Online measurement of highly oxygenated compounds from organic aerosol

Häkkinen, Ella; Zhao, Jun; Graeffe, Frans; Fauré, Nicolas; Krechmer, Jordan E.; Worsnop, Douglas R.; Timonen, Hilkka; Ehn, Mikael; Kangasluoma, Juha

doi:10.5194/egusphere-2022-933

Cited by 4 publications

(10 citation statements)

References 29 publications

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“…2c, larger molecules (C17 and C20 compounds) were found to evaporate at higher temperatures, while signals of smaller or more volatile molecules (C10 compounds) started to decrease at the highest temperatures. This effect is consistent with the previous results reported by Häkkinen et al (2022) and needs to be kept in mind when interpreting the particle-phase HOM mass spectra. Between the change of temperatures, the sampling line bypassed VIA to 195 obtain SOA mass concentration without heating.…”

Section: Chamber Experimentssupporting

confidence: 92%

“…From our earlier experiments, higher dimer than monomer concentrations were observed in the particle phase for four 95 different VOCs using this system (Häkkinen et al, 2022), in contrast to the measurements in the gas phase. However, those experiments were mainly focused on the particle phase and were conducted with high precursor conditions using a Potential Aerosol Mass (PAM) reactor (Kang et al, 2007;Lambe et al, 2011).…”

mentioning

confidence: 58%

“…70 Here, a novel particle evaporation inlet named VIA (Volatilization Inlet for Aerosols, Aerodyne Research, Inc.) combined with a NO3-CIMS was used to detect HOM in the particle phase at trace concentrations. There are several special features of this system compared to currently used/developed techniques (Häkkinen et al, 2022). Traditional molecular level SOA measurements were usually conducted in an offline or semi-online way, during which filter/metal surfaces are necessary to collect particles (Hallquist et al, 2009;Yatavelli et al, 2012;Mutzel et al, 2015).…”

mentioning

confidence: 99%

“…However, to avoid the additional losses and dilution, direct gas-phase HOM measurements were done by completely bypassing part b) of the setup. A more detailed characterization of this VIA-NO3-CIMS system was investigated in a previous work (Häkkinen et al, 2022). 140 c) Measurements, a suite of gas and particle phase instruments were deployed.…”

mentioning

confidence: 99%

“…nitrate monomer, dimer, and trimer). This calibration factor 145 was estimated using the sulfuric acid signals obtained by the VIA-NO3-CIMS system from several nanograms of AS assuming 70% evaporation at 300 o C (Häkkinen et al, 2022). Thus, a large uncertainty comes with this estimation, along with other factors including the total losses of HOM during evaporation and sampling.…”

mentioning

confidence: 99%

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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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Section: Chamber Experimentssupporting

confidence: 92%

mentioning

confidence: 58%

mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

See 3 more Smart Citations

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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Recent advances in mass spectrometry techniques for atmospheric chemistry research on molecular‐level

Wen

Zhang

2023

Mass Spectrometry Reviews

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The Earth's atmosphere is composed of an enormous variety of chemical species associated with trace gases and aerosol particles whose composition and chemistry have critical impacts on the Earth's climate, air quality, and human health. Mass spectrometry analysis as a powerful and popular analytical technique has been widely developed and applied in atmospheric chemistry for decades. Mass spectrometry allows for effective detection, identification, and quantification of a broad range of organic and inorganic chemical species with high sensitivity and resolution. In this review, we summarize recently developed mass spectrometry techniques, methods, and applications in atmospheric chemistry research in the past several years on molecular‐level. Specifically, new developments of ion‐molecule reactors, various soft ionization methods, and unique coupling with separation techniques are highlighted. The new mass spectrometry applications in laboratory studies and field measurements focused on improving the detection limits for traditional and emerging volatile organic compounds, characterizing multiphase highly oxygenated molecules, and monitoring particle bulk and surface compositions.

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Comparison of the Yield and Chemical Composition of Secondary Organic Aerosol Generated from the OH and Cl Oxidation of Decamethylcyclopentasiloxane

Avery

Alton

Canagaratna

et al. 2023

ACS Earth Space Chem.

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Cyclic volatile methyl siloxanes (cVMS) that are emitted from industrial processes and consumer products often dominate the burden of volatile organic compounds (VOCs) in occupied spaces. cVMS may contribute to oxygenated VOC and secondary organic aerosol (SOA) formation following oxidation by gas-phase radicals in both indoor and outdoor source regions. Several recent studies examined the SOA formation potential of decamethylcyclopentasiloxane (D 5 ) following exposure to hydroxyl radicals (OH) and found that this reaction generates SOA in high yield following multiple days of oxidative aging. Chlorine atoms (Cl) may compete with OH for the oxidative loss of D 5 in indoor and outdoor source regions with active chlorine chemistry, but the SOA formation potential of D 5 + Cl reactions has not been studied. Here, we characterized the yield and chemical composition of SOA generated from Cl oxidation of D 5 in an oxidation flow reactor (OFR) under dry [relative humidity (RH) < 5%] and humid (RH = 40%) conditions and compared results to the yield and composition of SOA generated from OH oxidation of D 5 . D 5 was oxidized using integrated OH and Cl exposures (OH exp and Cl exp ) ranging from 1.1 × 10 12 to 8.2 × 10 12 cm −3 s and from 1.6 × 10 10 to 1.6 × 10 12 cm −3 s, respectively. Like OH, Cl facilitated multistep SOA oxidative aging over the range of OFR conditions that were studied, with maximum SOA mass yields of 1.5 and 1.3 obtained following OH and Cl oxidation of D 5 under humid conditions. These results suggest that indoor and outdoor source regions that are significantly influenced by chlorine chemistry may enhance the atmospheric SOA formation potential of D 5 .

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Online measurement of highly oxygenated compounds from organic aerosol

Cited by 4 publications

References 29 publications

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

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

Recent advances in mass spectrometry techniques for atmospheric chemistry research on molecular‐level

Comparison of the Yield and Chemical Composition of Secondary Organic Aerosol Generated from the OH and Cl Oxidation of Decamethylcyclopentasiloxane

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