Characterization of Polar Organosulfates in Secondary Organic Aerosol from the Green Leaf Volatile 3-Z-Hexenal

Shalamzari, Mohammad Safi; Kahnt, Ariane; Vermeylen, Reinhilde; Kleindienst, Tadeusz E.; Lewandowski, Michael; Cuyckens, Filip; Maenhaut, Willy; Claeys, Magda

doi:10.1021/es503226b

Cited by 50 publications

(43 citation statements)

References 39 publications

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“…In addition to monoterpenes, smaller OSs might derive from greenleaf volatiles or even smaller compounds, e.g. methyl vinyl ketone and methacrolein, after oligomerisation, as reported by previous studies (Barbosa et al 2017;Nozière et al 2010;Shalamzari et al 2014Shalamzari et al , 2016. For example, several C 6 -C 9 green leaf volatile-derived OSs, such as C 6 H 10 O 6 S, C 6 H 12 O 6 S, C 6 H 10 O 7 S, and C 9 H 18 O 7 S, have been reported earlier (Barbosa et al 2017) and were abundant in NCP samples.…”

Section: Resultsmentioning

confidence: 55%

Quantification of known and unknown terpenoid organosulfates in PM10 using untargeted LC–HRMS/MS: contrasting summertime rural Germany and the North China Plain

et al. 2019

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Environmental context. Secondary organic aerosols account for a major fraction of atmospheric particulate matter, affecting both climate and human health. Organosulfates, abundant compounds in organic aerosols, are difficult to measure because of the lack of authentic standards. Here we quantify terpene-derived organosulfates in atmospheric particulate matter at a rural site in Germany and at the North China Plain using a combined target/non-target high-resolution mass spectrometry approach.Abstract. Organosulfates (OSs) are a ubiquitous class of compounds in atmospheric aerosol particles. However, a detailed quantification of OSs is commonly hampered because of missing authentic standards and the abundance of unknown OSs. Using a combined targeted and untargeted approach of high-resolution liquid chromatography-Orbitrap mass spectrometry (LC-Orbitrap MS), we quantified for the first time the total concentrations of known and unknown monoterpene (MT) and sesquiterpene (SQT) OSs in summertime PM 10 particulate matter from field studies in rural Germany (MEL) and the North China Plain (NCP). At each site, we observed more than 50 MT-OSs, 13 of which were detectable at both sites. For both locations, median concentrations of MT-OSs were in the range of 10 to 40 ng m À3 , to which the 13 common MT-OSs contributed on average .50 %. The main contributor to MT-OSs was C 9 H 16 O 7 S (MT-OS 267) with average mass concentrations of 2.23 and 6.38 ng m À3 for MEL and NCP respectively. The concentrations of MT-OSs correlated with the concentrations of MT oxidation products only for MEL. For NCP, the low concentrations of MT oxidation products (i.e. typically ,1 ng m À3 ) suggested a suppression of carboxylic acid formation under high concentrations of NO x and particulate sulfate. Furthermore, we observed 17 SQT-OSs for the MEL samples, whereas 40 SQT-OSs were detected in the NCP samples. Only five of these SQT-OSs were detectable at both sites. Correspondingly, the total concentrations of SQT-OSs were larger for NCP than for MEL, which suggested large differences in the particle chemistry. In particular, aerosol acidity was found to be a key factor during SQT-OS formation, and was probably not sufficient in the PM 10 from MEL.

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Section: Resultsmentioning

confidence: 55%

Quantification of known and unknown terpenoid organosulfates in PM10 using untargeted LC–HRMS/MS: contrasting summertime rural Germany and the North China Plain

et al. 2019

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“…Recently, it has been recognized that the release of GLVs would have an impact on atmospheric chemistry, for example through secondary organic aerosol formation following their O 3 and OH reactions. 7,8 The gas-phase reactions of O 3 with alkenes can initiate the atmospheric oxidation of alkenes. Furthermore, the ozone reactions are known to produce OH radicals, the most important atmospheric oxidant.…”

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confidence: 99%

Gas-phase Ozone Reactions with Z-3-Hexenal and Z-3-Hexen-1-ol: Formation Yields of OH Radical, Propanal, and Ethane

2015

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The formation yields of OH radical, propanal, and ethane from the reactions of ozone with Z-3-hexenal (3HA) and Z-3-hexen-1-ol (3HO) were measured under atmospheric conditions. These OH yields were determined to be 0.32 « 0.07 for 3HA and 0.28 « 0.06 for 3HO. The relative formation yield of the C 2 H 5 CHOO intermediate was estimated based upon the formation yields of propanal and ethane, which consistently suggested that C 2 H 5 CHOO is formed more efficiently from the O 3 + 3HA reaction than from the 3HO reaction.The green leaf volatiles (GLVs), Z-3-hexenal (3HA) and Z-3-hexen-1-ol (3HO) are emitted when plants are wounded. 1,2In lawn mowing activity, emission of 3HA and 3HO has been observed not only immediately following lawn mowing, but also from drying lawn clippings. Emissions from drying lawn clippings last for several hours, which suggests the emission of 3HA and 3HO into the atmosphere would typically continue into late afternoon.3,4 3HA and 3HO contain a C=C double bond and hence reactions with O 3 are an important atmospheric fate of these GLVs. Using the reported rate constants, 5,6 the lifetimes of 3HA and 3HO due to reactions with O 3 can be estimated to be 8 and 4 h ([O 3 ] = 40 ppb), respectively, which are comparable to the lifetimes with respect to OH reactions (a few hours). Recently, it has been recognized that the release of GLVs would have an impact on atmospheric chemistry, for example through secondary organic aerosol formation following their O 3 and OH reactions. 7,8The gas-phase reactions of O 3 with alkenes can initiate the atmospheric oxidation of alkenes. Furthermore, the ozone reactions are known to produce OH radicals, the most important atmospheric oxidant. OH formation from O 3 + alkene reactions is thought to be a potential source of OH not only during the nighttime but also in the daytime. 9 The initial step of O 3 + alkene reactions is believed to be the formation of an energized primary ozonide, followed by its rapid decomposition into a carbonyl oxide (Criegee intermediate, CI) and a carbonyl compound. The CI contains excess energy and can either be stabilized or decompose into other products, including OH radicals. The expected initial stage of the reaction of O 3 with 3HA/3HO is schematically shown in Figure 1.In this study, we measured the yields of OH radical formation from the reactions of O 3 with 3HA and 3HO. Furthermore, the formation yields of propanal and ethane were also measured in order to estimate the branching ratio of decomposition of the primary ozonide (º a and º b in Figure 1).All experiments were conducted using a 6 m 3 evacuable chamber at 1 atm and 298 « 2 K. Details of this chamber have been reported elsewhere. 5 The concentrations of gaseous species were monitored using a Fourier transform infrared (FTIR) spectrometer equipped with multireflection mirror optics (optical path length: 221.5 m). The initial concentrations of O 3 and substituted Z-3-hexenes (3HX, which are 3HA or 3HO) were 15 and 0.21 ppm, respectively.The OH formation yields from O 3 +...

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“…Many studies have shown that biogenic volatile organic compounds (BVOCs) such as isoprene, monoterpenes, sesquiterpenes, oxygenated derivatives and some green leaf alcohols play an important role in producing OSs (Surratt et al, 2007;Iinuma et al, 2007;Surratt et al, 2008;N. L. Ng, 2008;Riva et al, 2016a;Zhang and Worton, 2012;Mael et al, 2015;Schindelka et al, 2013;Shalamzari et al, 2014;Shalamzari et al, 2016;Liggio and Li, 2006;Iinuma et al, 2009;Perri et al, 2010;Chan et al, 2011;Darer et al, 2011;Chen and Jang, 2012;Barbosa et al, 2017;Szmigielski, 2016;Noziè re et al, 2010;McNeill et al, 2012). However, recent studies have focused on anthropogenic emissions (e.g.…”

Section: Introductionmentioning

confidence: 99%

Molecular Characterization of Organosulfates in Arctic Ocean and Antarctic atmospheric aerosols

Xie

Zhu

et al. 2019

Preprint

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Abstract. Organic aerosols are ubiquitous components of atmospheric aerosols. Organosulfate aerosols have been detected in the Arctic Ocean atmosphere and may play an important role in the radiative balance in Polar Regions. Aerosol samples from the Arctic Ocean and Antarctic atmosphere during 2014/2015 CHINARE were analysed by ultrahigh resolution mass spectrometry coupled with negative ion mode electrospray ionization (ESI(-)-UHRMS). Hundreds of organic compounds were detected and tentatively determined by their formulas, including organosulfates (OSs), nitrooxy-organosulfates (NOSs), organonitrates (ONs) and oxygenated hydrocarbons (OxyCs). The number of OSs/NOSs accounted for 28&ndash;32&thinsp;% of the total number of detected molecules at polar sites and ONs were 28&ndash;40&thinsp;%. Organic compounds of Arctic Ocean and Antarctic aerosols had high oxidation states for carbon and a large percentage of high molecular weight formulas; this indicated that <q>aged</q> organic aerosols likely comprise a significant part of the polar atmosphere. We hypothesized that highly oxidized HMW compounds tend to be transported to the polar area from stratospheric reservoirs. Dramatic differences of the molecular characteristics were observed when we compared aerosol samples between polar sites and Guangzhou sites, reflecting the different oxidation mechanisms and atmospheric transmission. The polar sites contained higher fractions of OSs/NOSs and lower fractions of ONs than the Guangzhou sites did; this indicated that the oxidation of NOx was weaker in the polar region. Observing that the fraction and oxidation states of polycyclic aromatic OSs/NOSs polar regions were similar to the Guangzhou urban area but not the rural area implied an anthropogenic influence on OSs/NOSs in remote polar areas. In addition, the contribution of potential precursors (anthropogenic and biogenic volatile organic compounds) to OS and NOS formation as well as the effects of nss-SO4 aerosols, pH and RH on OS formation in polar areas were discussed. Our study presents the first overview of OSs and ONs in the Arctic Ocean and Antarctic atmosphere and promotes the understanding of their characteristics and sources.

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Characterization of Polar Organosulfates in Secondary Organic Aerosol from the Green Leaf Volatile 3-Z-Hexenal

Cited by 50 publications

References 39 publications

Quantification of known and unknown terpenoid organosulfates in PM10 using untargeted LC–HRMS/MS: contrasting summertime rural Germany and the North China Plain

Quantification of known and unknown terpenoid organosulfates in PM10 using untargeted LC–HRMS/MS: contrasting summertime rural Germany and the North China Plain

Gas-phase Ozone Reactions with Z-3-Hexenal and Z-3-Hexen-1-ol: Formation Yields of OH Radical, Propanal, and Ethane

Molecular Characterization of Organosulfates in Arctic Ocean and Antarctic atmospheric aerosols

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