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

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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.

oilsands mining

oilsands product

Picture courtesy of Syncrude Canada Ltd..

wildlife

Picture courtesy of Syncrude Canada Ltd..

Athabasca oil sands

The Athabasca oil sands in Canada and represent a less conventional source of petroleum and are estimated to be able to provide 174 billion barrels of bitumen using current technology. These oil sands are a mixture of clay, water, sand, and bitumen, where the bitumen is extracted from the deposits and then "upgraded" to synthetic oil. During the extraction process, large quantities of water are involved: approximately three barrels of water are required to produce one barrel of oil from the oil sands. The water, known as oil sands process water (OSPW), can be recycled and is stored in large "tailings ponds."

Petroleum is a complex mixture, typically composed of thousands of components of differing size, structure, and heteroatom content. There is a need to study oil sands process water to determine which petroleum-related components may be entering the system and thus potentially enter the wider environment. Research has often been particularly focused upon the naphthenic acids from the oil sands.

Naphthenic acids

Naphthenic acids are carboxylic acids which are typically considered to possess one or more saturated ring structures, and these compounds represent an interest to different groups. Naphthenic acids have the empirical formula: CnH2n+ZO2, where Z is a negative, even value and is frequently referred to as the "hydrogen deficiency." The oil industry is concerned with the corrosive effects of such acids within crude oils, as the corrosion results in considerable costs which are ultimately passed on to the consumer. Environmental organizations are interested in naphthenic acids due to the presence in water supplies, and such acids represent a particular hazard to fish. Naphthenic acids are relatively poorly studied, primarily because of their complex nature and need for rugged methods for their determination in oilfields, soils, water, and oilsands tailings wastewater. As a group, they co-occur with a diverse range of petroleum hydrocarbons present in oil sands deposits.

FT-ICR mass spectrometry

A collaboration with Environment Canada has involved the study of a range of samples, originating from differing sources relating to mining of oilsands. A 9.4 T Bruker BioAPEX II FT-ICR mass spectrometer and, more recently, a 12 T Bruker solariX instrument have used for the study of a range of naphthenic acid samples. Ionization methods employed have included electrospray ionization (ESI), nanospray ionization, and atmospheric pressure photoionization (APPI). APPI has an advantage over ESI in being more amenable to the analysis of a broader range of compounds.

Both positive-ion and negative-ion modes have been used, and usage of negative-ion mode has been shown to lead to more selective ionization of the naphthenic acids. Once mass spectra have been obtained, the data can be processed and sorted according to hydrogen deficiency and heteroatom content, for instance, and the data can be displayed using a variety of visualization methods. This effectively creates fingerprints for different samples. The ultra-high resolving power of FT-ICR mass spectrometers affords the ability to observe species that would not be observable using mass spectrometers of lower performance. Furthermore, the inherently high mass accuracy of FT-ICR mass spectrometers also affords high levels of confidence in the assignments of elemental compositions. The combination of these advantages makes FT-ICR mass spectrometry uniquely suitable for the analysis of complex mixtures.

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. “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
  3. “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
  4. “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
  5. “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
  6. “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
  7. “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
  8. “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
  9. “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
  10. “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
  11. “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
  12. “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
  13. “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
  14. “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
  15. “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
  16. “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
  17. “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
  18. “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
  19. “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
  20. “Petroleomics: study of the old and the new,” Mark P. Barrow, Biofuels, 2010, 1, pp. 651-655 (Invited editorial)
  21. “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
  22. “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
  23. “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
  24. “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
  25. “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
  26. “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
  27. “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
  28. “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
  29. “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
  30. “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
  31. “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
  32. “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
  33. “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
  34. "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
  35. "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
  36. “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
  37. “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
  38. “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
  39. “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
  40. “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
  41. "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
  42. “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
  43. "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
  44. "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
  45. "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
  46. "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