Quantitative Identification of Nonpolar Perfluoroalkyl Substances by Mass Spectrometry.

Identifying and quantifying mixtures of compounds with very similar fragmentation patterns in their mass spectra presents a unique and challenging problem. In particular, the mass spectra of most per- and poly-fluoroalkyl substances (PFAS) lack a molecular ion. This complicates their identification, especially when using the absence of chromatographic separation. Here, we focus on linear, nonpolar, short-chain PFAS, which have received less attention than amphipathic PFAS despite their longer environmental lifetimes and greater global warming potentials. We identify and quantify n-C5F12 and n-C6F14 in binary mixtures by analyzing small changes in abundances of the main fragment ions following femtosecond tunnel laser ionization, without the need of chromatographic separation. Time-resolved femtosecond ionization mass spectrometry reveals that the metastable cation of both compounds undergoes predissociation within 1-2 ps of ion formation, with yields of C3F7+ showing evidence of coherent vibrational dynamics. These coherent oscillations are compared to low-level ion-state calculations and supported the idea that the oscillations in the C3F7+ ion yield are due to vibrations in the C5F12+• and C6F14+• radical cations and are associated with the predissociation dynamics of the metastable molecular ion. Surprisingly, we find that the fragment ions used for quantifying the mixtures have similar fragmentation dynamics. Conversely, the odd-electron C2F4+• fragment shows different time dependence between the two compounds, yet has negligible difference in the relative ion yield between the two compounds. Our findings indicate that femtosecond laser ionization may be a useful tool for identifying and quantifying mixtures of PFAS without the need of chromatography or high-resolution mass spectrometry.

Ultrafast disruptive probing: Simultaneously keeping track of tens of reaction pathways.

Ultrafast science depends on different implementations of the well-known pump-probe method. Here, we provide a formal description of ultrafast disruptive probing, a method in which the probe pulse disrupts a transient species that may be a metastable ion or a transient state of matter. Disruptive probing has the advantage of allowing for simultaneous tracking of the yield of tens of different processes. Our presentation includes a numerical model and experimental data on multiple products resulting from the strong-field ionization of two different molecules, partially deuterated methanol and norbornene. The correlated enhancement and depletion signals between all the different fragmentation channels offer comprehensive information on photochemical reaction pathways. In combination with ion imaging and/or coincidence momentum imaging or as complementary to atom-specific probing or ultrafast diffraction methods, disruptive probing is a particularly powerful tool for the study of strong-field laser-matter interactions.