Analysis of Photoirradiated Water Accommodated Fractions of Crude Oils Using Tandem TIMS and FT-ICR MS

Abstract

For the first time, trapped ion mobility spectrometry (TIMS) in tandem with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) is applied to the analysis of the low energy water accommodated fraction (WAF) of a crude oil as a function of the exposure to light. The TIMS-FT-ICR MS analysis provided, in addition to the heteroatom series identification, new insights into the WAF isomeric complexity (e.g., [m/z; chemical formula; collision cross section] datasets) for a better evaluation of the degree of chemical and structural photo-induced transformations. Inspection of the [m/z; chemical formula; collision cross section] datasets shows that the WAF composition changes as a function of the exposure to light in the first 115 hours by initial photo-solubilization of HC components and their photo-oxidation up to O4–5 of mainly high double bond equivalence species (DBE > 9). The addition of high resolution TIMS (resolving power of 90–220) to ultrahigh resolution FT-ICR MS (resolving power over 400k) permitted the identification of a larger number of molecular components in a single analysis (e.g., over 47k using TIM-MS compared to 12k by MS alone), with instances of over 6-fold increase in the number of molecular features per nominal mass due to the WAF isomeric complexity. This work represents a stepping stone towards a better understanding of the WAF components and highlights the need for better experimental and theoretical approaches to characterize the WAF structural diversity.

Structural Study of Analogues of Titan’s Haze by Trapped Ion Mobility Coupled with a Fourier Transform Ion Cyclotron Mass Spectrometer

“…The complexity of tholins was previously pointed out but the previous direct infusion experiments missing the added dimension of mobility separation and, thus, the further structural information. [12] The mass spectral inset in Figure 1 emphasizes the mass spectral complexity. The ultra-high resolving power of the FTICR mass analyzer could fully resolve those close signals.…”

“…TIMS-FTICR MS was recently deployed for the description of petroleum and other complex natural mixtures. [11][12][13] To the best of the author's knowledge, this is the first proof of principle study addressing a planetary science subject. As an example, the soluble fraction of a tholins sample is investigated by electrospray ionization (ESI) coupled to TIMS-FTICR MS.…”

Molecular Level Analysis Reveals Changes in Chemical Composition of Dissolved Organic Matter From South Texas Rivers After High Flow Events

“…The lower isomer percentages indicate that DOM formation may have gone through certain biochemical pathways, and that there are additional constraints on the bonds breaking and formation processes of natural DOM. This is in sharp contrast with crude oil, in which the isomers of a given hydrocarbon are more evenly distributed (Benigni et al, 2017). The formation of crude oil involves random chemical reactions under high pressure and heat (e.g., Tissot et al, 1974;Vandenbroucke and Largeau, 2007), while the biogeochemical pathways, key to DOM formation, may not be random.…”

Coupling trapped ion mobility spectrometry to mass spectrometry: trapped ion mobility spectrometry–time‐of‐flight mass spectrometry versus trapped ion mobility spectrometry–Fourier transform ion cyclotron resonance mass spectrometry

“…With the advent of high-resolution mobility analyzers (R >80), there is a natural push for their integration to high-resolution mass analyzers for the analysis of complex mixtures. 21,[24][25][26][27][28][29][30][31][32] Our team has pioneered the integration of TIMS with FT-ICR MS since 2015, 33 and several reports have shown the unique advantages of TIMS with FT-ICR MS. [34][35][36][37][38][39][40] In the work presented here, we evaluated the performance of a TIMS analyzer when coupled to TOF MS and FT-ICR MS for the analysis of a complex mixture standard (i.e., Suwannee River Fulvic Acid Standard). The goal was to study the reproducibility of TIMS across platforms, applicability range, and potential challenges during routine analysis.…”

“…Oxygen class distribution (A) and van Krevelen plots obtained from the SRFA complex mixture analysis using TIMS-TOF MS (B) and TIMS-FT-ICR MS (C) [Color figure can be viewed at wileyonlinelibrary.com]The peak list was used for extraction of the ion mobility spectra using an m/z window of 0.001 from the TIMS-MS datasets using batch processing in the DataAnalysis package (version 5.1, Bruker Daltonics) followed by external mobility calibration. The TIMS spectrum for each molecular formula was processed using a custom-built Software Assisted Molecular Elucidation (SAME) packagea specifically designed two-dimensional (2D) TIMS-MS data processing script written in Python version 2.7 37. The SAME package utilizes noise removal, mean gap filling, "asymmetric least squares smoothing" baseline correction, peak detection by continuous wavelet transform-based peak detection algorithm (SciPy package), and Gaussian fitting with nonlinear least squares functions (Levenberg-Marquardt algorithm).…”