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. “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
  2. “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
  3. “Petroleomics: study of the old and the new,” Mark P. Barrow, Biofuels, 2010, 1, pp. 651-655 (Invited editorial)
  4. “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
  5. “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
  6. “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
  7. “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
  8. “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
  9. “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
  10. “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
  11. “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
  12. “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
  13. "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
  14. “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
  15. "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
  16. "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
  17. "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
  18. "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