High-frequency gaseous and particulate chemical characterization using extractive electrospray ionization mass spectrometry (Dual-Phase-EESI-TOF)

Lee, Chuan Ping; Surdu, Mihnea; Bell, David M.; Dommen, Josef; Xiao, Mao; Zhou, Xueqin; Baccarini, Andrea; Giannoukos, Stamatios; Wehrle, G.; Schneider, Pascal; Prévôt, Andrê S. H.; Slowik, Jay G.; Lamkaddam, Houssni; Wang, Dongyu; Baltensperger, Urs; Haddad, Imad El

doi:10.5194/amt-15-3747-2022

Cited by 15 publications

(11 citation statements)

References 67 publications

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“…Therefore, both the difference in the charging scheme and in the experimental conditions favor the detection of the lower oxidized products. The fact that we mostly detect oxidation products with low oxidation states, O 3 showing the highest signal, suggests that the main ionization mechanism is SESI instead of EESI, as similar results have been recently reported …”

Section: Resultssupporting

confidence: 89%

Section: Resultsmentioning

confidence: 99%

“…The fact that we mostly detect oxidation products with low oxidation states, O 3 showing the highest signal, suggests that the main ionization mechanism is SESI instead of EESI, as similar results have been recently reported. 33 In addition to these early-stage oxidation products, compounds with less than 10 carbon atoms were detected. There are some differences also when comparing mass spectra between negative reagent ions.…”

Section: ■ Resultsmentioning

confidence: 99%

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Isomer-Resolved Mobility-Mass Analysis of α-Pinene Ozonolysis Products

et al. 2022

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Highly oxygenated organic molecules (HOMs) are important sources of atmospheric aerosols. Resolving the molecular-level formation mechanisms of these HOMs from freshly emitted hydrocarbons improves the understanding of aerosol properties and their influence on the climate. In this study, we measure the electrical mobility and mass-to-charge ratio of α-pinene oxidation products using a secondary electrospray-differential mobility analyzer-mass spectrometer (SESI-DMA-MS). The mass-mobility spectrum of the oxidation products is measured with seven different reagent ions generated by the electrospray. We analyzed the mobility-mass spectra of the oxidation products C 9–10 H 14–18 O 2–6 . Our results show that acetate and chloride yield the highest charging efficiencies. Analysis of the mobility spectra suggests that the clusters have 1–5 isomeric structures (i.e., ion-molecule cluster structures with distinct mobilities), and the number is affected by the reagent ion. Most of the isomers are likely cluster isomers originating from binding of the reagent ion to different sites of the molecule. By comparing the number of observed isomers and measured mobilities and collision cross sections between standard pinanediol and pinonic acid to the values observed for C 10 H 18 O 2 and C 10 H 16 O 3 produced from oxidation of α-pinene, we confirm that pinanediol and pinonic acid are the only isomers for these elemental compositions in our experimental conditions. Our study shows that the SESI-DMA-MS produces new information from the first steps of oxidation of α-pinene.

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Section: Resultssupporting

confidence: 89%

Section: Resultsmentioning

confidence: 99%

Section: ■ Resultsmentioning

confidence: 99%

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Isomer-Resolved Mobility-Mass Analysis of α-Pinene Ozonolysis Products

et al. 2022

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“…This technique aims to provide the chemical composition of organic particles in real time. It is also possible to measure the gas-phase by using the dual configuration (Lee et al, 2022).…”

Section: Extractive Electrospray Na + Ionization Time-of-flight Mass ...mentioning

confidence: 99%

An intercomparison study of four different techniques for measuring the chemical composition of nanoparticles

Caudillo

Surdu

Lopez

et al. 2022

Preprint

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Abstract. Currently, the complete chemical characterization of nanoparticles (<100 nm) represents an analytical challenge, since these particles are abundant in number but have negligible mass. Several methods for particle-phase characterization have been recently developed to better detect and infer more accurately the sources and fates of ultra-fine particles, but a detailed comparison of different approaches is missing. Here we report on the chemical composition of secondary organic aerosol (SOA) nanoparticles from experimental studies of α-pinene ozonolysis at -50 ºC, -30 ºC, and -10 ºC, and inter-compare the results measured by different techniques. The experiments were performed at the Cosmics Leaving OUtdoor Droplets (CLOUD) chamber at the European Organization for Nuclear Research (CERN). The chemical composition was measured simultaneously by four different techniques: 1) Thermal Desorption-Differential Mobility Analyzer (TD-DMA) coupled to a NO3- chemical ionization-atmospheric-pressure-interface-time-of-flight (CI-APi-TOF) mass spectrometer, 2) Filter Inlet for Gases and AEROsols (FIGAERO) coupled to an I- high-resolution time-of-flight chemical-ionization mass spectrometer (HRToF-CIMS), 3) Extractive Electrospray Na+ Ionization time-of-flight mass spectrometer (EESI-TOF), and 4) Offline analysis of filters (FILTER) using Ultra-high-performance liquid chromatography (UHPLC) and heated electrospray ionization (HESI) coupled to an Orbitrap high-resolution mass spectrometer (HRMS). Intercomparison was performed by contrasting the observed chemical composition as a function of oxidation state and carbon number, by calculating the volatility and comparing the fraction of volatility classes, and by comparing the thermal desorption behavior (for the thermal desorption techniques: TD-DMA and FIGAERO) and performing positive matrix factorization (PMF) analysis for the thermograms. We found that the methods generally agree on the most important compounds that are found in the nanoparticles. However, they do see different parts of the organic spectrum. We suggest potential explanations for these differences: thermal decomposition, aging, sampling artifacts, etc. We applied PMF analysis and found insights of thermal decomposition in the TD-DMA and the FIGAERO.

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“…We tried to minimize unwanted surface 75 reactions of SOA by heating it directly within the sampling flow after removing the gases, which is important for the detection of labile organic compounds. Another online technique that was recently develop is the Extractive Electrospray Ionization (EESI) inlet combined with a mass spectrometer, aim at providing rapid online molecular detection of SOA (Lopez-Hilfiker et al, 2019;Pospisilova et al, 2020) and updated to a dual-phase inlet by Lee et al (2022). The EESI has proven very useful for SOA detection, but it cannot provide comparable gas-phase measurements.…”

mentioning

confidence: 99%

A Combined Gas- and Particle-phase Analysis of Highly Oxygenated Organic Molecules (HOM) from α-pinene Ozonolysis

Zhao

Häkkinen²,

Graeffe³

et al. 2022

Preprint

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Abstract. Highly oxygenated organic molecules (HOM) are important for the formation of secondary organic aerosol (SOA), which poses serious health risks and exerts great influence on Earth’s climate. However, the speciation of particle-phase HOM and its relationship with gas-phase HOM formation has been limited by the lack of suitable analytical techniques. Here, combining a novel particle evaporation inlet VIA (Volatilization Inlet for Aerosols) with a nitrate chemical ionization mass spectrometer (NO3-CIMS), gas- and particle-phase HOM products of α-pinene ozonolysis were studied under different conditions. Within the 50-min residence time of our Teflon chamber, we observed enhancement of C16-C19 HOM dimers in particles compared to the HOM that were condensing. In particular, gas-phase dimer formation was considerably suppressed in experiments with the addition of CO or NO, but dimers still made up a considerable fraction of the observed SOA. In addition to the generally shorter carbon skeletons of the particle phase dimers (i.e. C16-C19) compared to the gas phase (C19-C20), average O / C ratios of the HOM (especially in the dimer range) also decreased slightly in the particle phase. C17H26Oz compounds, which have often been reported by previous offline measurements, dominate the particle-phase HOM mass spectra in α-pinene ozonolysis experiments. Our results indicate that these C17 compounds might be related to particle-phase processes within one hour after HOM condensation. However, the new VIA-NO3-CIMS system used in this work will require more detailed characterization to better understand how the thermal desorption and wall effects may modify the measured particle-phase HOM distributions. Nevertheless, for example organic nitrate measured by this novel VIA-NO3-CIMS system was consistent with the measurements of an Aerodyne Aerosol Mass Spectrometer (AMS), showing the capability of this system as a promising technique for particle-phase HOM measurements. Taken together, we believe that this system is a promising technique for combined online gas- and particle-phase HOM measurements.

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High-frequency gaseous and particulate chemical characterization using extractive electrospray ionization mass spectrometry (Dual-Phase-EESI-TOF)

Cited by 15 publications

References 67 publications

Isomer-Resolved Mobility-Mass Analysis of α-Pinene Ozonolysis Products

Isomer-Resolved Mobility-Mass Analysis of α-Pinene Ozonolysis Products

An intercomparison study of four different techniques for measuring the chemical composition of nanoparticles

A Combined Gas- and Particle-phase Analysis of Highly Oxygenated Organic Molecules (HOM) from α-pinene Ozonolysis

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