Mass spectrometric characterization of organosulfates related to secondary organic aerosol from isoprene

Shalamzari, Mohammad Safi; Ryabtsova, Oksana V.; Kahnt, Ariane; Vermeylen, Reinhilde; Hérent, Marie‐France; Quetin-Leclercq, Joëlle; Veken, Pieter Van der; Maenhaut, Willy; Claeys, Magda

doi:10.1002/rcm.6511

Cited by 67 publications

(73 citation statements)

References 47 publications

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“…However, these compounds were either below the threshold for MS 2 analysis or were below the limit of detection of the LC-MS analysis and without standards or product ion mass spectra it is impossible to confirm the identity of these species. There are other sources that may contribute to these OS species (Shalamzari et al, 2013;Surratt et al, 2008), for example the MW 214 species may be related to 2-or 4-pentenal SOA . The formation pathways of organosulfates remains unclear with epoxides from isoprene and methacrylic acid oxidation (Lin et al, 2013) and sulfate radical chemistry (Nozière et al, 2010;Schindelka et al, 2013) both potential routes.…”

Section: Molecular Compositionmentioning

confidence: 99%

Linking biogenic hydrocarbons to biogenic aerosol in the Borneo rainforest

et al. 2013

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Abstract. Emissions of biogenic volatile organic compounds are though to contribute significantly to secondary organic aerosol formation in the tropics, but understanding these transformation processes has proved difficult, due to the complexity of the chemistry involved and very low concentrations. Aerosols from above a Southeast Asian tropical rainforest in Borneo were characterised using liquid chromatography-ion trap mass spectrometry, high-resolution aerosol mass spectrometry and Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) techniques. Oxygenated compounds were identified in ambient organic aerosol that could be directly traced back to isoprene, monoterpenes and sesquiterpene emissions, by combining field data on chemical structures with mass spectral data generated from synthetically produced products created in a simulation chamber. Eighteen oxygenated species of biogenic origin were identified in the rainforest aerosol from the precursors isoprene, α-pinene, limonene, α-terpinene and β-caryophyllene. The observations provide the unambiguous field detection of monoterpene and sesquiterpene oxidation products in SOA above a pristine tropical rainforest. The presence of 2-methyl tetrol organosulfates and an associated sulfated dimer provides direct evidence that isoprene in the presence of sulfate aerosol can make a contribution to biogenic organic aerosol above tropical forests. High-resolution mass spectrometry indicates that sulfur can also be incorporated into oxidation products arising from monoterpene precursors in tropical aerosol.

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Section: Molecular Compositionmentioning

confidence: 99%

Linking biogenic hydrocarbons to biogenic aerosol in the Borneo rainforest

et al. 2013

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“…They are formed by reactions between organic material and sulfate, which are the main chemical components of atmospheric aerosols [ Murphy et al ., ; Zhang et al ., ]. Organosulfates have been detected in ambient aerosols [ Iinuma et al ., ; Surratt et al ., , ; Gomez‐Gonzalez et al ., ; Froyd et al ., ; Chan et al ., ; Hatch et al ., ; Olson et al ., ; Zhang et al ., ; Worton et al ., ; Shalamzari et al ., ] and cloud water [ Pratt et al ., ] and are estimated to comprise up to 5–10% of OA mass over the continental U.S. [ Tolocka and Turpin , ]. Organosulfates are thought to be good tracers for heterogeneous aerosol phase chemistry and SOA formation since the known formation mechanisms involve reactive uptake of gas phase organic species onto aerosol [ Surratt et al ., ; McNeill et al ., ; Zhang et al ., ].…”

Section: Introductionmentioning

confidence: 99%

Airborne measurements of organosulfates over the continental U.S.

et al. 2015

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Organosulfates are important secondary organic aerosol (SOA) components and good tracers for aerosol heterogeneous reactions. However, the knowledge of their spatial distribution, formation conditions, and environmental impact is limited. In this study, we report two organosulfates, an isoprene-derived isoprene epoxydiols (IEPOX) (2,3-epoxy-2-methyl-1,4-butanediol) sulfate and a glycolic acid (GA) sulfate, measured using the NOAA Particle Analysis Laser Mass Spectrometer (PALMS) on board the NASA DC8 aircraft over the continental U.S. during the Deep Convective Clouds and Chemistry Experiment (DC3) and the Studies of Emissions and Atmospheric Composition, Clouds, and Climate Coupling by Regional Surveys (SEAC4RS). During these campaigns, IEPOX sulfate was estimated to account for 1.4% of submicron aerosol mass (or 2.2% of organic aerosol mass) on average near the ground in the southeast U.S., with lower concentrations in the western U.S. (0.2–0.4%) and at high altitudes (<0.2%). Compared to IEPOX sulfate, GA sulfate was more uniformly distributed, accounting for about 0.5% aerosol mass on average, and may be more abundant globally. A number of other organosulfates were detected; none were as abundant as these two. Ambient measurements confirmed that IEPOX sulfate is formed from isoprene oxidation and is a tracer for isoprene SOA formation. The organic precursors of GA sulfate may include glycolic acid and likely have both biogenic and anthropogenic sources. Higher aerosol acidity as measured by PALMS and relative humidity tend to promote IEPOX sulfate formation, and aerosol acidity largely drives in situ GA sulfate formation at high altitudes. This study suggests that the formation of aerosol organosulfates depends not only on the appropriate organic precursors but also on emissions of anthropogenic sulfur dioxide (SO2), which contributes to aerosol acidity.Key PointsIEPOX sulfate is an isoprene SOA tracer at acidic and low NO conditions Glycolic acid sulfate may be more abundant than IEPOX sulfate globally SO2 impacts IEPOX sulfate by increasing aerosol acidity and water uptake

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“…Ion-pairing liquid chromatography/negative ion mass spectrometry for improved analysis of polar isoprenerelated organosulfates Fine particulate matter from vegetated areas contains as important constituents polar organosulfates (OSs), which are related to secondary organic aerosol (SOA) from the photooxidation of isoprene. [1][2][3][4][5] These polar OSs are of climatic relevance owing to their hydrophilic properties, which enhance the capacity of the aerosols to serve as cloud nucleation nuclei. Negative ion electrospray ionization mass spectrometry [(À)ESI-MS] is well suited for the sensitive detection of organosulfates because the sulfate group is readily deprotonated during the ionization process.…”

Section: Dear Editormentioning

confidence: 99%

“…LC retention and partial separation of the polar isoprene-related OSs, with, as major compounds, sulfate esters of 2-methyltetrols (MW 216), 2-methylglyceric acid (MW 200), and 1,2-dihydroxy-3-butanone (MW 184), have been achieved using di-or trifunctionally bonded C 18 -based stationary phases. [1][2][3][4][5] Hydrophilic interaction chromatography using a silica column has also been applied for the LC/(À)ESI-MS analysis of polar OSs; [6,7] as in the case of di-and trifunctionally C 18 -bonded stationary phases, limited retention and separation of OSs could be obtained. Ion-pairing LC/ (À)ESI-MS methods have been shown to offer a suitable approach to the analysis of very polar organophosphate drug metabolites, which, like the targeted OSs, are highly polar and ionic, in biological fluids.…”

Section: Dear Editormentioning

confidence: 99%

“…Details about the aerosol sample collection and sample processing are given in a recent article. [5] A fraction of the residue from a pooled sample containing 570 mg of organic carbon was redissolved in 1.5 mL of methanol/water (1:4; v/v) by first dissolving the fraction in 0.3 mL of methanol and then adding 1.2 mL of water. For the analysis of the ambient sample, the IP reagent was placed in the injection solution by adding 10 mL of 0.5 mol L -1 DBAA to 90 mL of the above reconstituted sample.…”

Section: Dear Editormentioning

confidence: 99%

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