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Reading the molecular fine print: Ultrahigh resolution mass spectrometry and the environmental impact of the Athabasca oil sands industry


   School of Life Sciences

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  Dr M Barrow  No more applications being accepted  Competition Funded PhD Project (Students Worldwide)

Warwick United Kingdom Climate Science Ecotoxicology Environmental Chemistry Molecular Biology Petrochemical Chemistry Soil Science

About the Project

Project Highlights:

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

Overview:

The oil sands industry in Alberta, Canada, represents an alternative source of petroleum which has positioned Canada as the leading supplier of oil to the USA. The oil sands material consist of clay, sand, water, and bitumen, where the bitumen can be extracted using an alkaline hot water extractions process.  Approximately three barrels of water are needed to produce one barrel of oil but this water, oil sands process affected water (OSPW), cannot be discharged back into the environment, due to federal regulations. As a result, the OSPW is stored in vast tailings ponds, currently estimated to hold approximately 1 trillion litres of water; these waters contain substances that are known to be toxic to aquatic environments. Recent studies have implicated a wide range of classical naphthenic acids as principal toxicants, along with heavy metals and salts. The anthropogenic impact of future release of OSPW upon the aquatic environment is thus of increasing concern. There is a strong need for improved methodologies for characterization of the oil sands naphthenic acids for environmental monitoring, particularly with respect to understanding the chemistry of highly complex environmental samples. The comprehensive characterization of the organic fraction of OSPW with regards to fate and transport in aquatic environments is an ongoing challenge.  Ultrahigh resolution mass spectrometry, particularly Fourier transform ion cyclotron resonance (FTICR) mass spectrometry (MS), has played a key role in the molecular characterization of environmental samples, leading to complex data sets which subsequently serve as “profiles” or “fingerprints” of the organic components in OSPW. The proposed work will, for the first time, utilize advances in proprietary software tools, developed at the University of Warwick, to improve and expand the molecular characterization of principal toxic components in OSPW, including providing greater insight into isomeric structures. This research will also combine natural abundance ‘intramolecular’ carbon and sulphur isotope analyses of OSPW that were previously used to discriminate natural versus mining-related organic constituents in environmental samples from the oil sands region. In addition, a novel isotopic approach to characterise OSPW components using natural abundance hydrogen isotopes will be evaluated over the course of this project.

Methodology:

This study will fingerprint naphthenic acids in groundwater samples collected along a hydraulic gradient from an Athabasca oil sands region tailings pond to an adjacent wetland hosting abundant organic matter. A better understanding of the influence of environmental processes upon the molecular profiles is required, as it can be used to build a model of the environmental fate of oil sands components. In order to address this, the transport of oil sands components through soil and their subsequent microbial degradation will be experimentally investigated in the laboratory. The resulting samples will be characterized using a suite of isotopic analyses and ultrahigh resolution mass spectrometry; amongst the smallest mass differences observed in the mass spectra of naphthenic acid mixtures is 3.4 mDa, resulting from the contributions of Ox and SOx species. The project will also refine the interpretation and comparison of data to better characterize naphthenic acids in aquatic environments.

Training and skills:

Students will be awarded CENTA2 Training Credits (CTCs) for participation in CENTA2-provided and ‘free choice’ external training. One CTC equates to 1⁄2 day session and students must accrue 100 CTCs across the three years of their PhD.

The student will gain training and expertise in the field of geochemical and environmental analysis, including sample collection and preparation. The student will have the option to work in-house in Saskatoon, Canada, and in Québec City, Canada (Delta-Lab). This international exposure will provide hands-on training in oil sands environmental chemistry and innovative isotope geochemistry method development. 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 (including CASE):

Dr. Barrow has approximately 20 years of experience of working with FTICR mass spectrometry and analysis of complex mixtures, collaborating with industry and with environmental organizations. Prof. Bending will provide expertise on microbial profiling, metagenomics, and soil microcosm type systems. Dr. Headley has approximately 40 years of 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. Ahad has approximately 20 years of experience with isotope geochemistry, including 12 years working on oil sands-related research at the Geological Survey of Canada.

COVID-19 Resilience of the Project:

The Ion Cyclotron Resonance Laboratory has assessed the circumstances pertaining to the coronavirus pandemic and has established new working practices that enable safe continuation of research. The focus of the mitigation efforts has been the acquisition of new FTICR data and these measures have been in place since the summer of 2020. Arrangements have also been put in place which permit remote data analysis and remote meetings at/between Warwick, Environment and Climate Change Canada, and Natural Resources Canada, which grant researchers increased flexibility and offer a resilient approach should there be a resurgence of the coronavirus. 

Possible timeline:

Year 1: Introduction to FTICR mass spectrometry, training on the 12 T solariX, introduction to data analysis methods, analysis of initial samples.

Year 2: Intent to coordinate field sampling during two week period with collaborators (Dr. Jason Ahad) for groundwater samples in the Athabasca oil sands region, Alberta, Canada. Analysis and data interpretation. If the pandemic does not permit this, we have samples already which can be used instead.

Year 3: Continue with data interpretation and preparation of manuscript.


Funding Notes

Home (UK) students who have been ordinarily resident in the UK for at least three years can apply for full awards covering tuition fees and annual stipend for living costs.
International students (including EU Students) can apply for jointly funded awards covering tuition fees in full and annual stipend for living costs.
Successful International candidates would need to cover all other costs themselves including Health Surcharge, visa and flights.

References

Ahad, J.M.E., Pakdel, H., Savard, M.M., Simard, M.-C. & Smirnoff, A. (2012) "Extraction, separation and intramolecular carbon isotope characterization of Athabasca oil sands acids in environmental samples" Anal. Chem., 84(23), pp. 10419−10425.
Ahad, J.M.E., Pakdel, H., Savard, M.M., Calderhead, A.I., Gammon, P.R., Rivera, A., Headley, J.V. & Peru, K.M. (2013) "Characterization and Quantification of Mining-Related “Naphthenic Acids” in Groundwater near a Major Oil Sands Tailings Pond" Environ. Sci. Technol., 47(10), pp. 5023−5030.
Ahad, J.M.E., Pakdel, H., Gammon, P.R., Mayer, B., Savard, M.M., Peru, K.M. & Headley, J.V. (2020) "Distinguishing Natural from Anthropogenic Sources of Acid Extractable Organics in Groundwater near Oil Sands Tailings Ponds" Environ. Sci. Technol., 54(5), pp. 2790-2799.
Barrow, M.P., Peru, K.M. & Headley, J.V. (2014) "An Added Dimension: GC Atmospheric Pressure Chemical Ionization FTICR MS and the Athabasca Oil Sands." Anal. Chem., 86(16), pp. 8281-8288.
Barrow, M.P., Witt, M., Headley, J.V. & Peru, K.M. (2010) "Athabasca Oil Sands Process Water: Characterization by Atmospheric Pressure Photoionization and Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry" Anal. Chem., 82(9), pp. 3727-3735.
Barrow, M.P., Peru, K.M., McMartin, D.W. & Headley, J.V. (2016) "Effects of Extraction pH on the Fourier Transform Ion Cyclotron Resonance Mass Spectrometry Profiles of Athabasca Oil Sands Process Water" Energy & Fuels, 30(5), pp. 3615-3621.
Headley, J.V., Barrow, M.P., Peru, K.M., Fahlman, B., Frank, R.A., Bickerton, G., McMaster, M.E., Parrott, J. & Hewitt, L.M. (2011) "Preliminary fingerprinting of Athabasca oil sands polar organics in environmental samples using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry." Rapid Commun. Mass Spectrom., 25(13), pp. 1899-1909.
Headley, J.V., Peru, K.M. & Barrow, M.P. (2016) "Advances in mass spectrometric characterization of naphthenic acids fraction compounds in oil sands environmental samples and crude oil-a review." Mass Spectrom. Rev., 35(2), pp. 311-328.
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