Biogenic VOC oxidation and organic aerosol formation in an urban nocturnal boundary layer: aircraft vertical profiles in Houston, TX

Brown, Steven S.; Dubé, W. P.; Bahreini, R.; Middlebrook, A. M.; Brock, C. A.; Warneke, C.; Gouw, J. A. de; Washenfelder, R. A.; Atlas, Elliot L.; Peischl, J.; Ryerson, Thomas B.; Holloway, J. S.; Schwarz, J. P.; Spackman, R.; Trainer, M.; Parrish, D. D.; Fehshenfeld, F. C.; Ravishankara, A. R.

doi:10.5194/acp-13-11317-2013

Cited by 65 publications

(57 citation statements)

References 70 publications

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“…Organic nitrate functional groups formed as a secondary but nonnegligible branch of RO 2 +NO have been observed to contribute significantly to atmospheric aerosol in field studies [ Brown et al ., ; Day et al ., ; Zaveri et al ., ; Beaver et al ., ; Rollins et al ., ; Brown et al ., ; Fry et al ., ; Lin et al ., ; Xu et al ., , ; Lee et al ., ] and chamber experiments [e.g., Boyd et al ., ; D'Ambro et al ., ; J. Liu et al ., ]. The importance of BVOC+NO 3 chemistry as a nighttime SOA formation mechanism has gained recent attention [ Griffin et al ., ; Ng et al ., ; Rollins et al ., ; Fry et al ., ; Boyd et al ., ; Rindelaub et al ., ; Xu et al ., ; Nah et al ., ], as described in a recent review [ Ng et al ., ].…”

Section: Biogenic Emissions and Soa Formationmentioning

confidence: 98%

Recent advances in understanding secondary organic aerosol: Implications for global climate forcing

Shrivastava

Cappa

Fan

et al. 2017

Reviews of Geophysics

723

668

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Anthropogenic emissions and land use changes have modified atmospheric aerosol concentrations and size distributions over time. Understanding preindustrial conditions and changes in organic aerosol due to anthropogenic activities is important because these features (1) influence estimates of aerosol radiative forcing and (2) can confound estimates of the historical response of climate to increases in greenhouse gases. Secondary organic aerosol (SOA), formed in the atmosphere by oxidation of organic gases, represents a major fraction of global submicron‐sized atmospheric organic aerosol. Over the past decade, significant advances in understanding SOA properties and formation mechanisms have occurred through measurements, yet current climate models typically do not comprehensively include all important processes. This review summarizes some of the important developments during the past decade in understanding SOA formation. We highlight the importance of some processes that influence the growth of SOA particles to sizes relevant for clouds and radiative forcing, including formation of extremely low volatility organics in the gas phase, acid‐catalyzed multiphase chemistry of isoprene epoxydiols, particle‐phase oligomerization, and physical properties such as volatility and viscosity. Several SOA processes highlighted in this review are complex and interdependent and have nonlinear effects on the properties, formation, and evolution of SOA. Current global models neglect this complexity and nonlinearity and thus are less likely to accurately predict the climate forcing of SOA and project future climate sensitivity to greenhouse gases. Efforts are also needed to rank the most influential processes and nonlinear process‐related interactions, so that these processes can be accurately represented in atmospheric chemistry‐climate models.

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Section: Biogenic Emissions and Soa Formationmentioning

confidence: 98%

Recent advances in understanding secondary organic aerosol: Implications for global climate forcing

Shrivastava

Cappa

Fan

et al. 2017

Reviews of Geophysics

723

668

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“…As NO 3 concentration depends on the availability of NO x , a substantial fraction of the biogenic SOA formed at night is controlled by anthropogenic emissions, as has been observed and predicted in several regions across the United States, Europe, and China (Ayres et al, 2015; Brown et al, 2013; Fry et al, 2018; Kiendler‐Scharr et al, 2016; Pye et al, 2015; Rollins et al, 2012; Yu et al, 2019; Zaveri et al, 2010). We report here on nighttime biogenic SOA formation in a polluted residual layer over Sacramento, California, during the Carbonaceous Aerosols and Radiative Effects Study (CARES) in June 2010 (Zaveri et al, 2012).…”

Section: Introductionmentioning

confidence: 85%

“…The NO 3 radicals, produced from the reaction of nitrogen dioxide (NO 2 ) with O 3 , can reach appreciable concentrations at night in the absence of losses due to photolysis and rapid reaction with nitric oxide (NO). The olefinic bonds in isoprene and monoterpenes can react with NO 3 to form organic nitrates (RONO2), some of which can partially partition to the particle phase to form SOA (Ayres et al, 2015; Beaver et al, 2012; Brown et al, 2013; Fisher et al, 2016; Fry et al, 2009, 2014; Hallquist et al, 1999; B. H. Lee et al, 2016; Paulot et al, 2009; Rollins et al, 2012; Rollins et al, 2009; Schwantes et al, 2015; Starn et al, 1998). The SOA yields for NO 3 oxidation pathway are generally much larger than those for OH and O 3 oxidation (Fry et al, 2009, 2014; Hallquist et al, 1999; Ng et al, 2008; Rollins et al, 2009; Schwantes et al, 2015) because the addition of the NO 3 group lowers the vapor pressure by a larger amount than most other single functionalities.…”

Section: Introductionmentioning

confidence: 99%

Efficient Nighttime Biogenic SOA Formation in a Polluted Residual Layer

et al. 2020

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Organic nitrates formed from nighttime reaction between anthropogenic nitrate radicals (NO3) and biogenic volatile organic compounds (BVOCs) are an important but highly uncertain source of secondary organic aerosol (SOA). Here we report on the enhanced nighttime biogenic SOA formation observed in a polluted residual layer over Sacramento, California, the morning of 15 June 2010 during the Carbonaceous Aerosols and Radiative Effects Study (CARES). Trajectory analysis showed that the residual layer air, containing isoprene and trace amounts of monoterpenes left over after nighttime oxidation, was influenced by the San Francisco Bay Area emissions the previous evening. The residual layer aerosol was also enriched in nitrate, with about 64% of it estimated to be in the form of organic nitrates. The nitrate:organic mass ratio of the SOA was about 0.47 ± 0.044, which corresponds to the range typically found in isoprene mononitrates. Assuming the SOA was composed of organic mononitrates, its nominal molecular weight was estimated at 186 ± 11 g mol−1, consistent with the highly functionalized isoprene hydroxynitrates that have been observed in the particle phase in the southeast United States. Overall, our findings show that the efficiency of nighttime biogenic SOA formation, expressed as the change in organic aerosol mass relative to carbon monoxide (∆OA/∆CO), equals ~100 μg m−3 ppmv and is comparable to the range previously estimated for enhanced daytime SOA formation from mixed anthropogenic and biogenic emissions during CARES. Assuming the SOA was formed from isoprene oxidation by NO3, we estimated mass yields of up to 0.55, consistent with previous field estimates.

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“…Depending on the relative amount of these different types of organic nitrates, the overall hydrolysis rate could be different for organic nitrates formed from NO 3 oxidation and photooxidation in the presence of NO x . Recently, there has been increasing evidence from field measurements that organic nitrates hydrolyze in the particle phase, producing HNO 3 (Liu et al, 2012b;Browne et al, 2013). This has been only a limited focus of chamber experiments to date .…”

Section: Mechanismsmentioning

confidence: 99%

Review response

Brown¹

2016

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Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO 3 ) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than 3 decades, during which time a large body of research has emerged from laboratory, field, and modeling studies. NO 3 -BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone, and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number of important uncertainties remain. These include an incomplete understanding of the rates, mechanisms, and organic aerosol yields for NO 3 -BVOC reactions, lack of constraints on the role of heterogeneous oxidative processes associated with the NO 3 radical, the difficulty of characterizing the spatial distributions of BVOC and NO 3 within the poorly mixed nocturnal atmosphere, and the challenge of constructing appropriate boundary layer schemes and non-photochemical mechanisms for use in state-of-the-art chemical transport and chemistry-climate models.This review is the result of a workshop of the same title held at the Georgia Institute of Technology in June 2015. The first half of the review summarizes the current literature on NO 3 -BVOC chemistry, with a particular focus on recent advances in instrumentation and models, and in organic nitrate and secondary organic aerosol (SOA) formation chemistry. Building on this current understanding, the second half of the review outlines impacts of NO 3 -BVOC chemistry on air quality and climate, and suggests critical research needs to better constrain this interaction to improve the predictive capabilities of atmospheric models. Isoprene Monoterpenes O 3 •NO 3 NO x Nitrates Aerosol Biogenic VOCs NO, NO 2 Air quality Climate Atmos.

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Biogenic VOC oxidation and organic aerosol formation in an urban nocturnal boundary layer: aircraft vertical profiles in Houston, TX

Cited by 65 publications

References 70 publications

Recent advances in understanding secondary organic aerosol: Implications for global climate forcing

Recent advances in understanding secondary organic aerosol: Implications for global climate forcing

Efficient Nighttime Biogenic SOA Formation in a Polluted Residual Layer

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