Project highlights

  • State-of-the-art mass spectrometry instrumentation (amongst world-leading)
  • International environmental research
  • Supervisory team consists of world leaders in petroleum environmental chemistry, microbial profiling, and complex mixture analysis

Overview

The oiling of coastal waters can produce long term contamination to receiving ecologic systems through the dissolution of the well-known polycyclic aromatic hydrocarbons (PAHs) and also the degraded petroleum products produced from weathering ​(NASEM, 2022)​. These weathered crude oil compounds, such as those oxidized by microbial or photodegradation, have been shown to induce a syndrome of toxic effects characteristic of baseline toxicity (narcosis), similar to PAHs. Furthermore, oxidation can increase the solubility of petroleum compounds, increasing their bioavailability within aquatic ecosystems ​(Lara-Jacobo et al., 2021)​. This fraction of degraded crude oil, however, is not well defined and limited information exists on the profile of potential chemical species that may be responsible for toxicity. As such, the impacts of oiled costal environments to fish and fish habitat would be underestimated following accidental spill event, particularly when remediation personnel opt for natural attenuation.  

Crude oils spilled into aquatic environments will undergo oxidative transformation processes as a result of natural forms of microbial degradation and photodegradation. Such oxidative processes have been demonstrated to increase the water solubility and subsequent bioavailability of these petroleum compounds within the water column ​(Barron, 2017; Bekins et al., 2020)​. These oxidized petroleum products have also been demonstrated to induce acute and sublethal toxicity to receiving aquatic organisms, with their characterization and potential impacts in aquatic environments having been identified as a significant research priority ​(Aeppli et al., 2018; Lee et al., 2015; Ward et al., 2018)​. Furthermore, the majority of standardized analytical techniques used to characterize the risk of petroleum contamination to aquatic systems, such as total petroleum hydrocarbon or aromatic hydrocarbon analyses, cannot detect the more polar and water-soluble fractions that contain these oxidized petroleum toxicants ​(Mohler et al., 2020; Zito et al., 2019)​.  

As UV light can penetrate to the shallow depths of coastal environments, freshly spilled crude and sunken weathered oils all provide ample opportunity for the production of the more bioavailable oxidized petroleum toxicants within the water column. Furthermore, recent studies have demonstrated that certain oil types, such as diluted bitumen from Western Canada, naturally contain higher proportions of the oxidized compounds which induce significant acute and sublethal toxicity to aquatic organisms in freshwater ​(Hepditch et al., 2024a, 2024b)​. Currently, it is not known if such oxidized compounds within diluted bitumen would present a similar risk to coastal dwelling organisms nor has there been many studies to investigate the potential production of oxidized compounds resultant of microbial and photooxidative processes in saltwater.  

The specific objectives of this work are: 

  1. Conduct controlled photooxidative weathering experiments upon diluted bitumen spilled into saltwater to imitate the production of photo-oxidized petroleum compounds following accidental spill events. 
  2. Characterize the oxidized petroleum fraction of photo-oxidized diluted bitumen using High Resolution FTICR MS. 
  3. Conduct acute and chronic toxicity assays using the Eastern oyster (Crassostrea virginica) as a representative indicator species of the ecologic health in Canadian coastal environments to correlate the toxicity of photo-oxidized petroleum constituents with the Orbitrap mass spectrometry analyses. 

Benefits: 

  • The results and conclusions from this study will provide the most in-depth characterization of profile of photo-oxidized petroleum compounds produced following the spill of diluted bitumen within coastal waters of Canada. 
  • Results will allow more accurate comprehension of the transport, behaviour and effects of photo-oxidized products of diluted bitumen following accidental oil spills in coastal environments, information pertinent for modeling the impacts of such accidental spills. 

A photograph of a FTICR mass spectrometer, with accompanying graphs of data.

Figure 1: FTICR mass spectrometer, used to characterize complex samples. The data can be analyzed and visualized, producing a detailed molecular fingerprint for individual samples. 

Host

University of Warwick

Theme

  • Climate and Environmental Sustainability
  • Organisms and Ecosystems

Supervisors

Project investigator

Co-investigators

How to apply

Methodology

Dr. Headley and Prof. Langlois will provide samples from Canada and expertise on petroleum environmental chemistry and toxicity, and Dr. Barrow and his research group will provide expertise for the 12 T and 15 T FTICR mass spectrometers and data analysis.  Ultrahigh resolution mass spectrometry will offer new information for a range of environmental samples, where lower resolution techniques provide less detailed profiles and key details can be lost.  Sample collection in the environment, sample extraction/preparation methods in the laboratory, ionization methods, and fragmentation methods will be explored to develop a fuller picture of the composition of complex samples.  State-of-the-art data analysis methods, originally arising from research into petroleum analysis, will be used to analyze the visualize the data, where samples can then be compared.  Data processing methods will also be explored to optimize the sample comparisons. Small mass difference of oxy-petroleum products such as naphthenic acid mixtures is 3.4 mDa, resulting from the complex mixture rich in Ox and SOx isobars. Only the inherent ultrahigh resolution and mass accuracy of FTICR and Orbitrap mass spectrometers can provide unequivocal molecular formula assignments.  

Training and skills

DRs will be awarded CENTA Training Credits (CTCs) for participation in CENTA-provided and ‘free choice’ external training. One CTC can be earned per 3 hours training, and DRs must accrue 100 CTCs across the three and a half years of their PhD.  

The student will gain training and expertise in the field of environmental analysis, including sample collection and preparation.  The student will spend 3 months  in-house in Saskatoon, Canada, with the research team of Dr Headley. This international exposure will provide hands-on training in petroleum environmental chemistry.  At the University of Warwick, the student will gain expertise from one of the world’s leading FTICR laboratories, learning FTICR mass spectrometry and including use of different ionization, fragmentation, and data analysis techniques. 

Partners and collaboration

Dr. Barrow has approximately 23 years of experience of working with FTICR mass spectrometry, petroleum-related samples, environmental samples, and data analysis and visualization of complex mixtures, collaborating with industry and with environmental organizations, as well as more than 100 publications.  Dr. Headley has approximately 40 years of research experience and is amongst the world’s leading experts on the oil sands industry, with more than 26 years of working at Environment and Climate Change Canada.   Dr. Headley has more than 150 publications in the scientific literature and works closely with the Ministry of the Environment and Climate Change, Government of Canada.  Professor Langlois is a senior researcher at the Institut national de la recherche scientifique (INRS), one of the 10 Université du Québec and the only one dedicated exclusively to graduate level research and training.  

Further details

For further information, please contact us directly: 

The Institut national de la recherche scientifique (INRS), one of the 10 Université du Québec and the only one dedicated exclusively to graduate level research and training. Founded in 1969 by the Quebec government to help develop Quebec society through research and graduate training, INRS serves society through its discoveries and training of highly skilled researchers capable of scientific, social, and technological innovation. INRS is made up of four thematic and interdisciplinary research and training centres in Quebec City, Montreal, Laval, and Varennes: Armand-Frappier Santé Biotechnologie; Eau Terre Environnement; Énergie Matériaux Télécommunications; and Urbanisation Culture Société. The INRS – Centre Eau Terre Environnement relies on a multidisciplinary approach, which is essential to the understanding and integrated management of water and georesources and is committed to developing workable solutions for protecting the environment. 

To apply to this project:  

  • You must include a CV with the names of at least two referees (preferably three) who can comment on your academic abilities.  

Applications must be submitted by 23:59 GMT on Wednesday 8th January 2025.  

Possible timeline

Year 1

Introduction to FTICR mass spectrometry, training on the 12 T and 15 T solariX instruments, introduction to data analysis methods, analysis of initial samples. 

Year 2

Develop FTICR MS protocols to analyze photo-oxidized petroleum.

Year 3

Apply FTICR MS method to weathered petroleum samples and evaluate toxicity of photo-oxidized petroleum diluted bitumen solutions.  

The focus of the work will be the water accommodated fractions (WAFs) of diluted bitumen oil, produced according to the methods described by ​Bérubé et al. (2023)​, with the addition of a solar radiance lamp to generate solar irradiation. Aquatic toxicity assays will be conducted using the Eastern oyster (Crassostrea virginica) to characterize the aquatic toxicity of oxidized petroleum products. Toxicity assays will follow those listed by ​Lebordais et al. (2021)​. Briefly, oysters will be collected in the beginning of fall before hibernation stage with a diameter of 6.4 to 7.6 cm, ensuring adults of age 3-4 years. Reconstituted seawater will be created to ensure uniform water chemistry among experiments which will be conducted at 20 °C. One-week exposures will be conducted with daily renewal of exposure water with freshly irradiated diluted bitumen WAF. Orbitrap Mass Spectrometry (Orbitrap MS) will be used to characterize the oxidized petroleum fraction present within water because of photooxidation processes The work will entail advance development of soft-ionization techniques. 

Further reading

  1. “Petroleomics: study of the old and the new,” Barrow, M. P., Biofuels 2010, 1, 651-655. 
  2. “Athabasca Oil Sands Process Water: Characterization by Atmospheric Pressure Photoionization and Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry,” Barrow, M. P.; Witt, M.; Headley, J. V.; Peru, K. M., Anal. Chem. 2010, 82, 3727-3735 
  3. “Preliminary fingerprinting of Athabasca oil sands polar organics in environmental samples using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry,” Headley, J. V.; Barrow, M. P.; Peru, K. M.; Fahlman, B.; Frank, R. A.; Bickerton, G.; McMaster, M. E.; Parrott, J.; Hewitt, L. M., Rapid Commun. Mass Spectrom. 2011, 25, 1899-1909. 
  4. “An Added Dimension: GC Atmospheric Pressure Chemical Ionization FTICR MS and the Athabasca Oil Sands,” Barrow, M. P.; Peru, K. M.; Headley, J. V., Anal. Chem. 2014, 86, 8281-8288. 
  5. “Advances in mass spectrometric characterization of naphthenic acids fraction compounds in oil sands environmental samples and crude oil-a review,” Headley, J. V.; Peru, K. M.; Barrow, M. P., Mass Spectrom. Rev. 2016, 35, 311-328.10.1002/mas.2147 
  6. “Effects of Extraction pH on the Fourier Transform Ion Cyclotron Resonance Mass Spectrometry Profiles of Athabasca Oil Sands Process Water,”  
  7. Barrow, M. P.; Peru, K. M.; McMartin, D. W.; Headley, J. V., Energy Fuels 2016, 30, 3615-3621. 
  8. ​​Aeppli, C., Swarthout, R. F., O’Neil, G. W., Katz, S. D., Nabi, D., Ward, C. P., Nelson, R. K., Sharpless, C. M., & Reddy, C. M. (2018). How Persistent and Bioavailable Are Oxygenated Deepwater Horizon Oil Transformation Products? Environmental Science & Technology, 52(13), 7250–7258. https://doi.org/10.1021/acs.est.8b01001 
  9. ​Barron, M. G. (2017). Photoenhanced Toxicity of Petroleum to Aquatic Invertebrates and Fish. Archives of Environmental Contamination and Toxicology, 73(1), 40–46. https://doi.org/10.1007/s00244-016-0360-y 
  10. ​Bekins, B. A., Brennan, J. C., Tillitt, D. E., Cozzarelli, I. M., Illig, J. M. G., & Martinović-Weigelt, D. (2020). Biological Effects of Hydrocarbon Degradation Intermediates: Is the Total Petroleum Hydrocarbon Analytical Method Adequate for Risk Assessment? Environmental Science and Technology, 54(18), 11396–11404. https://doi.org/10.1021/acs.est.0c02220 
  11. ​Bérubé, R., Garnier, C., Lefebvre-Raine, M., Gauthier, C., Bergeron, N., Triffault-Bouchet, G., Langlois, V. S., & Couture, P. (2023). Early developmental toxicity of Atlantic salmon exposed to conventional and unconventional oils. Ecotoxicology and Environmental Safety, 250, 114487. https://doi.org/10.1016/j.ecoenv.2022.114487 
  12. ​Feng, Q., An, C., Chen, Z., Owens, E., Niu, H., & Wang, Z. (2021). Assessing the coastal sensitivity to oil spills from the perspective of ecosystem services: A case study for Canada’s pacific coast. Journal of Environmental Management, 296, 113240. https://doi.org/10.1016/J.JENVMAN.2021.113240 
  13. ​Hepditch, S. L. J., Ahad, J. M. E., Martel, R., To, T. A., Gutierrez-Villagomez, J. M., Larocque, È., Vander Meulen, I. J., Headley, J. V., Xin, Q., & Langlois, V. (2024). Behavior and Fate of Spilled Diluted Bitumen and Conventional Heavy Crude Oil in Shallow Groundwater Systems. Available at SSRN: Https://Ssrn.Com/Abstract=4726089 or Http://Dx.Doi.Org/10.2139/Ssrn.4726089. https://doi.org/10.2139/SSRN.4726089 
  14. ​Hepditch, S. L. J., Gutierrez-Villagomez, J. M., To, T. A., Larocque, E., Xin, Q., Heshka, N. E., Headley, J. V., Vander Meulen, I. J., Dettman, H. D., Triffault-Bouchet, G., Ahad, J. M. E., & Langlois, V. (2024). Aquatic Toxicity and Chemical Fate of Diluted Bitumen Spills in Freshwater Under Natural Weathering. Available at SSRN: Https://Ssrn.Com/Abstract=4799040 or Http://Dx.Doi.Org/10.2139/Ssrn.4799040. https://doi.org/10.2139/SSRN.4799040 
  15. ​Lara-Jacobo, L. R., Gauthier, C., Xin, Q., Dupont, F., Couture, P., Bouchet, T., Dettman, H. D., & Langlois, V. S. (2021). Fate and Fathead Minnow Embryotoxicity of Weathering Crude Oil in a Pilot‐Scale Spill Tank. Environmental Toxicology and Chemistry, 40(1), 127–138. https://doi.org/10.1002/etc.4891 
  16. ​Lebordais, M., Gutierrez-Villagomez, J. M., Gigault, J., Baudrimont, M., & Langlois, V. S. (2021). Molecular impacts of dietary exposure to nanoplastics combined with arsenic in Canadian oysters (Crassostrea virginica) and bioaccumulation comparison with Caribbean oysters (Isognomon alatus). Chemosphere, 277, 130331. https://doi.org/10.1016/J.CHEMOSPHERE.2021.130331 
  17. ​Lee, K., Boufadel, M., Chen, B., Foght, J., Hodson, P., Swanson, S., & Venosa, A. (2015). Expert Panel Report on the Behaviour and Environmental Impacts of Crude Oil Released into Aqueous Environments (Issue November). Royal Society of Canada. 
  18. ​Mallet, A. L., Carver, C. E., Doiron, S., & Thériault, M. H. (2013). Growth performance of Eastern oysters Crassostrea virginica in Atlantic Canada: Effect of the culture gear. Aquaculture, 396–399, 1–7. https://doi.org/10.1016/J.AQUACULTURE.2013.02.019 
  19. ​Mehvar, S., Filatova, T., Dastgheib, A., de Ruyter van Steveninck, E., & Ranasinghe, R. (2018). Quantifying Economic Value of Coastal Ecosystem Services: A Review. Journal of Marine Science and Engineering 2018, Vol. 6, Page 5, 6(1), 5. https://doi.org/10.3390/JMSE6010005 
  20. ​Mohler, R. E., Ahn, S., O’Reilly, K., Zemo, D. A., Espino Devine, C., Magaw, R., & Sihota, N. (2020). Towards comprehensive analysis of oxygen containing organic compounds in groundwater at a crude oil spill site using GC×GC-TOFMS and Orbitrap ESI-MS. Chemosphere, 244. https://doi.org/10.1016/j.chemosphere.2019.125504 
  21. ​NASEM. (2022). Oil in the Sea IV: Inputs, Fates, and Effects. https://doi.org/10.17226/26410 
  22. ​O’Connor, T. P. (2002). National distribution of chemical concentrations in mussels and oysters in the USA. Marine Environmental Research, 53(2), 117–143. https://doi.org/10.1016/S0141-1136(01)00116-7 
  23. ​Ward, C. P., Sharpless, C. M., Valentine, D. L., French-McCay, D. P., Aeppli, C., White, H. K., Rodgers, R. P., Gosselin, K. M., Nelson, R. K., & Reddy, C. M. (2018). Partial Photochemical Oxidation Was a Dominant Fate of Deepwater Horizon Surface Oil. Environmental Science and Technology, 52(4), 1797–1805. https://doi.org/10.1021/ACS.EST.7B05948/SUPPL_FILE/ES7B05948_SI_001.PDF 
  24. ​Zito, P., Podgorski, D. C., Johnson, J., Chen, H., Rodgers, R. P., Guillemette, F., Kellerman, A. M., Spencer, R. G. M., & Tarr, M. A. (2019). Molecular-level composition and acute toxicity of photosolubilized petrogenic carbon. Environmental Science and Technology, 53(14), 8235–8243. https://doi.org/10.1021/ACS.EST.9B01894/SUPPL_FILE/ES9B01894_SI_001.PDF