Effect of Acidity on Secondary Organic Aerosol Formation from Isoprene

Surratt, Jason D.; Lewandowski, Michael; Offenberg, John H.; Jaoui, Mohammed; Kleindienst, Tadeusz E.; Edney, Edward O.; Seinfeld, John H.

doi:10.1021/es0704176

Cited by 496 publications

(540 citation statements)

References 37 publications

(92 reference statements)

Supporting

Mentioning

496

Contrasting

Unclassified

Order By: Relevance

“…The ESI tandem MS was operated with nebulizer pressure at 0.8 bar and a dry gas flow of 10 L min −1 . A solution of camphor sulfonic acid (Sigma-Aldrich, USA) was used to optimize ionization and fragmentation parameters to gain high intensity of [M−H] − , the resulting ionization voltage was 4 kV and the fragmentor was 120 V. 34 S-containing isotopic peaks coincident with the target ions provided an additional confirmation of 32 Scontaining formulas. 35 For pNOSs, additional MS/MS product ions with m/z 247 (loss of HNO 2 ) and m/z 231 (loss of HNO 3 ) were detected.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…In contrast, pNOSs are formed by heterogeneous reactions on acidic particles. 9,34,57 High sulfate levels would promote pNOSs' formation. 26 Since there was no significant difference in aerosol acidity between summer and fall (p > 0.05), aerosol acidity should not be the major factor leading to the seasonal differences in correlations between terpenoic acids and pNOSs.…”

Section: Environmental Science and Technologymentioning

confidence: 99%

“…31 A previous study found that the correlation between aerosol acidity and 2-methyltetrols, which could be also formed by the uptake of IEPOX, was much weaker in the air of South China 32 as compared with that in chamber studies. 33,34 Thus, more field studies in highly polluted regions are needed to provide insight into the formation mechanisms of biogenic OSs under the impact of anthropogenic pollution.…”

Section: ■ Introductionmentioning

confidence: 99%

See 2 more Smart Citations

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

View full text Add to dashboard Cite

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...

show abstract

Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: Environmental Science and Technologymentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

See 1 more Smart Citation

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

View full text Add to dashboard Cite

show abstract

“…Aromatic peroxy radicals (RO 2 ) react with HO 2 under low NO x conditions to form non-volatile SOA while they reacted with NO under high NO x conditions to form semi-volatile SOA. In addition, the Base model treats the acid enhancement of isoprene SOA (Surratt et al, 2007) and irreversible particle-phase oligomerization (Kalberer et al, 2004), which converts semi-volatile condensed-phase species into non-volatile species. We do not consider SOA formation from IVOCs or via aqueous-phase processing.…”

Section: Base Soa Modelmentioning

confidence: 99%

Multi-generational oxidation model to simulate secondary organic aerosol in a 3-D air quality model

et al. 2015

View full text Add to dashboard Cite

Abstract. Multi-generational gas-phase oxidation of organic vapors can influence the abundance, composition and properties of secondary organic aerosol (SOA). Only recently have SOA models been developed that explicitly represent multigenerational SOA formation. In this work, we integrated the statistical oxidation model (SOM) into SAPRC-11 to simulate the multi-generational oxidation and gas/particle partitioning of SOA in the regional UCD/CIT (University of California, Davis/California Institute of Technology) air quality model. In the SOM, evolution of organic vapors by reaction with the hydroxyl radical is defined by (1) the number of oxygen atoms added per reaction, (2) the decrease in volatility upon addition of an oxygen atom and (3) the probability that a given reaction leads to fragmentation of the organic molecule. These SOM parameter values were fit to laboratory smog chamber data for each precursor/compound class. SOM was installed in the UCD/CIT model, which simulated air quality over 2-week periods in the South Coast Air Basin of California and the eastern United States. For the regions and episodes tested, the two-product SOA model and SOM produce similar SOA concentrations but a modestly different SOA chemical composition. Predictions of the oxygen-tocarbon ratio qualitatively agree with those measured globally using aerosol mass spectrometers. Overall, the implementation of the SOM in a 3-D model provides a comprehensive framework to simulate the atmospheric evolution of organic aerosol.

show abstract

“…chamber research. Studies have shown that the mass of SOC and the acidity of laboratory-generated aerosol exhibited a linear relationship (Surratt et al, 2007). In this study, the relationship between WSOC and acidity was explored for the purpose of providing the direct evidence for enhanced WSOC formation at high level of acidity in the field-based research.…”

Section: àmentioning

confidence: 99%

Source and formation characteristics of water-soluble organic carbon in the anthropogenic-influenced Yellow River Delta, North China

Zong

Wang

Tian

et al. 2016

Atmospheric Environment

View full text Add to dashboard Cite

h i g h l i g h t sHigh intensity measurement of WSOC in PM 2.5 was conducted at Yellow River Delta. WSOC concentration in day time was obviously higher than night time. WSOC was mostly secondary formation product and was enhanced at high level of acidity. Biogenic and biomass burning (B&B) was the major source of WSOC. Fossil fuel contribution, mainly vehicle emission, could not be ignored. High intensity measurement of water-soluble organic carbon (WSOC) in PM 2.5 was conducted at Yellow River Delta (YRD), North China, from 29 May to 1 July 2013. On average, concentration of WSOC was 3.09 ± 2.45 mg m À3 with a relative high WSOC/OC mass ratio (56.39%), implying organic aerosol in YRD was aged. WSOC concentration in day time was obviously higher than night time, which was mainly attributed to the decrease of source emission. While secondary formation of WSOC was strengthen in night time under stable atmospheric condition. The significant relationship between WSOC and SOC indicated WSOC was mostly secondary formation product. Furthermore, WSOC formation was enhanced at high level of acidity, providing direct evidence for the great impact of aerosol acidity on WSOC formation. WSOC correlated well with nss-K þ , nss-SO 4 2À , NO 3 À , Zn and Cu, suggesting a major part of observed WSOC and/or its precursors was of biomass burning and fossil fuel combustion origin. Moreover, vehicle emission may make great proportion in the fossil fuel combustion. Conditional probability function (CPF) analysis showed significant contribution of WSOC occurred when wind came from southerly (135e195 ) and northwesterly (285, 345 ) directions. In order to further confirm the source of WSOC, two merged samples representing the two directions were selected for radiocarbon ( 14 C) measurement. 14 C results demonstrated the average value of G c (WSOC) was 0.57 ± 0.01, implying biogenic and biomass burning (B&B) was the major source of WSOC. However, fossil fuel contribution could not be ignored in North China in summer.

show abstract

Effect of Acidity on Secondary Organic Aerosol Formation from Isoprene

Cited by 496 publications

References 37 publications

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

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

Multi-generational oxidation model to simulate secondary organic aerosol in a 3-D air quality model

Source and formation characteristics of water-soluble organic carbon in the anthropogenic-influenced Yellow River Delta, North China

Contact Info

Product

Resources

About