuels, amongst others. Electrospray ionization (ESI), or a derivative such as nanospray, and atmospheric pressure photoionization (APPI) are typically used as the ionization methods of first choice, depending upon requirements. Both techniques are relatively soft ionization methods and thus minimize fragmentation. ESI is more suitable for ionic and highly polar compounds, while APPI can be used for characterizing less polar compounds which are not observed using ESI (e.g. less polar, sulfur-containing species). The ultra-high resolving power and mass accuracy (sub-ppm) associated with FT-ICR mass spectrometry afford a high degree of confidence in the mass assignments, and therefore the technique is well-suited to the analysis of complex mixtures such as petroleum-related samples.

Naphthenic acids

Naphthenic acids are one such class of compound found within crude oils and have the empirical formula: CnH2n+ZO2, where Z is a negative value and is frequently referred to as the "hydrogen deficiency." Such species can cause corrosion in refinery equipment, resulting in costs that are ultimately passed on to the consumer, and the corrosiveness of the acids is believed to be linked to their size and structure.

The total acid number (TAN) of an oil, defined as the number of milligrams of potassium hydroxide required to neutralize one gram of crude oil, has always been believed to be indicative of the naphthenic acid content, but it is increasingly being accepted that the TAN of an oil is not such a reliable guide. A new method for characterizing the naphthenic acid content of crude oils is therefore highly desirable. In addition to the potential corrosiveness, naphthenic acids are also known to be toxic to a range of aquatic organisms. Environmental regulators too, consequently, have an interest in characterization of naphthenic acids in water samples, and the oil industry has additional concerns about how to dispose of the unwanted acids. Work performed at the University of Warwick has demonstrated the naphthenic acid profiles can act as fingerprints for different oilfields.

Related references:

  1. “Throwing Light on Petroleum: Simulated Exposure of Crude Oil to Sunlight and Characterization Using Atmospheric Pressure Photoionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry,” Matthew T. Griffiths, Raffaello Da Campo, Peter B. O'Connor, and Mark P. Barrow, Anal. Chem., 2014, , 86, pp. 527-534
  2. “Application of Phase Correction to Improve the Interpretation of Crude Oil Spectra Obtained Using 7 T Fourier Transform Ion Cyclotron Resonance Mass Spectrometry,” Yunju Cho, Yulin Qi, Peter B. O'Connor, Mark P. Barrow, Sunghwan Kim, J. Am. Soc. Mass Spectrom., 2014, , 25, pp. 154-157
  3. “Chemical Fingerprinting of Oil Sands Naphthenic Acids in Environmental Samples - A Review of Analytical Methods,” John V. Headley, Kerry M. Peru, Richard A. Frank, Jonathan W. Martin, Roderick R. O. Hazewinkle, David Humphries, Narine P. Gurprasad, L. Mark Hewitt, Derek C. G. Muir, Dorothy Lindeman, Richard Strub, Rozlyn F. Young, David M. Grewer, Randy M. Whittal, Phillip M. Fedorak, D. A. Birkholz, Ralph Hindle, Rick Reisdorph, Xiaomeng Wang, Kim Kasperski, C. Hamilton, M. Woudneh, G. Wang, Barry Loescher, Andrea Farwell, D. George Dixon, Matthew Ross, Alberto Dos Santos Pereira, Emily King, Mark P. Barrow, Brian Fahlman, Jonathan Bailey, Dena W. McMartin, Christoph H. Borchers, C. H. Ryan, N. S.Toor, H. Martin Gillis, L. Zuin, G. Bickerton, M. McMaster, Ed Sverko, Dayue Shang, and Fred J. Wrona, J. Environ. Science and Health, Part A, 2013, 48, pp. 1145-1163
  4. “Throwing light on petroleum: simulated exposure of crude oil to sunlight and characterization using atmospheric pressure photoionization Fourier transform ion cyclotron resonance mass spectrometry,” Matthew T. Griffiths, Raffaello Da Campo, Peter B. O'Connor, and Mark P. Barrow, Annual Meeting of the British Mass Spectrometry Society, Eastbourne, United Kingdom, September 9th - 11th, 2013
  5. “Studying the effects of simulated solar radiation upon crude oil using Fourier transform ion cyclotron resonance mass spectrometry,” Matthew T. Griffiths, Raffaello Da Campo, Peter B. O'Connor, and Mark P. Barrow, ASMS Conference on Mass Spectrometry, Minneapolis, Minnesota, June 9th - 13th, 2013
  6. “Studying the effects of simulated solar radiation upon crude oil using high field Fourier transform ion cyclotron resonance mass spectrometry,” Mark P. Barrow, Matthew T. Griffiths, Raffaello Da Campo, and Peter B. O'Connor, Chemistry in the Oil Industry XIII: Oilfield Chemistry - New Frontiers, Manchester, United Kingdom, November 4th - 6th, 2013
  7. “Preliminary characterization of Athabasca samples using gas chromatography atmospheric pressure chemical ionization Fourier transform ion cyclotron resonance mass spectrometry,” Mark P. Barrow, Kerry M. Peru, and John V. Headley, Chemistry in the Oil Industry XIII: Oilfield Chemistry - New Frontiers, Manchester, United Kingdom, November 4th - 6th, 2013
  8. “Simulated Exposure of Crude Oil to Sunlight and Characterization Using Atmospheric Pressure Photoionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry,” Matthew T. Griffiths, Raffaello Da Campo, Peter B. O'Connor, and Mark P. Barrow, Goldschmidt 2013, Florence, Italy, August 25th - 30th, 2013
  9. “Preliminary analysis of Athabasca samples using gas chromatography atmospheric pressure chemical ionization Fourier transform ion cyclotron resonance mass spectrometry,” Mark P. Barrow, Kerry M. Peru, and John V. Headley, ASMS Conference on Mass Spectrometry, Minneapolis, Minnesota, June 9th - 13th, 2013, Abstract 644
  10. “Application of atmospheric pressure photoionization Fourier transform ion cyclotron mass spectrometry for the comparison of water from natural sources and areas of oil sands activity,” Mark P. Barrow, John V. Headley, Kerry M. Peru, Brian Fahlman, Richard Frank, and L. Mark Hewitt, 10th European Fourier Transform Mass Spectrometry Workshop, University of Warwick, Coventry, April 1st - 5th, 2012
  11. “Environmental Monitoring of Waters from Areas of Oil Sands Activity Using Fourier Transform Ion Cyclotron Resonance Mass Spectrometry,” Mark P. Barrow, Kerry M. Peru, Brian Fahlman, Richard A. Frank, L. Mark Hewitt, and John V. Headley, Warwick Mass Spectrometry 80/60 Conference, University of Warwick, December 10th - 11th, 2012
  12. “Profiling waters from natural sources and areas of oil sands activity using Fourier transform ion cyclotron resonance mass spectrometry,” Mark P. Barrow, Kerry M. Peru, Brian Fahlman, Richard A. Frank, L. Mark Hewitt, and John V. Headley, 19th International Mass Spectrometry Conference, Kyoto, Japan, September 15th - 21st, 2012, Abstract PTh-056
  13. “Comparison of Water from Natural Sources and Areas of Oil Sands Activity Using APPI FTICR Mass Spectrometry,” Mark P. Barrow, John V. Headley, Kerry M. Peru, Brian Fahlman, Richard A. Frank, and L. Mark Hewitt, 60th ASMS Conference on Mass Spectrometry, Vancouver, Canada, May 20th - 24th, 2012, Abstract TP 621
  14. “Preliminary fingerprinting of Athabasca oil sands polar organics in environmental samples using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry,” John V. Headley, Mark P. Barrow, Kerry M. Peru, Brian Fahlman, Richard A. Frank, Gregory Bickerton, Mark E. McMaster, Joanne Parrott, and L. Mark Hewitt, Rapid Commun. Mass Spectrom., 2011, 25, pp. 1899-1909
  15. “Combined Influence of Salinity and Solvent Effects on the Characterization of Naphthenic Acids from Athabasca Oil Sands Using Electrospray Ionization,” John V. Headley, Mark P. Barrow, Kerry M. Peru, and Peter J. Derrick, J. Environ. Science and Health, Part A, 2011, 46, pp. 844-854
  16. “Oil sands process water: Characterization using atmospheric pressure photoionization and electrospray ionization coupled with high field Fourier transform ion cyclotron resonance mass spectrometry,” Mark P. Barrow, Analytical Strategies for Naphthenic Acids, Saskatoon, Saskatchewan, Canada, November 24th - 25th, 2011
  17. “Characterization of oil sands process waters and natural waters from the Athabasca River Basin using high field Fourier transform ion cyclotron resonance mass spectrometry,” Mark P. Barrow, John V. Headley, Kerry M. Peru, Brian Fahlman, Richard A. Frank, Greg Bickerton, Mark McMaster, Joanne Parrott, and L. Mark Hewitt, Annual Meeting of the British Mass Spectrometry Society, Cardiff, September 11th - 14th, 2011
  18. “Comparison of oil sands process waters and natural water using Fourier transform ion cyclotron resonance mass spectrometry,” Mark P. Barrow, John V. Headley, Kerry M. Peru, Brian Fahlman, Richard A. Frank, Greg Bickerton, Mark McMaster, Joanne Parrott, and L. Mark Hewitt, Goldschmidt 2011, Prague, Czech Republic, August 14th - 19th, 2011
  19. “Petroleomics: Using high field Fourier transform ion cyclotron resonance mass spectrometry to study petroleum and the environment,” Mark P. Barrow, Royal Society of Chemistry lecture, University of Plymouth, February 2nd, 2011
  20. “Characterization of organic components present in oil sands process waters and natural waters using Fourier transform ion cyclotron resonance mass spectrometry,” Mark P. Barrow, John V. Headley, Kerry M. Peru, Brian Fahlman, Richard A. Frank, Greg Bickerton, Mark McMaster, Joanne Parrott, and L. Mark Hewitt, PetroPhase 2011, London, July 10th - 14th, 2011
  21. “Petroleomics: study of the old and the new,” Mark P. Barrow, Biofuels, 2010, 1, pp. 651-655 (Invited editorial)
  22. “Athabasca oil sands process water: characterization by atmospheric pressure photoionization and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry,” Mark P. Barrow, Matthias Witt, John V. Headley, and Kerry M. Peru, Anal. Chem., 2010, 82, pp. 3727-3735
  23. “Oil Sands Process Water: Beyond Naphthenic Acids,” Mark P. Barrow, John V. Headley, Matthias Witt, Kerry M. Peru, and Dena McMartin, 23rd Annual Tandem Mass Spectrometry Workshop, Lake Louise, Canada, December 1st - 4th, 2010
  24. “High Field Fourier Transform Ion Cyclotron Resonance Mass Spectrometry and Environmental Complex Mixtures,” Mark P. Barrow, Informal Meeting of Birmingham, Leicester, Nottingham, and Warwick Gas-Phase Research Groups, University of Warwick, September 22nd, 2010
  25. “Investigation of Athabasca Oil Sands Process Water by High Field Fourier Transform Ion Cyclotron Resonance Mass Spectrometry,” Mark P. Barrow, Matthias Witt, John V. Headley, Kerry M. Peru, and Michael L. Easterling, EnviroAnalysis 2010, Mississauga, Canada, May 15th - 13th, 2010
  26. “High Field Fourier Transform Ion Cyclotron Resonance Mass Spectrometry for the Study of Tailing Ponds Water,” Mark P. Barrow, Kerry M. Peru, John V. Headley, Annual Meeting of the British Mass Spectrometry Society, Cardiff, September 5th - 8th, 2010
  27. “Characterization of Athabasca Oil Sands Process Water by High Field Fourier Transform Ion Cyclotron Resonance Mass Spectrometry,” Mark P. Barrow, Matthias Witt, John V. Headley, and Kerry M. Peru, 9th European Fourier Transform Mass Spectrometry Workshop, Lausanne, Switzerland, April 6th - 9th, 2010
  28. “Analysis of Athabasca Oil Sands Process Water by ESI and APPI Fourier Transform Ion Cyclotron Resonance Mass Spectrometry,” Mark P. Barrow, Matthias Witt, John V. Headley, and Kerry M. Peru, PTAC Soil and Groundwater Forum, Calgary, Canada, March 15th, 2010
  29. “Analysis of Athabasca Oil Sands Process Water by ESI and APPI FT-ICR Mass Spectrometry,” Mark P. Barrow, Matthias Witt, John V. Headley, and Kerry M. Peru, Deutschen Gesellschaft für Massenspektrometrie, Halle, Germany, March 7th - 10th, 2010
  30. “Characterization of Naphthenic Acid Singly Charged Noncovalent Dimers and Their Dependence on the Accumulation Time within a Hexapole in Fourier Transform Ion Cyclotron Resonance Mass Spectrometry,” Raffaello Da Campo, Mark P. Barrow, Andrew G. Shepherd, Malcolm Salisbury, and Peter J. Derrick, Energy Fuels, 2009, 23, pp. 5544-5549
  31. “Data Visualization for the Characterization of Naphthenic Acids within Petroleum Samples,” Mark P. Barrow, John V. Headley, Kerry M. Peru, and Peter J. Derrick, Energy Fuels, 2009, 23, pp. 2592-2599
  32. “Mass Spectrometric Characterization of Naphthenic Acids in Environmental Samples: A Review,” John V. Headley, Kerry M. Peru, and Mark P. Barrow, Mass Spectrom. Rev., 2009, 28, pp. 121-134
  33. “Analysis of Athabasca Oil Sands Process Water by ESI and APPI Fourier Transform Ion Cyclotron Resonance Mass Spectrometry,” Mark P. Barrow, Matthias Witt, John V. Headley, and Kerry M. Peru, 18th International Mass Spectrometry Conference, Bremen, Germany, August 30th - September 4th, 2009
  34. “Combined Influence of Salinity and Solvent Effects on the Characterization of Naphthenic Acids from Athabasca Oil Sands Using Electrospray Ionization,” John V. Headley, Kerry M. Peru, Mark P. Barrow, and Peter J. Derrick, 18th International Mass Spectrometry Conference, Bremen, Germany, August 30th - September 4th, 2009
  35. "Challenges Arising During the Analysis of Crude Oils and Environmental Samples," Mark P. Barrow, John V. Headley, and Kerry M. Peru, European Conference on Complex Systems 2009, University of Warwick, September 21st - 25th, 2009
  36. "Characterization of Petroleum-based Complex Mixtures Using Fourier Transform Ion Cyclotron Resonance Mass Spectrometry," Mark P. Barrow, Informal Meeting of Birmingham, Leicester, Nottingham, and Warwick Gas-Phase Research Groups, University of Birmingham, September 18th, 2009
  37. “Analysis of naphthenic acids from Athabasca oil sands using Fourier transform ion cyclotron resonance mass spectrometry,” Mark P. Barrow, Kerry M. Peru, John V. Headley, and Peter J. Derrick, 30th Annual Meeting of the British Mass Spectrometry Society, University of York, September 7th - 10th, 2008
  38. “Characterization of naphthenic acids from Athabasca oil sands for environmental analysis using Fourier transform ion cyclotron resonance mass spectrometry,” Mark P. Barrow, Kerry M. Peru, John V. Headley, and Peter J. Derrick, 56th ASMS Conference on Mass Spectrometry, Denver, Colorado, June 1st - 5th, 2008
  39. “Characterization of Naphthenic Acids from Athabasca Oil Sands Using Electrospray Ionization: The Significant Influence of Solvents,” John V. Headley, Kerry M. Peru, Mark P. Barrow, and Peter J. Derrick, Anal. Chem., 2007, 79, pp. 6222-6229
  40. “Solvent Effects During Characterization of Naphthenic Acid Mixtures Using Nanospray Fourier Transform Ion Cyclotron Resonance Mass Spectrometry,” Mark P. Barrow, Kerry M. Peru, John V. Headley, and Peter J. Derrick, 55th ASMS Conference on Mass Spectrometry, Indianapolis, Indiana, June 3rd - 7th, 2007
  41. “Aggregation of Naphthenic Acids Studied by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry,” Raffaello Da Campo, Mark P. Barrow, Malcolm Salisbury, Andrew Shepherd, and Peter J. Derrick, 55th ASMS Conference on Mass Spectrometry, Indianapolis, Indiana, June 3rd - 7th, 2007
  42. "Solvent Effects in Electrospray Ionization of Naphthenic Acids From Athabasca Oil Sands," John V Headley, Kerry M. Peru, Mark P. Barrow, and Peter J. Derrick, 55th ASMS Conference on Mass Spectrometry, Indianapolis, Indiana, June 3rd - 7th, 2007
  43. “Principles of Fourier transform ion cyclotron resonance mass spectrometry and its application in structural biology,” Mark P. Barrow, William I. Burkitt, and Peter J. Derrick, Analyst, 2005, 130, pp. 18-28
  44. "Characterization of Naphthenic Acid Mixtures for Environmental Analysis using Fourier Transform Ion Cyclotron Resonance Mass Spectrometry," Mark P. Barrow, John V. Headley, Kerry M. Peru, and Peter J. Derrick, 2nd Trapped Ion Mass Spectrometry Meeting, University of Oxford, March 22nd, 2005
  45. "Fourier transform ion cyclotron resonance mass spectrometry of principal components in oilsands naphthenic acids," Mark P. Barrow, John V. Headley, Kerry M. Peru, and Peter J. Derrick, J. Chrom. A, 2004, 1058, pp. 51-59
  46. "Nanospray Ionization and Fourier Transform Ion Cyclotron Resonance Mass Spectrometry for the Characterization of Naphthenic Acids with Respect to Environmental Analysis," Mark P. Barrow, John V. Headley, Kerry M. Peru, and Peter J. Derrick, 27th Annual Meeting of the British Mass Spectrometry Society, University of Derby, September 5th - 8th, 2004
  47. "Characterization of Naphthenic Acids For Environmental Analysis Using Nanospray Ionization and Fourier Transform Ion Cyclotron Resonance Mass Spectrometry," Mark P. Barrow, John V. Headley, Kerry M. Peru, Pascal Manuelli, Bernard Escoffier, and Peter J. Derrick, 52nd ASMS Conference on Mass Spectrometry, Nashville, Tennessee, May 23rd - 27th, 2004
  48. "Investigating Corrosion through the Characterization of the Naphthenic Acid Content of Crude Oils Using Negative-Ion Nanospray Fourier Transform Ion Cyclotron Resonance Mass Spectrometry," Mark P. Barrow, Liam A. McDonnell, Xidong Feng, Jérémie Walker, Pascal Manuelli, and Peter J. Derrick, 16th International Mass Spectrometry Conference, Edinburgh International Conference Centre, August 31st - September 5th, 2003
  49. “Determination of the Nature of Naphthenic Acids Present in Crude Oils Using Nanospray Fourier Transform Ion Cyclotron Resonance Mass Spectrometry: The Continued Battle Against Corrosion,” Mark P. Barrow, Liam A. McDonnell, Xidong Feng, Jérémie Walker, and Peter J. Derrick, Anal. Chem., 2003, 75, pp. 860-866
  50. “Investigating Corrosion, Calcium Deposition, and Emulsion Formation through the Characterization of the Naphthenic Acid Content of Crude Oils Using Negative-Ion Nanospray Fourier Transform Ion Cyclotron Resonance Mass Spectrometry,” Mark P. Barrow, Liam A. McDonnell, Xidong Feng, Jérémie Walker, Peter J. Derrick, 26th Annual Meeting of the British Mass Spectrometry Society, University of Loughborough, September 8th - 11th, 2002