Articles | Volume 16, issue 3
17 Feb 2016
Research article | 17 Feb 2016
Organic peroxides' gas-particle partitioning and rapid heterogeneous decomposition on secondary organic aerosol
Huan Li et al.
No articles found.
Jiayun Xu, Zhongming Chen, Xuan Qin, and Ping Dong
Atmos. Chem. Phys. Discuss.,
Preprint under review for ACPShort summary
We investigated the photooxidation of isoprene in the presence of water. We found that water enhanced the formation of methacrolein and methyl vinyl ketone in the first-generation reactions by changing the structures of the reaction intermediates and raised formic acid and acetic acid yields considerably in the multi-generation reactions. The results of this study help understand the fate of isoprene in the atmosphere and improve the effect of the atmospheric simulations.
Jingcheng Hu, Zhongming Chen, Xuan Qin, and Ping Dong
Atmos. Chem. Phys., 22, 6971–6987,Short summary
The gas–particle partitioning process of glyoxal and methylglyoxal could contribute to secondary organic aerosol formation. Here, we launched five observations in different seasons and simultaneously measured glyoxal and methylglyoxal in the gas and particle phases. Compared to reversible pathways, irreversible pathways played a dominant role with a proportion of more than 90 % in the ambient atmosphere, and the proportion was influenced by relative humidity and inorganic components in aerosols.
Yiwei Gong and Zhongming Chen
Atmos. Chem. Phys., 21, 813–829,Short summary
Stabilized Criegee intermediates (SCIs) are important factors in estimating aerosol formation in the atmosphere. Here the results show that SCIs account for more than 60 % of aerosol formation in limonene ozonolysis and water is an uncertainty in SCI performances. The aerosol formation potential of SCIs under high-humidity conditions is double that under dry and low-humidity conditions, suggesting SCI reactions are still important in contributing to aerosols at high relative humidity.
Xiaoning Xuan, Zhongming Chen, Yiwei Gong, Hengqing Shen, and Shiyi Chen
Atmos. Chem. Phys., 20, 5513–5526,Short summary
In this study, we found that the effective field-derived Henry's law constant for the ground rainwater and the gas-phase H2O2 was about 2.5 times that of the theoretical value, and the effective gas–particle partitioning coefficient for the aerosol particle and the gas-phase H2O2 was 4 orders of magnitude higher than the theoretical one. We suggested the missing source of H2O2 in the particulate phase, e.g. the contribution from the decomposition/hydrolysis of organic peroxides.
Yiwei Gong, Zhongming Chen, and Huan Li
Atmos. Chem. Phys., 18, 15105–15123,Short summary
In limonene ozonolysis, the endocyclic double bond is inclined to generate hydroxy radicals, while the exocyclic double bond has a higher fraction of forming stabilized Criegee intermediates. The oxidation that happens on the exocyclic double bond greatly contributes to the organic peroxides, which account for a considerable proportion of secondary organic aerosol. Terpenes with multiple double bonds may have more complex effects on the atmosphere than previously thought.
Yin Wang, Zhongming Chen, Qinqin Wu, Hao Liang, Liubin Huang, Huan Li, Keding Lu, Yusheng Wu, Huabin Dong, Limin Zeng, and Yuanhang Zhang
Atmos. Chem. Phys., 16, 10985–11000,Short summary
Comparison of modeled and measured peroxide concentrations at a rural site in the summer North China Plain demonstrated an underestimation during biomass burning events and an overestimation on haze days, which were related to the direct production of peroxides from biomass burning and the heterogeneous uptake of peroxides by aerosols, respectively. Our findings are of great significance for comprehensively understanding the chemical budget of atmospheric peroxides in detail.
Q. Q. Wu, L. B. Huang, H. Liang, Y. Zhao, D. Huang, and Z. M. Chen
Atmos. Chem. Phys., 15, 6851–6866,Short summary
The present study provides the first measurement for the uptake coefficient of gaseous peroxide compounds including peroxyacetic acid and hydrogen peroxide on the ambient particles (PM2.5 and Asian Storm Dust) over a wide range of relative humidity. The measured uptake coefficient values suggest that the heterogeneous reaction on the ambient particles plays an important role in the atmospheric budgets of peroxide compounds and potentially affects the components of aerosols in the atmosphere.
H. Liang, Z. M. Chen, D. Huang, Q. Q. Wu, and L. B. Huang
Atmos. Chem. Phys. Discuss.,
Revised manuscript not acceptedShort summary
The present field measurements have provided strong evidence for the existence of peroxyformic acid (HC(O)OOH) in the atmosphere for the first time. Moreover, the potential impact of peroxyformic acid chemistry on the formic acid production and the radical budget has been evaluated on the basis of model calculations. Our findings are of importance for a full understanding of the cycling of oxidants and the source of organic acids in the atmosphere.
H. Liang, Z. M. Chen, D. Huang, Y. Zhao, and Z. Y. Li
Atmos. Chem. Phys., 13, 11259–11276,
R. Zhang, J. Jing, J. Tao, S.-C. Hsu, G. Wang, J. Cao, C. S. L. Lee, L. Zhu, Z. Chen, Y. Zhao, and Z. Shen
Atmos. Chem. Phys., 13, 7053–7074,
D. Huang, Z. M. Chen, Y. Zhao, and H. Liang
Atmos. Chem. Phys., 13, 5671–5683,
Related subject area
Subject: Gases | Research Activity: Laboratory Studies | Altitude Range: Troposphere | Science Focus: Chemistry (chemical composition and reactions)Impact of cooking style and oil on semi-volatile and intermediate volatility organic compound emissions from Chinese domestic cookingObservations of gas-phase products from the nitrate-radical-initiated oxidation of four monoterpenesInvestigation of the limonene photooxidation by OH at different NO concentrations in the atmospheric simulation chamber SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction Chamber)Kinetic study of the atmospheric oxidation of a series of epoxy compounds by OH radicalsAn experimental study of the reactivity of terpinolene and β-caryophyllene with the nitrate radicalOxidation product characterization from ozonolysis of the diterpene ent-kaureneKinetics of OH + SO2 + M: temperature-dependent rate coefficients in the fall-off regime and the influence of water vapourFormation of organic sulfur compounds through SO2-initiated photochemistry of PAHs and dimethylsulfoxide at the air-water interfaceStable carbon isotopic composition of biomass burning emissions – implications for estimating the contribution of C3 and C4 plantsEvaluation of the daytime tropospheric loss of 2-methylbutanalInvestigations into the gas-phase photolysis and OH radical kinetics of nitrocatechols: implications of intramolecular interactions on their atmospheric behaviourReproducing Arctic springtime tropospheric ozone and mercury depletion events in an outdoor mesocosm sea ice facilityN2O5 uptake onto saline mineral dust: a potential missing source of tropospheric ClNO2 in inland ChinaNO3 chemistry of wildfire emissions: a kinetic study of the gas-phase reactions of furans with the NO3 radicalMarine gas-phase sulfur emissions during an induced phytoplankton bloomBiomass burning plume chemistry: OH-radical-initiated oxidation of 3-penten-2-one and its main oxidation product 2-hydroxypropanalAtmospheric photo-oxidation of myrcene: OH reaction rate constant, gas-phase oxidation products and radical budgetsCharacterization of ambient volatile organic compounds, source apportionment, and the ozone–NOx–VOC sensitivities in a heavily polluted megacity of central China: effect of sporting events and emission reductionsAtmospheric oxidation of α,β-unsaturated ketones: kinetics and mechanism of the OH radical reactionReactions of NO3 with aromatic aldehydes: gas-phase kinetics and insights into the mechanism of the reactionAtmospheric photooxidation and ozonolysis of Δ3-carene and 3-caronaldehyde: rate constants and product yieldsMeasurement report: Biogenic volatile organic compound emission profiles of rapeseed leaf litter and its secondary organic aerosol formation potentialHighly oxygenated organic molecules produced by the oxidation of benzene and toluene in a wide range of OH exposure and NOx conditionsMolecular composition and volatility of multi-generation products formed from isoprene oxidation by nitrate radicalHighly oxygenated organic molecule (HOM) formation in the isoprene oxidation by NO3 radicalVolatile organic compound emissions from solvent- and water-borne coatings – compositional differences and tracer compound identificationsEvaluated kinetic and photochemical data for atmospheric chemistry: volume VIII – gas-phase reactions of organic species with four, or more, carbon atoms ( ≥ C4)Chemical characterisation of benzene oxidation products under high- and low-NOx conditions using chemical ionisation mass spectrometryEmissions of non-methane volatile organic compounds from combustion of domestic fuels in Delhi, IndiaA comparative and experimental study of the reactivity with nitrate radical of two terpenes: α-terpinene and γ-terpinenePhotooxidation of pinonaldehyde at ambient conditions investigated in the atmospheric simulation chamber SAPHIRReaction between CH3C(O)OOH (peracetic acid) and OH in the gas phase: a combined experimental and theoretical study of the kinetics and mechanismSnow heterogeneous reactivity of bromide with ozone lost during snow metamorphismEvaluated kinetic and photochemical data for atmospheric chemistry: Volume VII – Criegee intermediatesTechnical Note: Effect of varying the λ = 185 and 254 nm photon flux ratio on radical generation in oxidation flow reactorsKinetics of dimethyl sulfide (DMS) reactions with isoprene-derived Criegee intermediates studied with direct UV absorptionDetermination of the absorption cross sections of higher-order iodine oxides at 355 and 532 nmEvolution of NO3 reactivity during the oxidation of isopreneRate coefficients for reactions of OH with aromatic and aliphatic volatile organic compounds determined by the multivariate relative rate techniqueAtmospheric fate of two relevant unsaturated ketoethers: kinetics, products and mechanisms for the reaction of hydroxyl radicals with (E)-4-methoxy-3-buten-2-one and (1E)-1-methoxy-2-methyl-1-penten-3-oneThe nitrogen budget of laboratory-simulated western US wildfires during the FIREX 2016 Fire Lab studyImportance of isomerization reactions for OH radical regeneration from the photo-oxidation of isoprene investigated in the atmospheric simulation chamber SAPHIRKinetics of the OH + NO2 reaction: effect of water vapour and new parameterization for global modellingKinetic and mechanistic study of the reaction between methane sulfonamide (CH3S(O)2NH2) and OHDimensionality-reduction techniques for complex mass spectrometric datasets: application to laboratory atmospheric organic oxidation experimentsAtmospheric fate of a series of saturated alcohols: kinetic and mechanistic studyMulti-generation OH oxidation as a source for highly oxygenated organic molecules from aromaticsPhotolysis and oxidation by OH radicals of two carbonyl nitrates: 4-nitrooxy-2-butanone and 5-nitrooxy-2-pentanonePotential dual effect of anthropogenic emissions on the formation of biogenic secondary organic aerosol (BSOA)Effect of NOx on 1,3,5-trimethylbenzene (TMB) oxidation product distribution and particle formation
Kai Song, Song Guo, Yuanzheng Gong, Daqi Lv, Yuan Zhang, Zichao Wan, Tianyu Li, Wenfei Zhu, Hui Wang, Ying Yu, Rui Tan, Ruizhe Shen, Sihua Lu, Shuangde Li, Yunfa Chen, and Min Hu
Atmos. Chem. Phys., 22, 9827–9841,Short summary
Emissions from four typical Chinese domestic cooking and fried chicken using four kinds of oils were investigated to illustrate the impact of cooking style and oil. Of the estimated SOA, 10.2 %–32.0 % could be explained by S/IVOC oxidation. Multiway principal component analysis (MPCA) emphasizes the importance of the unsaturated fatty acid-alkadienal volatile product mechanism (oil autoxidation) accelerated by the cooking and heating procedure.
Michelia Dam, Danielle C. Draper, Andrey Marsavin, Juliane L. Fry, and James N. Smith
Atmos. Chem. Phys., 22, 9017–9031,Short summary
We performed chamber experiments to measure the composition of the gas-phase reaction products of nitrate-radical-initiated oxidation of four monoterpenes. The total organic yield, effective oxygen-to-carbon ratio, and dimer-to-monomer ratio were correlated with the observed particle formation for the monoterpene systems with some exceptions. The Δ-carene system produced the most particles, followed by β-pinene, with the α-pinene and α-thujene systems producing no particles.
Jacky Yat Sing Pang, Anna Novelli, Martin Kaminski, Ismail-Hakki Acir, Birger Bohn, Philip T. M. Carlsson, Changmin Cho, Hans-Peter Dorn, Andreas Hofzumahaus, Xin Li, Anna Lutz, Sascha Nehr, David Reimer, Franz Rohrer, Ralf Tillmann, Robert Wegener, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 22, 8497–8527,Short summary
This study investigates the radical chemical budget during the limonene oxidation at different atmospheric-relevant NO concentrations in chamber experiments under atmospheric conditions. It is found that the model–measurement discrepancies of HO2 and RO2 are very large at low NO concentrations that are typical for forested environments. Possible additional processes impacting HO2 and RO2 concentrations are discussed.
Carmen Maria Tovar, Ian Barnes, Iustinian Gabriel Bejan, and Peter Wiesen
Atmos. Chem. Phys., 22, 6989–7004,Short summary
This work explores the kinetics and reactivity of epoxides towards the OH radical using two different simulation chambers. Estimation of the rate coefficients has also been made using different structure–activity relationship (SAR) approaches. The results indicate a direct influence of the structural and geometric properties of the epoxides not considered in SAR estimations, influencing the reactivity of these compounds. The outcomes of this work are in very good agreement with previous studies.
Axel Fouqueau, Manuela Cirtog, Mathieu Cazaunau, Edouard Pangui, Jean-François Doussin, and Bénédicte Picquet-Varrault
Atmos. Chem. Phys., 22, 6411–6434,Short summary
Biogenic volatile organic compounds are intensely emitted by forests and crops and react with the nitrate radical during the nighttime to form functionalized products. The purpose of this study is to furnish kinetic and mechanistic data for terpinolene and β-caryophyllene, using simulation chamber experiments. Rate constants have been measured using both relative and absolute methods, and mechanistic studies have been conducted in order to identify and quantify the main reaction products.
Yuanyuan Luo, Olga Garmash, Haiyan Li, Frans Graeffe, Arnaud P. Praplan, Anssi Liikanen, Yanjun Zhang, Melissa Meder, Otso Peräkylä, Josep Peñuelas, Ana María Yáñez-Serrano, and Mikael Ehn
Atmos. Chem. Phys., 22, 5619–5637,Short summary
Diterpenes were only recently observed in the atmosphere, and little is known of their atmospheric fates. We explored the ozonolysis of the diterpene kaurene in a chamber, and we characterized the oxidation products for the first time using chemical ionization mass spectrometry. Our findings highlight similarities and differences between diterpenes and smaller terpenes during their atmospheric oxidation.
Wenyu Sun, Matias Berasategui, Andrea Pozzer, Jos Lelieveld, and John N. Crowley
Atmos. Chem. Phys., 22, 4969–4984,Short summary
The reaction between OH and SO2 is a termolecular process that in the atmosphere results in the formation of H2SO4 and thus aerosols. We present the first temperature- and pressure-dependent measurements of the rate coefficients in N2. This is also the first study to examine the effects of water vapour on the kinetics of this reaction. Our results indicate the rate coefficient is larger than that recommended by evaluation panels, with deviations of up to 30 % in some parts of the atmosphere.
Haoyu Jiang, Yingyao He, Yiqun Wang, Sheng Li, Bin Jiang, Luca Carena, Xue Li, Lihua Yang, Tiangang Luan, Davide Vione, and Sasho Gligorovski
Atmos. Chem. Phys., 22, 4237–4252,Short summary
Heterogeneous oxidation of SO2 is suggested to be one of the most important pathways for sulfate formation during extreme haze events in China, yet the exact mechanism remains highly uncertain. Our study reveals that ubiquitous compounds at the sea surface PAHS and DMSO, when exposed to SO2 under simulated sunlight irradiation, generate abundant organic sulfur compounds, providing implications for air-sea interaction and secondary organic aerosols formation processes.
Roland Vernooij, Ulrike Dusek, Maria Elena Popa, Peng Yao, Anupam Shaikat, Chenxi Qiu, Patrik Winiger, Carina van der Veen, Thomas Callum Eames, Natasha Ribeiro, and Guido R. van der Werf
Atmos. Chem. Phys., 22, 2871–2890,Short summary
Landscape fires are a major source of greenhouse gases and aerosols, particularly in sub-tropical savannas. Stable carbon isotopes in emissions can be used to trace the contribution of C3 plants (e.g. trees or shrubs) and C4 plants (e.g. savanna grasses) to greenhouse gases and aerosols if the process is well understood. This helps us to link individual vegetation types to emissions, identify biomass burning emissions in the atmosphere, and improve the reconstruction of historic fire regimes.
María Asensio, María Antiñolo, Sergio Blázquez, José Albaladejo, and Elena Jiménez
Atmos. Chem. Phys., 22, 2689–2701,Short summary
The diurnal atmospheric degradation of 2-methylbutanal, 2 MB, emitted by sources like vegetation or the poultry industry is evaluated in this work. Sunlight and oxidants like hydroxyl (OH) radicals and chlorine (Cl) atoms initiate this degradation. Measurements of how fast 2 MB is degraded and what products are generated are presented. The lifetime of 2 MB is around 1 h at noon, when the OH reaction dominates. Thus, 2 MB will not be transported far, affecting only local air quality.
Claudiu Roman, Cecilia Arsene, Iustinian Gabriel Bejan, and Romeo Iulian Olariu
Atmos. Chem. Phys., 22, 2203–2219,Short summary
Gas-phase reaction rate coefficients of OH radicals with four nitrocatechols have been investigated for the first time by using ESC-Q-UAIC chamber facilities. The reactivity of all investigated nitrocatechols is influenced by the formation of the intramolecular H-bonds that are connected to the deactivating electromeric effect of the NO2 group. For the 3-nitrocatechol compounds, the electromeric effect of the
freeOH group is diminished by the deactivating E-effect of the NO2 group.
Zhiyuan Gao, Nicolas-Xavier Geilfus, Alfonso Saiz-Lopez, and Feiyue Wang
Atmos. Chem. Phys., 22, 1811–1824,Short summary
Every spring in the Arctic, a series of photochemical events occur over the ice-covered ocean, known as bromine explosion events, ozone depletion events, and mercury depletion events. Here we report the re-creation of these events at an outdoor sea ice facility in Winnipeg, Canada, far away from the Arctic. The success provides a new platform with new opportunities to uncover fundamental mechanisms of these Arctic springtime phenomena and how they may change in a changing climate.
Haichao Wang, Chao Peng, Xuan Wang, Shengrong Lou, Keding Lu, Guicheng Gan, Xiaohong Jia, Xiaorui Chen, Jun Chen, Hongli Wang, Shaojia Fan, Xinming Wang, and Mingjin Tang
Atmos. Chem. Phys., 22, 1845–1859,Short summary
Via combining laboratory and modeling work, we found that heterogeneous reaction of N2O5 with saline mineral dust aerosol could be an important source of tropospheric ClNO2 in inland regions.
Mike J. Newland, Yangang Ren, Max R. McGillen, Lisa Michelat, Véronique Daële, and Abdelwahid Mellouki
Atmos. Chem. Phys., 22, 1761–1772,Short summary
Wildfires are increasing in extent and severity, driven by climate change. Such fires emit large amounts of volatile organic compounds (VOCs) to the atmosphere. Many of these, such as the furans studied here, are very reactive and are rapidly converted to other VOCs, which are expected to have negative health effects and to further impact the climate. Here, we establish the importance of the nitrate radical for removing these compounds both during the night and during the day.
Delaney B. Kilgour, Gordon A. Novak, Jon S. Sauer, Alexia N. Moore, Julie Dinasquet, Sarah Amiri, Emily B. Franklin, Kathryn Mayer, Margaux Winter, Clare K. Morris, Tyler Price, Francesca Malfatti, Daniel R. Crocker, Christopher Lee, Christopher D. Cappa, Allen H. Goldstein, Kimberly A. Prather, and Timothy H. Bertram
Atmos. Chem. Phys., 22, 1601–1613,Short summary
We report measurements of gas-phase volatile organosulfur molecules made during a mesocosm phytoplankton bloom experiment. Dimethyl sulfide (DMS), methanethiol (MeSH), and benzothiazole accounted for on average over 90 % of total gas-phase sulfur emissions. This work focuses on factors controlling the production and emission of DMS and MeSH and the role of non-DMS molecules (such as MeSH and benzothiazole) in secondary sulfate formation in coastal marine environments.
Niklas Illmann, Iulia Patroescu-Klotz, and Peter Wiesen
Atmos. Chem. Phys., 21, 18557–18572,Short summary
Understanding the chemistry of biomass burning plumes is of global interest. Within this work we investigated the OH radical reaction of 3-penten-2-one, which has been identified in biomass burning emissions. We observed the primary formation of peroxyacetyl nitrate (PAN), a key NOx reservoir species. Besides, PAN precursors were also identified as main oxidation products. 3-Penten-2-one is shown to be an example explaining rapid PAN formation within young biomass burning plumes.
Zhaofeng Tan, Luisa Hantschke, Martin Kaminski, Ismail-Hakki Acir, Birger Bohn, Changmin Cho, Hans-Peter Dorn, Xin Li, Anna Novelli, Sascha Nehr, Franz Rohrer, Ralf Tillmann, Robert Wegener, Andreas Hofzumahaus, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 21, 16067–16091,Short summary
The photo-oxidation of myrcene, a monoterpene species emitted by plants, was investigated at atmospheric conditions in the outdoor simulation chamber SAPHIR. The chemical structure of myrcene is partly similar to isoprene. Therefore, it can be expected that hydrogen shift reactions could play a role as observed for isoprene. In this work, their potential impact on the regeneration efficiency of hydroxyl radicals is investigated.
Shijie Yu, Fangcheng Su, Shasha Yin, Shenbo Wang, Ruixin Xu, Bing He, Xiangge Fan, Minghao Yuan, and Ruiqin Zhang
Atmos. Chem. Phys., 21, 15239–15257,Short summary
This study measured 106 VOC species using a GC-MS/FID. Meanwhile, the WRF-CMAQ model was used to investigate the nonlinearity of the O3 response to precursor reductions. This study highlights the effectiveness of stringent emission controls in relation to solvent utilization and coal combustion. However, unreasonable emission reduction may aggravate ozone pollution during control periods. It is suggested that emission-reduction ratios of the precursors (VOC : NOx) should be more than 2.
Niklas Illmann, Rodrigo Gastón Gibilisco, Iustinian Gabriel Bejan, Iulia Patroescu-Klotz, and Peter Wiesen
Atmos. Chem. Phys., 21, 13667–13686,Short summary
Within this work we determined the rate coefficients and products of the reaction of unsaturated ketones with OH radicals in an effort to complete the gaps in the knowledge needed for modelling chemistry in the atmosphere. Both substances are potentially emitted by biomass burning, industrial activities or formed in the troposphere by oxidation of terpenes. As products we identified aldehydes and ketones which in turn are known to be responsible for the transportation of NOx species.
Yangang Ren, Li Zhou, Abdelwahid Mellouki, Véronique Daële, Mahmoud Idir, Steven S. Brown, Branko Ruscic, Robert S. Paton, Max R. McGillen, and A. R. Ravishankara
Atmos. Chem. Phys., 21, 13537–13551,Short summary
Aromatic aldehydes are a family of compounds emitted into the atmosphere from both anthropogenic and biogenic sources that are formed from the degradation of aromatic hydrocarbons. Their atmospheric degradation may impact air quality. We report on their atmospheric degradation through reaction with NO3, which is useful to estimate their atmospheric lifetimes. We have also attempted to elucidate the mechanism of these reactions via studies of isotopic substitution and quantum chemistry.
Luisa Hantschke, Anna Novelli, Birger Bohn, Changmin Cho, David Reimer, Franz Rohrer, Ralf Tillmann, Marvin Glowania, Andreas Hofzumahaus, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 21, 12665–12685,Short summary
The reactions of Δ3-carene with ozone and the hydroxyl radical (OH) and the photolysis and OH reaction of caronaldehyde were investigated in the simulation chamber SAPHIR. Reaction rate constants of these reactions were determined. Caronaldehyde yields of the ozonolysis and OH reaction were determined. The organic nitrate yield of the reaction of Δ3-carene and caronaldehyde-derived peroxy radicals with NO was determined. The ROx budget (ROx = OH+HO2+RO2) was also investigated.
Letizia Abis, Carmen Kalalian, Bastien Lunardelli, Tao Wang, Liwu Zhang, Jianmin Chen, Sébastien Perrier, Benjamin Loubet, Raluca Ciuraru, and Christian George
Atmos. Chem. Phys., 21, 12613–12629,Short summary
Biogenic volatile organic compound (BVOC) emissions from rapeseed leaf litter have been investigated by means of a controlled atmospheric simulation chamber. The diversity of emitted VOCs increased also in the presence of UV light irradiation. SOA formation was observed when leaf litter was exposed to both UV light and ozone, indicating a potential contribution to particle formation or growth at local scales.
Xi Cheng, Qi Chen, Yong Jie Li, Yan Zheng, Keren Liao, and Guancong Huang
Atmos. Chem. Phys., 21, 12005–12019,Short summary
In this study, we conducted laboratory studies to investigate the formation of gas-phase highly oxygenated organic molecules (HOMs). We provide a thorough analysis on the importance of multistep auto-oxidation and multigeneration OH reactions. We also give an intensive investigation on the roles of high-NO2 conditions that represent a wide range of anthropogenically influenced environments.
Rongrong Wu, Luc Vereecken, Epameinondas Tsiligiannis, Sungah Kang, Sascha R. Albrecht, Luisa Hantschke, Defeng Zhao, Anna Novelli, Hendrik Fuchs, Ralf Tillmann, Thorsten Hohaus, Philip T. M. Carlsson, Justin Shenolikar, François Bernard, John N. Crowley, Juliane L. Fry, Bellamy Brownwood, Joel A. Thornton, Steven S. Brown, Astrid Kiendler-Scharr, Andreas Wahner, Mattias Hallquist, and Thomas F. Mentel
Atmos. Chem. Phys., 21, 10799–10824,Short summary
Isoprene is the biogenic volatile organic compound with the largest emissions rates. The nighttime reaction of isoprene with the NO3 radical has a large potential to contribute to SOA. We classified isoprene nitrates into generations and proposed formation pathways. Considering the potential functionalization of the isoprene nitrates we propose that mainly isoprene dimers contribute to SOA formation from the isoprene NO3 reactions with at least a 5 % mass yield.
Defeng Zhao, Iida Pullinen, Hendrik Fuchs, Stephanie Schrade, Rongrong Wu, Ismail-Hakki Acir, Ralf Tillmann, Franz Rohrer, Jürgen Wildt, Yindong Guo, Astrid Kiendler-Scharr, Andreas Wahner, Sungah Kang, Luc Vereecken, and Thomas F. Mentel
Atmos. Chem. Phys., 21, 9681–9704,Short summary
The reaction of isoprene, a biogenic volatile organic compound with the globally largest emission rates, with NO3, an nighttime oxidant influenced heavily by anthropogenic emissions, forms a large number of highly oxygenated organic molecules (HOM). These HOM are formed via one or multiple oxidation steps, followed by autoxidation. Their total yield is much higher than that in the daytime oxidation of isoprene. They may play an important role in nighttime organic aerosol formation and growth.
Chelsea E. Stockwell, Matthew M. Coggon, Georgios I. Gkatzelis, John Ortega, Brian C. McDonald, Jeff Peischl, Kenneth Aikin, Jessica B. Gilman, Michael Trainer, and Carsten Warneke
Atmos. Chem. Phys., 21, 6005–6022,Short summary
Volatile chemical products are emerging as a large source of petrochemical organics in urban environments. We identify markers for the coatings category by linking ambient observations to laboratory measurements, investigating volatile organic compound (VOC) composition, and quantifying key VOC emissions via controlled evaporation experiments. Ingredients and sales surveys are used to confirm the prevalence and usage trends to support the assignment of water and solvent-borne coating tracers.
Abdelwahid Mellouki, Markus Ammann, R. Anthony Cox, John N. Crowley, Hartmut Herrmann, Michael E. Jenkin, V. Faye McNeill, Jürgen Troe, and Timothy J. Wallington
Atmos. Chem. Phys., 21, 4797–4808,Short summary
Volatile organic compounds play an important role in atmospheric chemistry. This article, the eighth in the series, presents kinetic and photochemical data sheets evaluated by the IUPAC Task Group on Atmospheric Chemical Kinetic Data Evaluation. It covers the gas-phase reactions of organic species with four, or more, carbon atoms (≥ C4) including thermal reactions of closed-shell organic species with HO and NO3 radicals and their photolysis. These data are important for atmospheric models.
Michael Priestley, Thomas J. Bannan, Michael Le Breton, Stephen D. Worrall, Sungah Kang, Iida Pullinen, Sebastian Schmitt, Ralf Tillmann, Einhard Kleist, Defeng Zhao, Jürgen Wildt, Olga Garmash, Archit Mehra, Asan Bacak, Dudley E. Shallcross, Astrid Kiendler-Scharr, Åsa M. Hallquist, Mikael Ehn, Hugh Coe, Carl J. Percival, Mattias Hallquist, Thomas F. Mentel, and Gordon McFiggans
Atmos. Chem. Phys., 21, 3473–3490,Short summary
A significant fraction of emissions from human activity consists of aromatic hydrocarbons, e.g. benzene, which oxidise to form new compounds important for particle growth. Characterisation of benzene oxidation products highlights the range of species produced as well as their chemical properties and contextualises them within relevant frameworks, e.g. MCM. Cluster analysis of the oxidation product time series distinguishes behaviours of CHON compounds that could aid in identifying functionality.
Gareth J. Stewart, W. Joe F. Acton, Beth S. Nelson, Adam R. Vaughan, James R. Hopkins, Rahul Arya, Arnab Mondal, Ritu Jangirh, Sakshi Ahlawat, Lokesh Yadav, Sudhir K. Sharma, Rachel E. Dunmore, Siti S. M. Yunus, C. Nicholas Hewitt, Eiko Nemitz, Neil Mullinger, Ranu Gadi, Lokesh K. Sahu, Nidhi Tripathi, Andrew R. Rickard, James D. Lee, Tuhin K. Mandal, and Jacqueline F. Hamilton
Atmos. Chem. Phys., 21, 2383–2406,Short summary
Biomass burning is a major source of trace gases to the troposphere; however, the composition and quantity of emissions vary greatly between different fuel types. This work provided near-total quantitation of non-methane volatile organic compounds from combustion of biofuels from India. Emissions from cow dung cake combustion were significantly larger than conventional fuelwood combustion, potentially indicating that this source has a disproportionately large impact on regional air quality.
Axel Fouqueau, Manuela Cirtog, Mathieu Cazaunau, Edouard Pangui, Jean-François Doussin, and Bénédicte Picquet-Varrault
Atmos. Chem. Phys., 20, 15167–15189,
Michael Rolletter, Marion Blocquet, Martin Kaminski, Birger Bohn, Hans-Peter Dorn, Andreas Hofzumahaus, Frank Holland, Xin Li, Franz Rohrer, Ralf Tillmann, Robert Wegener, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 20, 13701–13719,Short summary
The photooxidation of pinonaldehyde is investigated in a chamber study under natural sunlight and low NO conditions with and without an added hydroxyl radical (OH) scavenger. The experimentally determined pinonaldehyde photolysis frequency is faster by a factor of 3.5 than currently used parameterizations in atmospheric models. Yields of degradation products are measured in the presence and absence of OH. Measurements are compared to current atmospheric models and a theory-based mechanism.
Matias Berasategui, Damien Amedro, Luc Vereecken, Jos Lelieveld, and John N. Crowley
Atmos. Chem. Phys., 20, 13541–13555,Short summary
Peracetic acid is one of the most abundant organic peroxides in the atmosphere. We combine experiments and theory to show that peracetic acid reacts orders of magnitude more slowly with OH than presently accepted, which results in a significant extension of its atmospheric lifetime.
Jacinta Edebeli, Jürg C. Trachsel, Sven E. Avak, Markus Ammann, Martin Schneebeli, Anja Eichler, and Thorsten Bartels-Rausch
Atmos. Chem. Phys., 20, 13443–13454,Short summary
Earth’s snow cover is very dynamic and can change its physical properties within hours, as is well known by skiers. Snow is also a well-known host of chemical reactions – the products of which impact air composition and quality. Here, we present laboratory experiments that show how the dynamics of snow make snow essentially inert with respect to gas-phase ozone with time despite its content of reactive chemicals. Impacts on polar atmospheric chemistry are discussed.
R. Anthony Cox, Markus Ammann, John N. Crowley, Hartmut Herrmann, Michael E. Jenkin, V. Faye McNeill, Abdelwahid Mellouki, Jürgen Troe, and Timothy J. Wallington
Atmos. Chem. Phys., 20, 13497–13519,Short summary
Criegee intermediates, formed from alkene–ozone reactions, play a potentially important role as tropospheric oxidants. Evaluated kinetic data are provided for reactions governing their formation and removal for use in atmospheric models. These include their formation from reactions of simple and complex alkenes and removal by decomposition and reaction with a number of atmospheric species (e.g. H2O, SO2). An overview of the tropospheric chemistry of Criegee intermediates is also provided.
Jake P. Rowe, Andrew T. Lambe, and William H. Brune
Atmos. Chem. Phys., 20, 13417–13424,Short summary
We conducted a series of experiments in which the 185 to 254 nm photon flux ratio (I185 : I254) emitted by low-pressure mercury lamps installed in an oxidation flow reactor (OFR) was systematically varied using multiple novel lamp configurations. Integrated OH exposure values achieved for each lamp type were obtained as a function of OFR operating conditions. A photochemical box model was used to develop a generalized OH exposure estimation equation as a function of [H2O], [O3], and OH reactivity.
Mei-Tsan Kuo, Isabelle Weber, Christa Fittschen, Luc Vereecken, and Jim Jr-Min Lin
Atmos. Chem. Phys., 20, 12983–12993,Short summary
Dimethyl sulfide (DMS) is the major sulfur-containing species in the troposphere. Previous work by Newland et al. (2015) reported very high reactivity of isoprene-derived Criegee intermediates (CIs) towards DMS. By monitoring CIs with direct UV absorption, we found CI + DMS reactions are very slow, in contrast to the results of Newland et al. (2015), suggesting these CIs would not oxidize atmospheric DMS at any substantial level.
Thomas R. Lewis, Juan Carlos Gómez Martín, Mark A. Blitz, Carlos A. Cuevas, John M. C. Plane, and Alfonso Saiz-Lopez
Atmos. Chem. Phys., 20, 10865–10887,Short summary
Iodine-bearing gasses emitted from the sea surface are chemically processed in the atmosphere, leading to iodine accumulation in aerosol and transport to continental ecosystems. Such processing involves light-induced break-up of large, particle-forming iodine oxides into smaller, ozone-depleting molecules. We combine experiments and theory to report the photolysis efficiency of iodine oxides required to assess the impact of iodine on ozone depletion and particle formation.
Patrick Dewald, Jonathan M. Liebmann, Nils Friedrich, Justin Shenolikar, Jan Schuladen, Franz Rohrer, David Reimer, Ralf Tillmann, Anna Novelli, Changmin Cho, Kangming Xu, Rupert Holzinger, François Bernard, Li Zhou, Wahid Mellouki, Steven S. Brown, Hendrik Fuchs, Jos Lelieveld, and John N. Crowley
Atmos. Chem. Phys., 20, 10459–10475,Short summary
We present direct measurements of NO3 reactivity resulting from the oxidation of isoprene by NO3 during an intensive simulation chamber study. Measurements were in excellent agreement with values calculated from measured isoprene amounts and the rate coefficient for the reaction of NO3 with isoprene. Comparison of the measurement with NO3 reactivities from non-steady-state and model calculations suggests that isoprene-derived RO2 and HO2 radicals account to ~ 50 % of overall NO3 losses.
Jacob T. Shaw, Andrew R. Rickard, Mike J. Newland, and Terry J. Dillon
Atmos. Chem. Phys., 20, 9725–9736,Short summary
This work expands upon the recently developed multivariate relative rate technique, presented in Shaw et al. (2019), for the measurement of rates of reaction between aromatic and aliphatic volatile organic compounds (VOCs) and OH. Knowledge of the rates of such reactions are important for understanding air quality in urban environments. This work also provides a key validation of structure–activity relationship models, which provide a theoretical method for estimating OH + VOC kinetics.
Rodrigo Gastón Gibilisco, Ian Barnes, Iustinian Gabriel Bejan, and Peter Wiesen
Atmos. Chem. Phys., 20, 8939–8951,Short summary
Environmental chamber studies were performed to evaluate atmospheric degradation initiated by OH radicals for two unsaturated methoxy ketones. The main gas-phase oxidation products identified and quantified from these reactions are carbonyls and long-lived nitrogen-containing compounds such as peroxyacetyl nitrate and peroxypropionyl nitrate. The kinetic rate constants and atmospheric lifetimes were estimated, degradation mechanisms were developed, and atmospheric implications were assessed.
James M. Roberts, Chelsea E. Stockwell, Robert J. Yokelson, Joost de Gouw, Yong Liu, Vanessa Selimovic, Abigail R. Koss, Kanako Sekimoto, Matthew M. Coggon, Bin Yuan, Kyle J. Zarzana, Steven S. Brown, Cristina Santin, Stefan H. Doerr, and Carsten Warneke
Atmos. Chem. Phys., 20, 8807–8826,Short summary
We measured total reactive nitrogen, Nr, in lab fires from western North American fuels, along with measurements of individual nitrogen compounds. We measured the amount of N that gets converted to inactive compounds (avg. 70 %), and the amount that is accounted for by individual species (85 % of remaining N). We provide guidelines for how the reactive nitrogen is distributed among individual compounds such as NOx and ammonia. This will help estimates and predictions of wildfire emissions.
Anna Novelli, Luc Vereecken, Birger Bohn, Hans-Peter Dorn, Georgios I. Gkatzelis, Andreas Hofzumahaus, Frank Holland, David Reimer, Franz Rohrer, Simon Rosanka, Domenico Taraborrelli, Ralf Tillmann, Robert Wegener, Zhujun Yu, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 20, 3333–3355,Short summary
Experimental evidence from a simulation chamber study shows that the regeneration efficiency of the hydroxyl radical is maintained globally at values higher than 0.5 for a wide range of nitrogen oxide concentrations as a result of isomerizations of peroxy radicals originating from the OH oxidation of isoprene. The available models were tested, and suggestions on how to improve their ability to reproduce the measured radical and oxygenated volatile organic compound concentrations are provided.
Damien Amedro, Matias Berasategui, Arne J. C. Bunkan, Andrea Pozzer, Jos Lelieveld, and John N. Crowley
Atmos. Chem. Phys., 20, 3091–3105,Short summary
Our laboratory experiments show that the rate coefficient for the termolecular reaction between OH and NO2 is enhanced in the presence of water vapour. Using a chemistry transport model we show that our new parameterization of the temperature, pressure, and bath-gas dependence of this reaction has a significant impact on, for example, NOx and the HNO2 / NO2 ratio when compared to present recommendations.
Matias Berasategui, Damien Amedro, Achim Edtbauer, Jonathan Williams, Jos Lelieveld, and John N. Crowley
Atmos. Chem. Phys., 20, 2695–2707,Short summary
We have determined the rate coefficient and mechanism for the reaction of the OH radical with methane sulphonamide, a trace gas which has recently been found in the atmosphere. The rate coefficient is 1.4 × 10−13 cm3 molec.−1 s−1, which indicates a tropospheric lifetime of > 2 months. The observation of CO, CO2, SO2, HNO3, HCOOH, and N2O products enabled us to derive a detailed reaction mechanism for the reaction, which proceeds predominantly by H abstraction from the CH3 group.
Abigail R. Koss, Manjula R. Canagaratna, Alexander Zaytsev, Jordan E. Krechmer, Martin Breitenlechner, Kevin J. Nihill, Christopher Y. Lim, James C. Rowe, Joseph R. Roscioli, Frank N. Keutsch, and Jesse H. Kroll
Atmos. Chem. Phys., 20, 1021–1041,Short summary
Oxidation chemistry of organic compounds in the atmosphere produces a diverse spectrum of products. This diversity is difficult to represent in air quality and climate models, and in laboratory experiments it results in large and complex datasets. This work evaluates several methods to simplify the chemistry of oxidation systems in environmental chambers, including positive matrix factorization, hierarchical clustering analysis, and gamma kinetics parameterization.
Inmaculada Colmenar, Pilar Martin, Beatriz Cabañas, Sagrario Salgado, Araceli Tapia, and Inmaculada Aranda
Atmos. Chem. Phys., 20, 699–720,Short summary
Saturated alcohols (SAs), such as (E)-4-methylcyclohexanol, 3,3-dimethyl-1-butanol, and 3,3-dimethyl-2-butanol, could be used as biofuels. The atmospheric reactivity of these compounds must be established in order to understand the consequences of the presence of these compounds in the atmosphere. The experimental results obtained in this work reveal that uncontrolled emissions of these saturated alcohols could have important atmospheric implications.
Olga Garmash, Matti P. Rissanen, Iida Pullinen, Sebastian Schmitt, Oskari Kausiala, Ralf Tillmann, Defeng Zhao, Carl Percival, Thomas J. Bannan, Michael Priestley, Åsa M. Hallquist, Einhard Kleist, Astrid Kiendler-Scharr, Mattias Hallquist, Torsten Berndt, Gordon McFiggans, Jürgen Wildt, Thomas F. Mentel, and Mikael Ehn
Atmos. Chem. Phys., 20, 515–537,Short summary
Highly oxygenated organic molecules (HOMs) facilitate aerosol formation in the atmosphere. Using NO3− chemical ionization mass spectrometry we investigated HOM composition and yield in oxidation of aromatic compounds at different reactant concentrations, in the presence of NOx and seed aerosol. Higher OH concentrations increased HOM yield, suggesting multiple oxidation steps, and affected HOM composition, potentially explaining in part discrepancies in published secondary organic aerosol yields.
Bénédicte Picquet-Varrault, Ricardo Suarez-Bertoa, Marius Duncianu, Mathieu Cazaunau, Edouard Pangui, Marc David, and Jean-François Doussin
Atmos. Chem. Phys., 20, 487–498,Short summary
Multifunctional organic nitrates are important atmospheric species that are known to play a key role in the transport of reactive nitrogen and in aerosol composition. However, very little is known about their atmospheric reactivity. Here we provide an experimental study on the photolysis and reaction of two carbonyl nitrates with OH radicals. Atmospheric implications and the influence of the chemical structure on the reactivity are discussed.
Eetu Kari, Liqing Hao, Arttu Ylisirniö, Angela Buchholz, Ari Leskinen, Pasi Yli-Pirilä, Ilpo Nuutinen, Kari Kuuspalo, Jorma Jokiniemi, Celia L. Faiola, Siegfried Schobesberger, and Annele Virtanen
Atmos. Chem. Phys., 19, 15651–15671,Short summary
We present, for the first time, the dual effect of GDI-vehicle exhaust on α-pinene SOA mass yield suppression. The first effect is a well-known NOx effect, but the second effect is more complex. Our results imply that this second effect is related to change of reaction pathways of α-pinene in the presence of GDI exhaust. The presence of vehicle exhaust caused more than 50 % suppression in α-pinene SOA mass yield compared to the α-pinene SOA mass yield measured in the absence of GDI emissions.
Epameinondas Tsiligiannis, Julia Hammes, Christian Mark Salvador, Thomas F. Mentel, and Mattias Hallquist
Atmos. Chem. Phys., 19, 15073–15086,Short summary
The role of anthropogenic VOCs (AVOCs) for SOA formation needs to be scrutinised. The aromatic 1,3,5-trimethylbenzene (TMB) was shown to form highly oxygenated organic molecules (HOMs) in NOx-free environments, possibly contributing to new particle formation (NPF). However, formation of HOMs and particles was suppressed in the presence of NOx, while the formation of organonitrates (ONs) was increased. Thus, aromatic AVOCs may not enhance NPF in urban air masses.
Aplincourt, P. and Anglada, J.: Theoretical studies on isoprene ozonolysis under tropospheric conditions. 1. Reaction of substituted carbonyl oxides with water, J. Phys. Chem. A, 107, 5798–5811, https://doi.org/10.1021/jp026868o, 2003.
Arellanes, C., Paulson, S. E., Fine, P. M., and Sioutas, C.: Exceeding of Henry's law by hydrogen peroxide associated with urban aerosols, Environ. Sci. Technol., 40, 4859–4866, https://doi.org/10.1021/es0513786, 2006.
Badali, K. M., Zhou, S., Aljawhary, D., Antiñolo, M., Chen, W. J., Lok, A., Mungall, E., Wong, J. P. S., Zhao, R., and Abbatt, J. P. D.: Formation of hydroxyl radicals from photolysis of secondary organic aerosol material, Atmos. Chem. Phys., 15, 7831–7840, https://doi.org/10.5194/acp-15-7831-2015, 2015.
Banerjee, D. K. and Budke, C. C.: Spectrophotometric Determination of Traces of Peroxides in Organic Solvents, Anal. Chem., 36, 792–796, https://doi.org/10.1021/ac60210a027, 1964.
Bateman, A. P., Nizkorodov, S. A., Laskin, J., and Laskin, A.: Photolytic processing of secondary organic aerosols dissolved in cloud droplets, Phys. Chem. Chem. Phys., 13, 12199–12212, https://doi.org/10.1039/c1cp20526a, 2011.
Baum, E.: Chemical property estimation: Theory and Application, CRC Press, Florida, 1997.
Becker, K. H., Brockmann, K. J., and Bechara, J.: Production of hydrogen peroxide in forest air by reaction of ozone with terpenes, Nature, 346, 256–258, https://doi.org/10.1038/346256a0, 1990.
Berndt, T., Böge, O., and Stratmann, F.: Gas-phase ozonolysis of α-pinene: gaseous products and particle formation, Atmos. Environ., 37, 3933–3945, https://doi.org/10.1016/S1352-2310(03)00501-6, 2003.
Berndt, T., Voigtländer, J., Stratmann, F., Junninen, H., Mauldin III, R. L., Sipilä, M., Kulmala, M., and Herrmann, H.: Competing atmospheric reactions of CH2OO with SO2 and water vapour, Phys. Chem. Chem. Phys., 16, 19130–19136, https://doi.org/10.1039/c4cp02345e, 2014.
Bonn, B., von Kuhlmann, R., and Lawrence, M. G.: High contribution of biogenic hydroperoxides to secondary organic aerosol formation, Geophys. Res. Lett., 31, L10108, https://doi.org/10.1029/2003GL019172, 2004.
Camredon, M., Hamilton, J. F., Alam, M. S., Wyche, K. P., Carr, T., White, I. R., Monks, P. S., Rickard, A. R., and Bloss, W. J.: Distribution of gaseous and particulate organic composition during dark a-pinene ozonolysis, Atmos. Chem. Phys., 10, 2893–2917, https://doi.org/10.5194/acp-10-2893-2010, 2010.
Chao, W., Hsieh, J.-T., and Chang, C.-H.: Direct kinetic measurement of the reaction of the simplest Criegee intermediate with water vapor, Science, 347, 751–754, https://doi.org/10.1126/science.1261549, 2015.
Chen, Z. M., Wang, H. L., Zhu, L. H., Wang, C. X., Jie, C. Y., and Hua, W.: Aqueous-phase ozonolysis of methacrolein and methyl vinyl ketone: a potentially important source of atmospheric aqueous oxidants, Atmos. Chem. Phys., 8, 2255–2265, https://doi.org/10.5194/acp-8-2255-2008, 2008.
Cocker III, D. R., Clegg, S. L., Flagan, R. C., and Seinfeld, J. H.: The effect of water on gas–particle partitioning of secondary organic aerosol. Part I: α-pinene/ozone system, Atmos. Environ., 35, 6049–6072, https://doi.org/10.1016/S1352-2310(01)00404-6, 2001.
Crehuet, R., Anglada, J. M., and Bofill, J. M.: Tropospheric formation of hydroxymethyl hydroperoxide, formic acid, H2O2, and OH from carbonyl oxide in the presence of water vapor: a theoretical study of the reaction mechanism, Chemistry-a European Journal, 7, 2227–2235, https://doi.org/10.1002/1521-3765(20010518)7:10<2227::AID-CHEM2227>3.3.CO;2-F, 2001.
Docherty, K. S., Wu, W., Lim, Y. B., and Ziemann, P. J.: Contributions of organic peroxides to secondary aerosol formed from reactions of monoterpenes with O3, Environ. Sci. Technol., 39, 4049–4059, https://doi.org/10.1021/es050228s, 2005.
Epstein, S. A., Blair, S. L., and Nizkorodov, S. A.: Direct photolysis of α-pinene ozonolysis secondary organic aerosol: effect on particle mass and peroxide content, Environ. Sci. Technol., 48, 11251–11258, https://doi.org/10.1021/es502350u, 2014.
Farina, S. C., Adams, P. J., and Pandis, S. N.: Modeling global secondary organic aerosol formation and processing with the volatility basis set: Implications for anthropogenic secondary organic aerosol, J. Geophys. Res.-Atmos., 115, D09202, https://doi.org/10.1029/2009JD013046, 2010.
Fu, H. B., Wang, X., Wu, H. B., Yin, Y., and Chen, J. M.: Heterogeneous uptake and oxidation of SO2 on iron oxides, J. Phys. Chem. C, 111, 6077–6085, https://doi.org/10.1021/jp070087b, 2007.
Gäb, S., Turner, W. V., Wolff, S., Becker, K. H., Ruppert, L., and Brockmann, K. J.: Formation of alkyl and hydroxyalkyl hydroperoxides on ozonolysis in water and in air, Atmos. Environ., 29, 2401–2407, https://doi.org/10.1016/1352-2310(95)00166-V, 1995.
Goodman, A., Bernard, E., and Grassian, V.: Spectroscopic study of nitric acid and water adsorption on oxide particles: Enhanced nitric acid uptake kinetics in the presence of adsorbed water, J. Phys. Chem. A, 105, 6443–6457, https://doi.org/10.1021/jp003722l, 2001.
Griffin, R. J., Cocker, D. R., Flagan, R. C., and Seinfeld, J. H.: Organic aerosol formation from the oxidation of biogenic hydrocarbons, J. Geophys. Res., 104, 3555–3567, https://doi.org/10.1029/1998JD100049, 1999.
Hellpointner, E. and Gäb, S.: Detection of methyl, hydroxymethyl and hydroxyethyl hydroperoxides in air and precipitation, Nature, 337, 631–634, https://doi.org/10.1038/337631a0, 1989.
Hewitt, C. N. and Kok, G. L.: Formation and occurrence of organic hydroperoxides in the troposphere: laboratory and field observations, J. Atmos. Chem., 12, 181–194, https://doi.org/10.1007/BF00115779, 1991.
Hoffmann, T., Odum, J. R., Bowman, F., Collins, D., Klockow, D., Flagan, R. C., and Seinfeld, J. H.: Formation of organic aerosols from the oxidation of biogenic hydrocarbons, J. Atmos. Chem., 26, 189–222, https://doi.org/10.1023/A:1005734301837, 1997.
Hua, W., Chen, Z. M., Jie, C. Y., Kondo, Y., Hofzumahaus, A., Takegawa, N., Chang, C. C., Lu, K. D., Miyazaki, Y., Kita, K., Wang, H. L., Zhang, Y. H., and Hu, M.: Atmospheric hydrogen peroxide and organic hydroperoxides during PRIDE-PRD'06, China: their concentration, formation mechanism and contribution to secondary aerosols, Atmos. Chem. Phys., 8, 6755–6773, https://doi.org/10.5194/acp-8-6755-2008, 2008.
Huang, D., Chen, Z. M., Zhao, Y., and Liang, H.: Newly observed peroxides and the water effect on the formation and removal of hydroxyalkyl hydroperoxides in the ozonolysis of isoprene, Atmos. Chem. Phys., 13, 5671–5683, https://doi.org/10.5194/acp-13-5671-2013, 2013.
Huang, L. B., Zhao, Y., Li, H., and Chen, Z. M.: Kinetics of heterogeneous reaction of sulfur dioxide on authentic mineral dust: effects of relative humidity and hydrogen peroxide, Environ. Sci. Technol., 49, 10797–10805, https://doi.org/10.1021/acs.est.5b03930, 2015.
Jenkin, M. E.: Modelling the formation and composition of secondary organic aerosol from α- and β-pinene ozonolysis using MCM v3, Atmos. Chem. Phys., 4, 1741–1757, https://doi.org/10.5194/acp-4-1741-2004, 2004.
Kamens, R. M. and Jaoui, M.: Modeling aerosol formation from α-pinene + NOx in the presence of natural sunlight using gas-phase kinetics and gas-particle partitioning theory, Environ. Sci. Technol., 35, 1394–1405, https://doi.org/10.1021/es001626s, 2001.
Khan, M., Cooke, M., Utembe, S., Xiao, P., Morris, W., Derwent, R., Archibald, A., Jenkin, M., Percival, C., and Shallcross, D.: The global budgets of organic hydroperoxides for present and pre-industrial scenarios, Atmos. Environ., 110, 65–74, https://doi.org/10.1016/j.atmosenv.2015.03.045, 2015.
Kidd, C., Perraud, V., and Finlayson-Pitts, B. J.: New insights into secondary organic aerosol from the ozonolysis of α-pinene from combined infrared spectroscopy and mass spectrometry measurements, Phys. Chem. Chem. Phys., 16, 22706–22716, https://doi.org/10.1039/c4cp03405h, 2014.
Kroll, J. H., Ng, N. L., Murphy, S. M., Varutbangkul, V., Flagan, R. C., and Seinfeld, J. H.: Chamber studies of secondary organic aerosol growth by reactive uptake of simple carbonyl compounds, J. Geophys. Res.-Atmos., 110, D23207, https://doi.org/10.1029/2005JD006004, 2005.
Kubistin, D., Harder, H., Martinez, M., Rudolf, M., Sander, R., Bozem, H., Eerdekens, G., Fischer, H., Gurk, C., Klüpfel, T., Königstedt, R., Parchatka, U., Schiller, C. L., Stickler, A., Taraborrelli, D., Williams, J., and Lelieveld, J.: Hydroxyl radicals in the tropical troposphere over the Suriname rainforest: comparison of measurements with the box model MECCA, Atmos. Chem. Phys., 10, 9705–9728, https://doi.org/10.5194/acp-10-9705-2010, 2010.
Lee, M., Heikes, B. G., and O'Sullivan, D. W.: Hydrogen peroxide and organic hydroperoxide in the troposphere: a review, Atmos. Environ., 34, 3475–3494, https://doi.org/10.1016/S1352-2310(99)00432-X, 2000.
Lewis, T. R., Blitz, M. A., Heard, D. E., and Seakins, P. W.: Direct evidence for a substantive reaction between the Criegee intermediate, CH2 OO, and the water vapour dimer, Phys. Chem. Chem. Phys., 17, 4859–4863, https://doi.org/10.1039/c4cp04750h, 2015.
Liggio, J., Li, S.-M., and McLaren, R.: Heterogeneous reactions of glyoxal on particulate matter: Identification of acetals and sulfate esters, Environ. Sci. Technol., 39, 1532–1541, https://doi.org/10.1021/es048375y, 2005.
Mertes, P., Pfaffenberger, L., Dommen, J., Kalberer, M., and Baltensperger, U.: Development of a sensitive long path absorption photometer to quantify peroxides in aerosol particles (Peroxide-LOPAP), Atmos. Meas. Tech., 5, 2339–2348, https://doi.org/10.5194/amt-5-2339-2012, 2012.
Nguyen, T. B., Bateman, A. P., Bones, D. L., Nizkorodov, S. A., Laskin, J., and Laskin, A.: High-resolution mass spectrometry analysis of secondary organic aerosol generated by ozonolysis of isoprene, Atmos. Environ., 44, 1032–1042, https://doi.org/10.1016/j.atmosenv.2009.12.019, 2010.
Odum, J. R., Hoffmann, T., Bowman, F., Collins, D., Flagan, R. C., and Seinfeld, J. H.: Gas/particle partitioning and secondary organic aerosol yields, Environ. Sci. Technol., 30, 2580–2585, https://doi.org/10.1021/es950943+, 1996.
Pankow, J. F.: An absorption model of the gas/aerosol partitioning involved in the formation of secondary organic aerosol, Atmos. Environ., 28, 189–193, https://doi.org/10.1016/1352-2310(94)90093-0, 1994.
Presto, A. A., Huff Hartz, K. E., and Donahue, N. M.: Secondary organic aerosol production from terpene ozonolysis. 2. Effect of NOx concentration, Environ. Sci. Technol., 39, 7046–7054, https://doi.org/10.1021/es050400s, 2005.
Prince, A. P., Kleiber, P., Grassian, V., and Young, M.: Heterogeneous interactions of calcite aerosol with sulfur dioxide and sulfur dioxide–nitric acid mixtures, Phys. Chem. Chem. Phys., 9, 3432–3439, https://doi.org/10.1039/B703296J, 2007.
Pye, H. O. T. and Seinfeld, J. H.: A global perspective on aerosol from low-volatility organic compounds, Atmos. Chem. Phys., 10, 4377–4401, https://doi.org/10.5194/acp-10-4377-2010, 2010.
Reeves, C. E. and Penkett, S. A.: Measurements of peroxides and what they tell us, Chem. Rev., 103, 5199–5218, https://doi.org/10.1021/cr0205053, 2003.
Rudich, Y., Donahue, N. M., and Mentel, T. F.: Aging of organic aerosol: Bridging the gap between laboratory and field studies, Annu. Rev. Phys. Chem., 58, 321–352, https://doi.org/10.1146/annurev.physchem.58.032806.104432, 2007.
Ryzhkov, A. B. and Ariya, P. A.: A theoretical study of the reactions of parent and substituted Criegee intermediates with water and the water dimer, Phys. Chem. Chem. Phys., 6, 5042–5050, https://doi.org/10.1039/B408414D, 2004.
Saathoff, H., Naumann, K.-H., Möhler, O., Jonsson, Å. M., Hallquist, M., Kiendler-Scharr, A., Mentel, Th. F., Tillmann, R., and Schurath, U.: Temperature dependence of yields of secondary organic aerosols from the ozonolysis of a-pinene and limonene, Atmos. Chem. Phys., 9, 1551–1577, https://doi.org/10.5194/acp-9-1551-2009, 2009.
Simonaitis, R., Olszyna, K., and Meagher, J.: Production of hydrogen peroxide and organic peroxides in the gas phase reactions of ozone with natural alkenes, Geophys. Res. Lett., 18, 9–12, 1991.
Surratt, J. D., Murphy, S. M., Kroll, J. H., Ng, N. L., Hildebrandt, L., Sorooshian, A., Szmigielski, R., Vermeylen, R., Maenhaut, W., and Claeys, M.: Chemical composition of secondary organic aerosol formed from the photooxidation of isoprene, J. Phys. Chem. A, 110, 9665–9690, https://doi.org/10.1021/jp061734m, 2006.
Tobias, H. J. and Ziemann, P. J.: Thermal desorption mass spectrometric analysis of organic aerosol formed from reactions of 1-tetradecene and O3 in the presence of alcohols and carboxylic acids, Environ. Sci. Technol., 34, 2105–2115, https://doi.org/10.1021/es9907156, 2000.
Tobias, H. J. and Ziemann, P. J.: Kinetics of the gas-phase reactions of alcohols, aldehydes, carboxylic acids, and water with the C13 stabilized Criegee intermediate formed from ozonolysis of 1-tetradecene, J. Phys. Chem. A, 105, 6129–6135, https://doi.org/10.1021/jp004631r, 2001.
Venkatachari, P. and Hopke, P. K.: Development and laboratory testing of an automated monitor for the measurement of atmospheric particle-bound reactive oxygen species (ROS), Aerosol Sci. Tech., 42, 629–635, https://doi.org/10.1039/b804357d, 2008.
Vereecken, L., Harder, H., and Novelli, A.: The reactions of Criegee intermediates with alkenes, ozone, and carbonyl oxides, Phys. Chem. Chem. Phys., 16, 4039–4049, https://doi.org/10.1039/c3cp54514h, 2014.
Wang, Y., Kim, H., and Paulson, S. E.: Hydrogen peroxide generation from α-and β-pinene and toluene secondary organic aerosols, Atmos. Environ., 45, 3149–3156, https://doi.org/10.1016/j.atmosenv.2011.02.060, 2011.
Yu, J. Z., Cocker III, D. R., Griffin, R. J., Flagan, R. C., and Seinfeld, J. H.: Gas-phase ozone oxidation of monoterpenes: Gaseous and particulate products, J. Atmos. Chem., 34, 207–258, https://doi.org/10.1023/A:1006254930583, 1999.
Zhang, X., Chen, Z. M., Wang, H. L., He, S. Z., and Huang, D. M.: An important pathway for ozonolysis of alpha-pinene and beta-pinene in aqueous phase and its atmospheric implications, Atmos. Environ., 43, 4465–4471, https://doi.org/10.1016/j.atmosenv.2009.06.028, 2009.
Zhao, Y., Chen, Z. M., and Zhao, J. N.: Heterogeneous reactions of methacrolein and methyl vinyl ketone on α-Al2O3 particles, Environ. Sci. Technol., 44, 2035–2041, https://doi.org/10.1021/es9037275, 2010.
Zhao, Y., Chen, Z. M., Shen, X. L., and Zhang, X.: Kinetics and mechanisms of heterogeneous reaction of gaseous hydrogen peroxide on mineral oxide particles, Environ. Sci. Technol., 45, 3317–3324, https://doi.org/10.1021/es104107c, 2011.
Zhao, Y., Huang, D., Huang, L. B., and Chen, Z. M.: Hydrogen peroxide enhances the oxidation of oxygenated volatile organic compounds on mineral dust particles: a case study of methacrolein, Environ. Sci. Technol., 48, 10614–10623, https://doi.org/10.1021/es5023416, 2014.
Zhou, X. L. and Lee, Y. N.: Aqueous solubility and reaction kinetics of hydroxymethyl hydroperoxide, J. Phys. Chem., 96, 265–272, https://doi.org/10.1021/j100180a051, 1992.
Ziemann, P. J.: Aerosol products, mechanisms, and kinetics of heterogeneous reactions of ozone with oleic acid in pure and mixed particles, Faraday Discuss., 130, 469–490, https://doi.org/10.1039/b417502f, 2005.
The formation, gas-particle partitioning, and evolution of atmospheric organic peroxides are unclear. We investigated the ozonolysis of α-pinene, and focused on peroxides. We found that gas-particle partitioning coefficients of peroxides are much higher than the values from our theoretical prediction, and some gaseous peroxides undergo rapid heterogeneous decomposition on SOA particles in the presence of water vapor, resulting in the additional production of hydrogen peroxide.
The formation, gas-particle partitioning, and evolution of atmospheric organic peroxides are...