Accessing the Low-Polar Molecular Composition of Boreal and Arctic Peat-Burning Organic Aerosol via Thermal Analysis and Ultrahigh-Resolution Mass Spectrometry: Structural Motifs and Their Formation.

Peatland fires emit organic carbon-rich particulate matter into the atmosphere. Boreal and Arctic peatlands are becoming more vulnerable to wildfires, resulting in a need for better understanding of the emissions of these special fires. Extractable, nonpolar, and low-polar organic aerosol species emitted from laboratory-based boreal and Arctic peat-burning experiments are analyzed by direct-infusion atmospheric pressure photoionization (APPI) ultrahigh-resolution mass spectrometry (UHRMS) and compared to time-resolved APPI UHRMS evolved gas analysis from the thermal analysis of peat under inert nitrogen (pyrolysis) and oxidative atmosphere. The chemical composition is characterized on a molecular level, revealing abundant aromatic compounds that partially contain oxygen, nitrogen, or sulfur and are formed at characteristic temperatures. Two main structural motifs are identified, single core and multicore, and their temperature-dependent formation is assigned to the thermal degradation of the lignocellulose building blocks and other parts of peat.

Detailed Comparison of Xenon APPI (9.6/8.4 eV), Krypton APPI (10.6/10.0 eV), APCI, and APLI (266 nm) for Gas Chromatography High Resolution Mass Spectrometry of Standards and Complex Mixtures.

Photoionization schemes for mass spectrometry, either by laser or discharge lamps, have been widely examined and deployed. In this work, the ionization characteristics of a xenon discharge lamp (Xe-APPI, 9.6/8.4 eV) have been studied and compared to established ionization schemes, such as atmospheric pressure chemical ionization, atmospheric pressure photoionization with a krypton discharge lamp (Kr-APPI, 10.6/10 eV) and atmospheric pressure laser ionization (266 nm). Addressing the gas-phase ionization behavior has been realized by gas chromatography coupled to high-resolution mass spectrometry without the usage of a dopant. For standard substances, it has been found that Xe-APPI is able to ionize a broad range of polycyclic aromatic hydrocarbons as well as their heteroatom-containing and alkylated derivatives. However, thiol and ester compounds could not be detected. Moreover, Xe-APPI revealed a high tendency to generate oxygenated artifacts, most likely due to a VUV absorption band of oxygen at 148 nm. Beneficially, almost no chemical background, commonly caused by APCI or Kr-APPI due to column blood, plasticizers or impurities, is observed. This advantage is noteworthy for evolved gas analysis without preseparation or for chromatographic coelution. For the complex mixtures, Xe-APPI revealed the predominant generation of radical cations via direct photoionization with a high selectivity toward aromatic core structures with low alkylation. Interestingly, both Xe-APPI and Kr-APPI could sensitively detect sterane cycloalkanes, validated by gas chromatographic retention. The narrowly ionized chemical space could let Xe-APPI find niche applications, e.g., for strongly contaminated samples to reduce the background.

Atmospheric Pressure Single Photon Laser Ionization (APSPLI) Mass Spectrometry Using a 157 nm Fluorine Excimer Laser for Sensitive and Selective Detection of Non- to Semipolar Hydrocarbons.

Atmospheric pressure single photon ionization (APSPLI) mass spectrometry utilizing a fluorine excimer laser (157 nm, 7.9 eV) is presented for the first time. For evaluation and optimization, polycyclic aromatic hydrocarbon (PAH) standard mixtures were used. The presented technique allowed for the selective ionization of semi- to nonpolar compounds in a single photon ionization process using VUV photons. Molecular radical cations were found as a base peak, whereas protonated species were almost absent. Although the ionization chamber is flushed by pure nitrogen, remaining oxygen and water traces caused unwanted oxidized ionization artifacts. Installation of water and oxygen filter cartridges significantly reduced the abundance of artifacts. For evaluating complex mixture analysis, APSPLI was applied to characterize a light crude oil. In addition to aromatic hydrocarbons, APSPLI allowed for the sensitive ionization of sulfur-containing aromatic constituents (PASH). A comparison of APSPLI to atmospheric pressure laser ionization (266 nm, 4.7 eV) revealed the additional compositional space accessible by the single photon process. APLI, conducted with UV radiation, is mainly restricted to PAH analysis. APSPLI overcomes this limitation, and PAH and PASH, which often occur simultaneously in complex mixtures, can be detected. This novel ionization concept is envisioned to have a high analytical potential further explored in the future.

Real time monitoring of slow pyrolysis of polyethylene terephthalate (PET) by different mass spectrometric techniques.

In the context of waste upgrading of polyethylene terephthalate (PET) by pyrolysis, this study presents three on-line mass spectrometric techniques with soft ionization for monitoring the emitted decomposition products and their thermal dependent evolution profiles. Pyrolysis experiments were performed using a thermogravimetric analyzer (TGA) under nitrogen atmosphere with a heating rate of 5 °C/min from 30 °C to 600 °C. Single-photon ionization (SPI at 118 nm/10.5 eV) and resonance enhanced multiple photon ionization (REMPI at 266 nm) were used with time-of-flight mass spectrometry (TOF-MS) for evolved gas analysis (TGA-SPI/REMPI-TOFMS). Additionally, the chemical signature of the pyrolysis products was investigated by atmospheric pressure chemical ionization (APCI) ultra high resolution Fourier Transform ion cyclotron resonance mass spectrometry (FT-ICR MS) which enables assignment of molecular sum formulas (TGA-APCI FT-ICR MS). Despite the soft ionization by SPI, the fragmentation of some compounds with the loss of the [O-CH = CH2] fragment is observed. The major compounds were acetaldehyde (m/z 44), benzoic acid (m/z 122) and a fragment of m/z 149. Using REMPI, aromatic species were selectively detected. Several series of pyrolysis products were observed in different temperature intervals, showing the presence of polycyclic aromatic hydrocarbons (PAHs), especially at high temperatures. FT-ICR MS data showed, that the CHO4 class was the most abundant compound class with a relative abundance of 45.5%. The major compounds detected with this technique corresponded to m/z 193.0495 (C10H9O4+) and 149.0233 (C8H5O3+). Based on detailed chemical information, bulk reaction pathways are proposed, showing the formation of both cyclic monomer/dimer and linear structures.