Organosulfates and oxidation products from biogenic hydrocarbons in fine aerosols from a forest in North West Europe during spring

Kristensen, Kasper; Glasius, Marianne

doi:10.1016/j.atmosenv.2011.05.063

Cited by 150 publications

(166 citation statements)

References 58 publications

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“…In the Amazon, Kourtchev et al (2016) previously found a similar subset of these unidentified CHOS compounds in SOA samples, suggesting a biogenic influence. Many organosulfates and nitrooxy-organosulfates, previously reported in laboratory studies, ambient aerosols, and cloud water as derived from monoterpene oxidation (Boone et al, 2015;Hamilton et al, 2013;Iinuma et al, 2007aIinuma et al, , b, 2009Kristensen et al, 2016;Kristensen and Glasius, 2011;Lin et al, 2012;Mazzoleni et al, 2012;Nguyen et al, 2012b;Nozière et al, 2010;O'Brien et al, 2014;Pratt et al, 2013;Stone et al, 2012;Surratt et al, 2008), were detected in the biogenic-influenced cloud water samples (Table 2), also consistent with monoterpene emissions along the air mass trajectories (Guenther et al, 2006). In this study, the required solid-phase extraction step precluded the detection of isoprene-derived organosulfates, which would have been removed prior to analysis.…”

Section: Biogenic Influencesupporting

confidence: 66%

Biogenic, urban, and wildfire influences on the molecular composition of dissolved organic compounds in cloud water

Cook¹,

Lin²,

Peng³

et al. 2017

Atmos. Chem. Phys.

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Abstract. Organic aerosol formation and transformation occurs within aqueous aerosol and cloud droplets, yet little is known about the composition of high molecular weight organic compounds in cloud water. Cloud water samples collected at Whiteface Mountain, New York, during AugustSeptember 2014 were analyzed by ultra-high-resolution mass spectrometry to investigate the molecular composition of dissolved organic carbon, with a focus on sulfur-and nitrogen-containing compounds. Organic molecular composition was evaluated in the context of cloud water inorganic ion concentrations, pH, and total organic carbon concentrations to gain insights into the sources and aqueous-phase processes of the observed high molecular weight organic compounds. Cloud water acidity was positively correlated with the average oxygen : carbon ratio of the organic constituents, suggesting the possibility for aqueous acid-catalyzed (prior to cloud droplet activation or during/after cloud droplet evaporation) and/or radical (within cloud droplets) oxidation processes. Many tracer compounds recently identified in laboratory studies of bulk aqueous-phase reactions were identified in the cloud water. Organosulfate compounds, with both biogenic and anthropogenic volatile organic compound precursors, were detected for cloud water samples influenced by air masses that had traveled over forested and populated areas. Oxidation products of long-chain (C 10−12 ) alkane precursors were detected during urban influence. Influence of Canadian wildfires resulted in increased numbers of identified sulfur-containing compounds and oligomeric species, including those formed through aqueous-phase reactions involving methylglyoxal. Light-absorbing aqueous-phase products of syringol and guaiacol oxidation were observed in the wildfire-influenced samples, and dinitroaromatic compounds were observed in all cloud water samples (wildfire, biogenic, and urban-influenced). Overall, the cloud water molecular composition depended on air mass source influence and reflected aqueous-phase reactions involving biogenic, urban, and biomass burning precursors.

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Section: Biogenic Influencesupporting

confidence: 66%

Biogenic, urban, and wildfire influences on the molecular composition of dissolved organic compounds in cloud water

Cook¹,

Lin²,

Peng³

et al. 2017

Atmos. Chem. Phys.

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“…Due to the lack of commercial standard, OSs were quantified using camphor sulfonic acid. 21,26 Seven-point linear calibration of peak area vs concentration (both normalized by the internal standard) were established with the correlation coefficient R 2 > 0.99. Three pNOS isomers with MW 295, iOS with MW 216 and MW 200 were quantified since the intensity of their peaks were high enough for quantifications (signal/noise > 3).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…The detection limit for camphor sulfonic acid was 0. 12,21 Asia, 37 and the U.S. 26,48 were in the range of 0.217−140 ng m −3 during the summer (Table 2). Our measurements were consistent with these reported values, although different instruments and standards were used for pNOSs quantification.…”

Section: Environmental Science and Technologymentioning

confidence: 99%

Organosulfates from Pinene and Isoprene over the Pearl River Delta, South China: Seasonal Variation and Implication in Formation Mechanisms

Ding

Wang

et al. 2014

Environ. Sci. Technol.

128

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Biogenic organosulfates (OSs) are important markers of secondary organic aerosol (SOA) formation involving cross reactions of biogenic precursors (terpenoids) with anthropogenic pollutants. Until now, there has been rare information about biogenic OSs in the air of highly polluted areas. In this study, fine particle (PM 2.5 ) samples were separately collected in daytime and nighttime from summer to fall 2010 at a site in the central Pearl River Delta (PRD), South China. Pinene-derived nitrooxyorganosulfates (pNOSs) and isoprene-derived OSs (iOSs) were quantified using a liquid chromatograph (LC) coupled with a tandem mass spectrometer (MS/MS) operated in negative electrospray ionization (ESI) mode. The pNOSs with MW 295 exhibited higher levels in fall (151 ± 86.9 ng m −3 ) than summer (52.4 ± 34.0 ng m −3 ), probably owing to the elevated levels of NOx and sulfate in fall when air masses mainly passed through city clusters in the PRD and biomass burning was enhanced. In contrast to observations elsewhere where higher levels occurred at nighttime, pNOS levels in the PRD were higher during the daytime in both seasons, indicating that pNOS formation was likely driven by photochemistry over the PRD. This conclusion is supported by several lines of evidence: the specific pNOS which could be formed through both daytime photochemistry and nighttime NO 3 chemistry exhibited no day− night variation in abundance relative to other pNOS isomers; the production of the hydroxynitrate that is the key precursor for this specific pNOS was found to be significant through photochemistry but negligible through NO 3 chemistry based on the mechanisms in the Master Chemical Mechanism (MCM). For iOSs, 2-methyltetrol sulfate ester which could be formed from isoprene-derived epoxydiols (IEPOX) under low-NOx conditions showed low concentrations (below the detection limit to 2.09 ng m −3 ), largely due to the depression of IEPOX formation by the high NOx levels over the PRD. ■ INTRODUCTIONBiogenic volatile organic compounds (BVOCs) including isoprene and monoterpenes 1 contribute significantly to the global secondary organic aerosol (SOA) budget. 2 Recent studies have shown that the conversion of BVOCs to SOA can be significantly promoted in the presence of high anthropogenic emissions. 3−6 As notable SOA products of BVOCs reacting with anthropogenic pollutants under acidic conditions, organosulfates (OSs) have been detected in both laboratory-generated SOA 7−10 and ambient aerosols. 11−18 Moreover, OSs could contribute a significant fraction of fine particles, accounting for up to 30% of organic matter (OM) 9,19−23 and up to 10% of total sulfate. 24,25 The formation mechanisms of OSs are still unclear. Previous chamber studies have demonstrated that both OH-photooxidation and NO 3 dark reactions can form pinene-derived nitrooxy-organosulfates (pNOSs) on acidic particles. 9 The pNOSs were only detected in nighttime samples in northeastern Bavaria, Germany, suggesting a role for nighttime NO 3 chemistry in pNOS formation. 15 How...

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“…Some studies have focused on the concentrations of the reaction products of α-and β-pinene (pinonic and pinic acids) in real atmospheres (Kavouras and Stephanou, 2002;Kourtchev et al, 2008Kourtchev et al, , 2009Zhang et al, 2010;Cheng et al, 2011;Kristensen and Glasius, 2011), but very little information is available on the concentrations of other terpenoic acids, mainly due to the lack of authentic standards. In some studies, the concentrations of other terpenoic acids were estimated by indirect calibration methods (GomezGonzalez et al, 2012;Fu et al, 2009;Warnke et al, 2006).…”

Section: Introductionmentioning

confidence: 99%

Acidic reaction products of monoterpenes and sesquiterpenes in atmospheric fine particles in a boreal forest

et al. 2014

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Abstract. Biogenic acids were measured in aerosols at the SMEAR II (Station for Measuring Forest EcosystemAtmosphere Relations II) station in Finland from June 2010 until October 2011. The analysed organic acids were pinic, pinonic, caric, limonic and caryophyllinic acids from oxidation of α-pinene, β-pinene, limonene, 3 -carene and β-caryophyllene, respectively. Due to a lack of authentic standards, the caric, limonic and caryophyllinic acids were synthesised for this study. The mean, median, maximum and minimum concentrations (ng m −3 ) were as follows: limonic acid (1.26, 0.80, 16.5, below detection limit (< LOD)), pinic acid (5.53, 3.25, 31.4, 0.15), pinonic acid (9.87, 5.07, 80.1, < LOD), caric acid (5.52, 3.58, 49.8, < LOD), and caryophyllinic acid (7.87, 6.07, 86.1, < LOD).The highest terpenoic acid concentrations were measured during the summer. Of the acids, β-caryophyllinic acid showed the highest concentrations in summer, but during other times of the year pinonic acid was the most abundant. The β-caryophyllinic acid contribution was higher than expected, based on the emission calculations of the precursor compounds and yields from oxidation experiments in smog chambers, implying that the β-caryophyllene emissions or β-caryophyllinic acid yields were underestimated. The concentration ratios between terpenoic acids and their precursors were clearly lower in summer than in winter, indicating stronger partitioning to the aerosol phase during the cold winter season. The β-caryophyllinic and caric acids were weakly correlated with the accumulation-mode particle number concentrations.

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Organosulfates and oxidation products from biogenic hydrocarbons in fine aerosols from a forest in North West Europe during spring

Cited by 150 publications

References 58 publications

Biogenic, urban, and wildfire influences on the molecular composition of dissolved organic compounds in cloud water

Biogenic, urban, and wildfire influences on the molecular composition of dissolved organic compounds in cloud water

Organosulfates from Pinene and Isoprene over the Pearl River Delta, South China: Seasonal Variation and Implication in Formation Mechanisms

Acidic reaction products of monoterpenes and sesquiterpenes in atmospheric fine particles in a boreal forest

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