Characterization of CHOS compounds in rainwater from continental and coastal storms by ultrahigh resolution mass spectrometry

Mead, Ralph N.; Felix, J. David; Avery, G. Brooks; Kieber, Robert J.; Willey, Joan D.; Podgorski, David C.

doi:10.1016/j.atmosenv.2015.01.057

Cited by 32 publications

(22 citation statements)

References 54 publications

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“…Note the different timescales in the figures that clearly show that the reaction is completed within about half of the time at low oxygen concentrations. This sensitivity to oxygen concentrations is in agreement with the generally faster oligomerization rate under low-oxygen conditions that is well known from polymer chemistry (Odian, 2004;Mendez et al, 2013). While the reaction cell represents an aqueous volume with a very small surface-volume ratio, it will be explored in Sect.…”

Section: Predicted Mvk Decaysupporting

confidence: 82%

Aqueous-phase oligomerization of methyl vinyl ketone through photooxidation – Part 2: Development of the chemical mechanism and atmospheric implications

et al. 2015

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Abstract. Laboratory experiments of efficient oligomerization from methyl vinyl ketone (MVK) in the bulk aqueous phase were simulated in a box model. Kinetic data are applied (if known) or fitted to the observed MVK decay and oligomer mass increase. Upon model sensitivity studies, in which unconstrained rate constants were varied over several orders of magnitude, a set of reaction parameters was found that could reproduce laboratory data over a wide range of experimental conditions. This mechanism is the first that comprehensively describes such radical-initiated oligomer formation. This mechanism was implemented into a multiphase box model that simulates secondary organic aerosol (SOA) formation from isoprene, as a precursor of MVK and methacrolein (MACR) in the aqueous and gas phases. While in laboratory experiments oxygen limitation might occur and lead to accelerated oligomer formation, such conditions are likely not met in the atmosphere. The comparison of predicted oligomer formation shows that MVK and MACR likely do negligibly contribute to total SOA as their solubilities are low and even reduced in aerosol water due to ionic strength effects (Setchenov coefficients). Significant contribution by oligomers to total SOA might only occur if a substantial fraction of particulate carbon acts as oligomer precursors and/or if oxygen solubility in aerosol water is strongly reduced due to salting-out effects.

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Section: Predicted Mvk Decaysupporting

confidence: 82%

Aqueous-phase oligomerization of methyl vinyl ketone through photooxidation – Part 2: Development of the chemical mechanism and atmospheric implications

et al. 2015

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“…In addition, more than 85% of the sulfur-containing compounds possessed (S + N)/O ≥ 0.5, indicating that reduced nitrogen or sulfur functional groups were present in the chemical structure. CHOS+ and CHONS+ compounds (36-56%) had Xc ≥ 2.50, indicating that they were aromatics containing reduced sulfur such as C 13 H 8 OS (Xc = 2.75), C 14 H 10 OS (Xc = 2.75), and C 16 H 12 OS (Xc = 2.78), which were from fossil fuel combustion (Mead et al, 2015). Only 20-30 signals for CHNS*À compounds were detected in Shanghai, representing less than 0.4% of the total abundance of organic compounds (Figure 1).…”

Section: Chos and Chons Compoundsmentioning

confidence: 99%

Chemical Characteristics of Organic Aerosols in Shanghai: A Study by Ultrahigh‐Performance Liquid Chromatography Coupled With Orbitrap Mass Spectrometry

et al. 2017

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Particulate matter 2.5 (PM2.5) filter samples were collected in July and October 2014 and January and April 2015 in urban Shanghai and analyzed using ultrahigh‐performance liquid chromatography coupled to Orbitrap mass spectrometry. The measured chromatogram‐mass spectra were processed by a nontarget screening approach to identify significant signals. In total, 810–1,510 chemical formulas of organic compounds in the negative polarity (negative electrospray ionization (ESI−)) and 860–1,790 in the positive polarity (ESI+), respectively, were determined. The chemical characteristics of organic aerosols (OAs) in Shanghai varied among different months and between daytime and nighttime. In the January samples, organics were generally richer in terms of both number and abundance, whereas those in the July samples were far lower. More CHO− (compounds containing only carbon, hydrogen, and oxygen and detected in ESI−) and CHOS− (sulfur‐containing organics) were found in the daytime samples, suggesting a photochemical source, whereas CHONS− (nitrogen‐ and sulfur‐containing organics) were more abundant in the nighttime samples, due to nocturnal nitrate radical chemistry. A significant number of monocyclic and polycyclic aromatic compounds, and nitrogen‐ and sulfur‐containing heterocyclic compounds, were detected in all samples, indicating that biomass burning and fossil fuel combustion made important contributions to the OAs in urban Shanghai. Additionally, precursor‐product pair analysis indicates that the epoxide pathway is an important formation route for organosulfates observed in Shanghai. Moreover, a similar analysis suggests that 35–57% of nitrogen‐containing compounds detected in ESI+ could be formed through reactions between ammonia and carbonyls. Our study presents a comprehensive overview of OAs in urban Shanghai, which helps to understand their characteristics and sources.

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“…One of the current essential issues to unravel our ability to forecast future climate change and air quality, implies a better understanding of natural processes leading to SOA formation, and in particular the formation and fate of macromolecules. The presence of macromolecules in the atmosphere has previously been monitored by ultrahigh resolution mass spectrometry techniques which have revealed the presence of organic molecules containing up to 35 carbon atoms (C 35 ) in aerosol (Kourtchev et al, 2014;LeClair et al, 2012;Mazzoleni et al, 2012;Rincón et al, 2012), in fog (Mazzoleni et al, 2010) and in rain (Mead et al, 2015(Mead et al, , 2013.…”

Section: Conclusion and Atmospheric Implicationsmentioning

confidence: 99%

Aqueous phase oligomerization of α,β-unsaturated carbonyls and acids investigated using ion mobility spectrometry coupled to mass spectrometry (IMS-MS)

Renard

Tlili

Ravier

et al. 2016

Atmospheric Environment

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One of the current essential issues to unravel our ability to forecast future climate change and air quality, implies a better understanding of natural processes leading of secondary organic aerosol (SOA) formation, and in particular the formation and fate of oligomers. The difficulty in characterizing macromolecules is to discern between large oxygenated molecules from series of oligomers containing repeated small monomers of diverse structures. In the present study, taking advantage from previously established radical vinyl oligomerization of methyl vinylketone (MVK) in the aqueous phase, where relatively simple oligomers containing up to 14 monomers were observed, we have investigated the same reactivity on several other unsaturated water soluble organic compounds (UWSOCs) and on a few mixtures of these precursor compounds. The technique used to characterize the formed oligomers was a traveling wave ion mobility spectrometry coupled to a hybrid quadrupoletime of flight mass spectrometer (IMS-MS) fitted with an electrospray source and ultra-high performance liquid chromatography (UPLC). The technique allows for an additional separation, especially for large ions, containing long carbon chains. We have shown the efficiency of the IMS-mass spectrometry technique to detect oligomers derived from MVK photooxidation in the aqueous phase. The results were then compared to other oligomers, derived from ten other individual biogenic UWSOCs. The technique allowed distinguishing 2 between different oligomers arising from different precursors. It also clearly showed that compounds bearing a non-conjugated unsaturation did not provide oligomerization. Finally, it was shown that the IMS-mass spectrometry technique, applied to mixtures of unsaturated conjugated precursors, exhibited the ability of these precursors to co-oligomerize, i.e. forming only one complex oligomer system bearing monomers of different structures. The results are discussed in terms of atmospheric implications for the detection of oligomers in complex chamber and/or field samples.

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Characterization of CHOS compounds in rainwater from continental and coastal storms by ultrahigh resolution mass spectrometry

Cited by 32 publications

References 54 publications

Aqueous-phase oligomerization of methyl vinyl ketone through photooxidation – Part 2: Development of the chemical mechanism and atmospheric implications

Aqueous-phase oligomerization of methyl vinyl ketone through photooxidation – Part 2: Development of the chemical mechanism and atmospheric implications

Chemical Characteristics of Organic Aerosols in Shanghai: A Study by Ultrahigh‐Performance Liquid Chromatography Coupled With Orbitrap Mass Spectrometry

Aqueous phase oligomerization of α,β-unsaturated carbonyls and acids investigated using ion mobility spectrometry coupled to mass spectrometry (IMS-MS)

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