Acid-catalyzed multiphase chemistry of isoprene epoxydiols (IEPOX) on sulfate aerosol produces substantial amounts of water-soluble secondary organic aerosol (SOA) constituents, including 2-methyltetrols, methyltetrol sulfates, and oligomers thereof in atmospheric fine particulate matter (PM 2.5 ). These constituents have commonly been measured by gas chromatography interfaced to electron ionization mass spectrometry (GC/EI-MS) with prior derivatization or by reverse-phase liquid chromatography interfaced to electrospray ionization high-resolution mass spectrometry (RPLC/ESI-HR-MS). However, both techniques have limitations in explicitly resolving and quantifying polar SOA constituents due either to thermal degradation or poor separation. With authentic 2-methyltetrol and methyltetrol sulfate standards synthesized in-house, we developed a hydrophilic interaction liquid chromatography (HILIC)/ESI-HR-quadrupole time-of-flight mass spectrometry (QTOFMS) protocol that can chromatographically resolve and accurately measure the major IEPOX-derived SOA constituents in both laboratory-generated SOA and atmospheric PM 2.5 . 2-Methyltetrols were simultaneously resolved along with 4–6 diastereomers of methyltetrol sulfate, allowing efficient quantification of both major classes of SOA constituents by a single non-thermal analytical method. The sum of 2-methyltetrols and methyltetrol sulfates accounted for approximately 92%, 62%, and 21% of the laboratory-generated β-IEPOX aerosol mass, laboratory-generated δ-IEPOX aerosol mass, and organic aerosol mass in the southeastern U.S., respectively, where the mass concentration of methyltetrol sulfates was 171–271% the mass concentration of methyltetrol. Mass concentrations of methyltetrol sulfates were 0.39 and 2.33 μg m −3 in a PM 2.5 sample collected from central Amazonia and the southeastern U.S., respectively. The improved resolution clearly reveals isomeric patterns specific to methyltetrol sulfates from acid-catalyzed multiphase chemistry of β- and δ-IEPOX. We also demonstrate that conventional GC/EI-MS analyses overestimate 2-methyltetrols by up to 188%, resulting (in part) from the thermal degradation of methyltetrol sulfates. Lastly, C 5 -alkene triols and 3-methyltetrahydrofuran-3,4-diols are found to be largely GC/EI-MS artifacts formed from thermal degradation of 2-methyltetrol sulfates and 3-methyletrol sulfates, respectively, and are not detected with HILIC/ESI-HR-QTOFMS.
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A non-derivatized method for simultaneous quantitation of proteinogenic, urea-cycle, and acetylated amino acids by liquid chromatography–high-resolution mass spectrometry
The quantification of amino acids as freely dissolved compounds or from hydrolyzed peptides and proteins is a common endeavor in biomedical and environmental sciences. In order to avoid the drawbacks of derivatization and application challenges of tandem mass spectrometry, we present here a robust 13-min liquid chromatography coupled with a full-scan mass spectrometry method to achieve rapid detection and quantification of 30 amino acids without derivatization. We combined hydrophilic interaction liquid chromatography with heated electrospray ionization and high-resolution mass spectrometry operated with polarity switching to analyze the 20 proteinogenic amino acids, ornithine, citrulline, homoserine, cystine, and six acetylated amino acids. We obtained high mass accuracy and good precision of the targeted amino acids. Limits of detection ranged from 0.017 to 1.3 μM. Noteworthy for environmental samples, we found comparable ionization efficiency and quantitative detection for the majority of the analytes prepared with pure water versus a high-salt solution. We applied the method to profile carbon source-dependent secretions of amino acids by Pseudomonas protegens Pf-5, a well-known plant-beneficial bacterium.
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- Award ID(s):
- 1653092
- PAR ID:
- 10123548
- Date Published:
- Journal Name:
- Environmental Chemistry Letters
- ISSN:
- 1610-3653
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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