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measurements, Rock-Eval pyrolysis, and hydrous pyrolysis, to name but a few,
made possible a more comprehensive analysis and a much better understanding of
the origin and fate of organic matter (OM) in the environment (Hunt et al. 2002;
Kvenvolden 2002).
Similarly, Fourier transform ion cyclotron resonance mass spectrometry
(FTICR-MS), a technology pioneered by Comisarow and Marshall (1974), at the
University of British Columbia, entered the field of complex organic mixtures analysis at the turn of the century, with the first practical applications of ultrahighresolution mass spectrometry (m/Δm50% > 100,000, where Δm50% is a mass
spectral peak width at half-maximum peak height), reported later on (Rodgers et al.
2001). Some recent improvements of this technique included the altering of the ICR
cell design (Nikolaev et al. 2011) and/or increasing the magnetic field strength
applied to the ion contents in the ICR cell (Hendrickson et al. 2015), resulting in an
unmatched mass resolution, e.g., 12 million at m/z 675 (Popov et al. 2014), and
unambiguous molecular identification.
Because of this, currently FTICR-MS is the technique of choice for characterization of the most complex mixtures of organic species, such as petroleum and petroleum residues (petroleomics), cellular constituents (proteomics, metabolomics, and
lipidomics), dissolved organic matter (DOM), and, more recently, sedimentary OM
(Han et al. 2008; Rodgers and Marshall 2007; Riedel and Dittmar 2014; Radović
et al. 2016a; Wörmer et al. 2014).
The use of FTICR-MS has expanded the analytical window of complex mixture analysis due to its diverse and selective ionization modes (electrospray, photoionization, laser desorption, etc.), broad range of spectral detection, and high
mass resolution, enabling it to access thousands of high molecular weight, nonvolatile, thermally unstable, and/or highly polar acidic and basic species, which
are typically not GC-amenable, Fig. 15.1 (McKenna et al. 2013). Some limitations
of this technique include the inability of the method to resolve all the possible
isomers of a compound (since they have the same exact m/z), and its component
quantitation capabilities. However, a correlation between the relative abundances
of equivalent species in FTICR-MS and GC-MS analyses has been demonstrated,
suggesting some rudimentary quantitative capabilities for FTICR-MS (Oldenburg
et al. 2014).
As to the FTICR-MS applications in oil spill studies, in the years following the
Deepwater Horizon (DWH) blowout, FTICR-MS made contributions to the characterization of spilled Macondo well (MW) oil, and its residues (McKenna et al. 2013;
Ruddy et al. 2014). Furthermore, it has been used to assess the oil-microbial aggregates (Hatcher et al. 2018; Wozniak et al. 2018), and the baseline organic geochemical compositions of GoM waters and sediments (Radović et al. 2016a, b;
Jaggi 2018). Finally, it has provided chemical characterization of potential future
sources of oil spills, such as heavy oils and oil sands bitumens (Radović et al. 2018).
In this chapter, we will highlight some of these applications.
J. R. Radović et al.
measurements, Rock-Eval pyrolysis, and hydrous pyrolysis, to name but a few,
made possible a more comprehensive analysis and a much better understanding of
the origin and fate of organic matter (OM) in the environment (Hunt et al. 2002;
Kvenvolden 2002).
Similarly, Fourier transform ion cyclotron resonance mass spectrometry
(FTICR-MS), a technology pioneered by Comisarow and Marshall (1974), at the
University of British Columbia, entered the field of complex organic mixtures analysis at the turn of the century, with the first practical applications of ultrahighresolution mass spectrometry (m/Δm50% > 100,000, where Δm50% is a mass
spectral peak width at half-maximum peak height), reported later on (Rodgers et al.
2001). Some recent improvements of this technique included the altering of the ICR
cell design (Nikolaev et al. 2011) and/or increasing the magnetic field strength
applied to the ion contents in the ICR cell (Hendrickson et al. 2015), resulting in an
unmatched mass resolution, e.g., 12 million at m/z 675 (Popov et al. 2014), and
unambiguous molecular identification.
Because of this, currently FTICR-MS is the technique of choice for characterization of the most complex mixtures of organic species, such as petroleum and petroleum residues (petroleomics), cellular constituents (proteomics, metabolomics, and
lipidomics), dissolved organic matter (DOM), and, more recently, sedimentary OM
(Han et al. 2008; Rodgers and Marshall 2007; Riedel and Dittmar 2014; Radović
et al. 2016a; Wörmer et al. 2014).
The use of FTICR-MS has expanded the analytical window of complex mixture analysis due to its diverse and selective ionization modes (electrospray, photoionization, laser desorption, etc.), broad range of spectral detection, and high
mass resolution, enabling it to access thousands of high molecular weight, nonvolatile, thermally unstable, and/or highly polar acidic and basic species, which
are typically not GC-amenable, Fig. 15.1 (McKenna et al. 2013). Some limitations
of this technique include the inability of the method to resolve all the possible
isomers of a compound (since they have the same exact m/z), and its component
quantitation capabilities. However, a correlation between the relative abundances
of equivalent species in FTICR-MS and GC-MS analyses has been demonstrated,
suggesting some rudimentary quantitative capabilities for FTICR-MS (Oldenburg
et al. 2014).
As to the FTICR-MS applications in oil spill studies, in the years following the
Deepwater Horizon (DWH) blowout, FTICR-MS made contributions to the characterization of spilled Macondo well (MW) oil, and its residues (McKenna et al. 2013;
Ruddy et al. 2014). Furthermore, it has been used to assess the oil-microbial aggregates (Hatcher et al. 2018; Wozniak et al. 2018), and the baseline organic geochemical compositions of GoM waters and sediments (Radović et al. 2016a, b;
Jaggi 2018). Finally, it has provided chemical characterization of potential future
sources of oil spills, such as heavy oils and oil sands bitumens (Radović et al. 2018).
In this chapter, we will highlight some of these applications.
J. R. Radović et al.