Peroxy radicals from night-time reaction of N03 with organic compounds

Nature ◽  
1990 ◽  
Vol 348 (6297) ◽  
pp. 147-149 ◽  
Author(s):  
U. Platt ◽  
G. LeBras ◽  
G. Poulet ◽  
J. P. Burrows ◽  
G. Moortgat
Keyword(s):  
Organic Compounds ◽  
Peroxy Radicals ◽  
Night Time

scholarly journals A Steady State Continuous Flow Chamber for the Study of Daytime and Night time Chemistry under Atmospherically Relevant NO levels

2018 ◽  
Author(s):  
Xuan Zhang ◽  
John Ortega ◽  
Yuanlong Huang ◽  
Stephen Shertz ◽  
Geoffrey S. Tyndall ◽  
...  
Keyword(s):  
Steady State ◽  
Atmospheric Chemistry ◽  
Continuous Flow ◽  
Anthropogenic Activities ◽  
The United States ◽  
Flow Chamber ◽  
Flow Mode ◽  
Peroxy Radicals ◽  
Night Time ◽  
Atmospheric Processes

Abstract. Experiments performed in laboratory chambers have contributed significantly to the understanding of the fundamental kinetics and mechanisms of the chemical reactions occurring in the atmosphere. Two chemical regimes, classified as high-NO versus zero-NO conditions, have been extensively studied in previous chamber experiments. Results derived from these two chemical scenarios are widely parameterized in chemical transport models to represent key atmospheric processes in urban and pristine environments. As the anthropogenic NOx emissions in the United States have decreased remarkably in the past few decades, the classic high-NO and zero-NO conditions are no longer applicable to many regions that are constantly impacted by both polluted and background air masses. We present here the development and characterization of the NCAR Atmospheric Simulation Chamber, which is operated in steady state continuous flow mode for the study of atmospheric chemistry under intermediate NO conditions. This particular chemical regime is characterized by constant sub-ppb levels of NO and can be created in the chamber by precise control of the inflow NO concentration and the ratio of chamber mixing to residence timescales. Over the range of conditions achievable in the chamber, the lifetime of peroxy radicals (RO2), a key intermediate from the atmospheric degradation of volatile organic compounds (VOCs), can be extended to several minutes, and a diverse array of reaction pathways, including unimolecular pathways and bimolecular reactions with NO and HO2, can thus be explored. Characterization experiments under photolytic and dark conditions were performed and, in conjunction with model predictions, provide a basis for interpretation of prevailing atmospheric processes in environments with intertwined biogenic and anthropogenic activities. We demonstrate the proof of concept of the steady state continuous flow chamber operation through measurements of major first-generation products, methacrolein (MACR) and methyl vinyl ketone (MVK), from OH- and NO3-initiated oxidation of isoprene.

scholarly journals Radicals in the marine boundary layer during NEAQS 2004: a model study of day-time and night-time sources and sinks

2009 ◽  
Vol 9 (9) ◽  
pp. 3075-3093 ◽  
Author(s):  
R. Sommariva ◽  
H. D. Osthoff ◽  
S. S. Brown ◽  
T. S. Bates ◽  
T. Baynard ◽  
...  
Keyword(s):  
Boundary Layer ◽  
New England ◽  
Gas Phase ◽  
Marine Boundary Layer ◽  
Peroxy Radical ◽  
Chemical Mechanism ◽  
Physical Parameters ◽  
Peroxy Radicals ◽  
Night Time ◽  
Aerosol Composition

Abstract. This paper describes a modelling study of several HOx and NOx species (OH, HO2, organic peroxy radicals, NO3 and N2O5) in the marine boundary layer. A model based upon the Master Chemical Mechanism (MCM) was constrained to observations of chemical and physical parameters made onboard the NOAA ship R/V Brown as part of the New England Air Quality Study (NEAQS) in the summer of 2004. The model was used to calculate [OH] and to determine the composition of the peroxy radical pool. Modelled [NO3] and [N2O5] were compared to in-situ measurements by Cavity Ring-Down Spectroscopy. The comparison showed that the model generally overestimated the measurements by 30–50%, on average. The model results were analyzed with respect to several chemical and physical parameters, including uptake of NO3 and N2O5 on fog droplets and on aerosol, dry deposition of NO3 and N2O5, gas-phase hydrolysis of N2O5 and reactions of NO3 with NMHCs and peroxy radicals. The results suggest that fog, when present, is an important sink for N2O5 via rapid heterogeneous uptake. The comparison between the model and the measurements were consistent with values of the heterogeneous uptake coefficient of N2O5 (γN2O5)>1×10−2, independent of aerosol composition in this marine environment. The analysis of the different loss processes of the nitrate radical showed the important role of the organic peroxy radicals, which accounted for a significant fraction (median: 15%) of NO3 gas-phase removal, particularly in the presence of high concentrations of dimethyl sulphide (DMS).

scholarly journals Peroxy radical chemistry and the control of ozone photochemistry at Mace Head, Ireland during the summer of 2002

2006 ◽  
Vol 6 (8) ◽  
pp. 2193-2214 ◽  
Author(s):  
Z. L. Fleming ◽  
P. S. Monks ◽  
A. R. Rickard ◽  
D. E. Heard ◽  
W. J. Bloss ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Production Rate ◽  
Marine Boundary Layer ◽  
Strong Dependence ◽  
Peroxy Radical ◽  
Chemical Mechanism ◽  
Ozone Production ◽  
Peroxy Radicals ◽  
Night Time ◽  
Model Measurement

Abstract. Peroxy radical (HO2+ΣRO2) measurements, using the PEroxy Radical Chemical Amplification (PERCA) technique at the North Atlantic Marine Boundary Layer EXperiment (NAMBLEX) at Mace Head in summer 2002, are presented and put into the context of marine, boundary-layer chemistry. A suite of other chemical parameters (NO, NO2, NO3, CO, CH4, O3, VOCs, peroxides), photolysis frequencies and meteorological measurements, are used to present a detailed analysis of the role of peroxy radicals in tropospheric oxidation cycles and ozone formation. Under the range of conditions encountered the peroxy radical daily maxima varied from 10 to 40 pptv. The diurnal cycles showed an asymmetric shape typically shifted to the afternoon. Using a box model based on the master chemical mechanism the average model measurement agreement was 2.5 across the campaign. The addition of halogen oxides to the model increases the level of model/measurement agreement, apparently by respeciation of HOx. A good correlation exists between j(HCHO).[HCHO] and the peroxy radicals indicative of the importance of HCHO in the remote atmosphere as a HOx source, particularly in the afternoon. The peroxy radicals showed a strong dependence on [NO2] with a break point at 0.1 ppbv, where the radicals increased concomitantly with the reactive VOC loading, this is a lower value than seen at representative urban campaigns. The HO2/(HO2+ΣRO2) ratios are dependent on [NOx] ranging between 0.2 and 0.6, with the ratio increasing linearly with NOx. Significant night-time levels of peroxy radicals were measured up to 25 pptv. The contribution of ozone-alkenes and NO3-alkene chemistry to night-time peroxy radical production was shown to be on average 59 and 41%. The campaign mean net ozone production rate was 0.11±0.3 ppbv h-1. The ozone production rate was strongly dependent on [NO] having linear sensitivity (dln(P(O3))/dln(NO)=1.0). The results imply that the N(O3) (the in-situ net photochemical rate of ozone production/destruction) will be strongly sensitive in the marine boundary layer to small changes in [NO] which has ramifications for changing NOx loadings in the European continental boundary layer.

scholarly journals Oxygenated products formed from OH-initiated reactions of trimethylbenzene: Autoxidation and accretion

2020 ◽  
Author(s):  
Yuwei Wang ◽  
Archit Mehra ◽  
Jordan E. Krechmer ◽  
Gan Yang ◽  
Xiaoyu Hu ◽  
...  
Keyword(s):  
Organic Compounds ◽  
Mass Spectrometer ◽  
Chemical Ionization ◽  
Flow Reactor ◽  
Time Of Flight ◽  
Oxidation Products ◽  
Urban Atmosphere ◽  
Reaction Pathways ◽  
Peroxy Radicals ◽  
Flight Mass Spectrometer

Abstract. Gas-phase oxidation pathways and products of anthropogenic volatile organic compounds (VOCs), mainly aromatics, are the subject of intensive research with attention paid to their contributions to secondary organic aerosol (SOA) formation and potentially, new particle formation (NPF) in the urban atmosphere. In this study, a series of OH-initiated oxidation experiments of trimethylbenzene (TMB, C9H12) including 1,2,4-TMB, 1,3,5-TMB, 1,2,3-TMB, and 1,2,4-(methyl-D3)-TMBs (C9H9D3) were investigated in an oxidation flow reactor (OFR), in the absence and presence of NOx. Products were measured using a suite of state-of-the-art instruments, i.e., a nitrate-based chemical ionization – atmospheric pressure interface time-of-flight mass spectrometer (Nitrate CI-APi-TOF), an iodide-adduct chemical ionization – time-of-flight mass spectrometer (Iodide CI-TOF) equipped with a Filter Inlet for Gases and AEROsols (FIGAERO), and a Vocus proton-transfer-reaction mass spectrometer (Vocus PTR). A large number of C9 products with 1–11 oxygen atoms and C18 products presumably formed from dimerization of C9 peroxy radicals were observed, hinting the extensive existence of autoxidation and accretion reaction pathways in the OH-initiated oxidation reactions of TMBs. Oxidation products of 1,2,4-(methyl-D3)-TMBs with deuterium atoms in different methyl substituents were then used as a molecular basis to propose potential autoxidation reaction pathways. Accretion of C9 peroxy radicals is the most significant for aromatics with meta-substituents and the least for aromatics with ortho-substituents, if the number and size of substituted groups are identical. The presence of NOx would suppress the formation of C18 highly oxygenated molecules (HOMs) and enhance the formation of organonitrates, and even dinitrate organic compounds. Our results show that the oxidation products of TMB are much more diverse and could be more oxygenated than the current mechanisms predict.

scholarly journals Tree water relations trigger monoterpene emissions from Scots pine stem during spring recovery

2015 ◽  
Vol 12 (10) ◽  
pp. 7783-7814 ◽  
Author(s):  
A. Vanhatalo ◽  
T. Chan ◽  
J. Aalto ◽  
J. F. Korhonen ◽  
P. Kolari ◽  
...  
Keyword(s):  
Organic Compounds ◽  
Scots Pine ◽  
Sap Flow ◽  
Environmental Drivers ◽  
Diurnal Pattern ◽  
Night Time ◽  
Tree Diameter ◽  
Tree Canopies ◽  
Volatile Organic ◽  
Winter Time

Abstract. Tree canopies are known to emit large amounts of VOCs (volatile organic compounds) such as monoterpenes to the surrounding air. The main source for these is considered to be the green biomass, i.e. foliage, but emissions from the woody compartments have not been quantified. A VOC emission anomaly has been observed during transition from winter to summer activity. We analyzed if non-foliar components could partially explain the anomaly. We measured the VOC emissions from Scots pine (Pinus sylvestris L.) stems and shoots during the dehardening phase of trees in field conditions in two consecutive springs. We observed a large, transient monoterpene burst from stems, while the shoot monoterpene emissions and transpiration remained low. The burst lasted about 12 h. Simultaneously, an unusual night-time sap flow and an anomalous diurnal pattern of tree diameter were detected. Hence, we suggest that the monoterpene burst was a consequence of the recovery of the stem from winter-time. This indicates that the dominant processes and environmental drivers triggering the monoterpene emissions are different between stems and foliage.

scholarly journals Highly oxygenated organic molecules (HOM) formation in the isoprene oxidation by NO<sub>3</sub> radical

2020 ◽  
Author(s):  
Defeng Zhao ◽  
Iida Pullinen ◽  
Hendrik Fuchs ◽  
Stephanie Schrade ◽  
Rongrong Wu ◽  
...  
Keyword(s):  
Double Bond ◽  
First Generation ◽  
Second Generation ◽  
Organic Molecules ◽  
Closed Shell ◽  
Direct Reaction ◽  
Peroxy Radicals ◽  
Night Time ◽  
Time Profiles ◽  
Carbon Double Bond

Abstract. Highly oxygenated organic molecules (HOM) are found to play an important role in the formation and growth of secondary organic aerosol (SOA). SOA is an important type of aerosol with significant impact on air quality and climate. Compared with the oxidation of volatile organic compounds by O3 and OH, HOM formation in the oxidation by NO3 radical, an important oxidant at night-time and dawn, has received less attention. In this study, HOM formation in the reaction of isoprene with NO3 was investigated in the SAPHIR chamber (Simulation of Atmospheric PHotochemistry In a large Reaction chamber). A large number of HOM including monomers (C5), dimers (C10), and trimers (C15), both closed-shell compounds and open-shell peroxy radicals, were identified and were classified into various series according to their formula. Their formation pathways were proposed based on the peroxy radicals observed and known mechanisms in the literature, which were further constrained by the time profiles of HOM after sequential isoprene addition to differentiate first- and second-generation products. HOM monomers containing one to three N atoms (1–3N monomers) were formed, starting with NO3 addition to carbon double bond, forming peroxy radicals (RO2), followed by autoxidation. 1N monomers were formed by both the direct reaction of NO3 with isoprene and of NO3 with first-generation products. 2N-monomers (e.g. C5H8N2On (n = 8–13), C5H10N2On (n = 8–14)) were likely the termination products of C5H9N2On•, which was formed by the addition of NO3 to C5-hydroxynitrate (C5H9NO4), a first-generation product containing one carbon double bond. 2N-monomers, which were second-generation products, dominated in monomers and accounted for ~34 % of all HOM, indicating the important role of second-generation oxidation in HOM formation in isoprene+NO3 under our reaction conditions. H-shift of alkoxy radicals to form peroxy radicals and subsequent autoxidation (alkoxy-peroxy pathway) was found to be an important pathway of HOM formation. HOM dimers were mostly formed by the accretion reaction of various HOM monomer RO2 and via the termination reactions of dimer RO2 formed by further reaction of closed-shell dimers with NO3 and possibly by the reaction of C5-RO2 with isoprene. HOM trimers were likely formed by the accretion reaction of dimer RO2 with monomer RO2. The concentrations of different HOM showed distinct time profiles during the reaction, which was linked to their formation pathway. HOM concentrations either showed a typical time profile of first-generation products, or of second-generation products, or a combination of both, indicating multiple formation pathways and/or multiple isomers. Total HOM molar yield was estimated to be 1.2 %+1.3 %−0.7 %, which corresponded to a SOA yield of ~3.6 % assuming the molecular weight of C5H9NO6 as the lower limit. This yield suggests that HOM may contribute a significant fraction to SOA yield in the reaction of isoprene with NO3.

scholarly journals An MCM modeling study of nitryl chloride (ClNO<sub>2</sub>) impacts on oxidation, ozone production and nitrogen oxide partitioning in polluted continental outflow

2014 ◽  
Vol 14 (8) ◽  
pp. 3789-3800 ◽  
Author(s):  
T. P. Riedel ◽  
G. M. Wolfe ◽  
K. T. Danas ◽  
J. B. Gilman ◽  
W. C. Kuster ◽  
...  
Keyword(s):  
Nitrogen Oxide ◽  
Organic Compounds ◽  
Field Measurements ◽  
Chemical Mechanism ◽  
Ozone Production ◽  
Peroxy Radicals ◽  
Model Framework ◽  
Dinitrogen Pentoxide ◽  
Nitryl Chloride ◽  
Hydrogen Oxide

Abstract. Nitryl chloride (ClNO2) is produced at night by reactions of dinitrogen pentoxide (N2O5) on chloride containing surfaces. ClNO2 is photolyzed during the morning hours after sunrise to liberate highly reactive chlorine atoms (Cl·). This chemistry takes place primarily in polluted environments where the concentrations of N2O5 precursors (nitrogen oxide radicals and ozone) are high, though it likely occurs in remote regions at lower intensities. Recent field measurements have illustrated the potential importance of ClNO2 as a daytime Cl· source and a nighttime NOx reservoir. However, the fate of the Cl· and the overall impact of ClNO2 on regional photochemistry remain poorly constrained by measurements and models. To this end, we have incorporated ClNO2 production, photolysis, and subsequent Cl· reactions into an existing master chemical mechanism (MCM version 3.2) box model framework using observational constraints from the CalNex 2010 field study. Cl· reactions with a set of alkenes and alcohols, and the simplified multiphase chemistry of N2O5, ClNO2, HOCl, ClONO2, and Cl2, none of which are currently part of the MCM, have been added to the mechanism. The presence of ClNO2 produces significant changes to oxidants, ozone, and nitrogen oxide partitioning, relative to model runs excluding ClNO2 formation. From a nighttime maximum of 1.5 ppbv ClNO2, the daytime maximum Cl· concentration reaches 1 × 105 atoms cm−3 at 07:00 model time, reacting mostly with a large suite of volatile organic compounds (VOC) to produce 2.2 times more organic peroxy radicals in the morning than in the absence of ClNO2. In the presence of several ppbv of nitrogen oxide radicals (NOx = NO + NO2), these perturbations lead to similar enhancements in hydrogen oxide radicals (HOx = OH + HO2). Neglecting contributions from HONO, the total integrated daytime radical source is 17% larger when including ClNO2, which leads to a similar enhancement in integrated ozone production of 15%. Detectable levels (tens of pptv) of chlorine containing organic compounds are predicted to form as a result of Cl· addition to alkenes, which may be useful in identifying times of active Cl· chemistry.

Characterization of gaseous and particulate phase organic compounds during a winter-time air pollution event

2020 ◽  
Author(s):  
Julien Kammer ◽  
Niall O’Sullivan ◽  
Elena Gomez Alvarez ◽  
Stig Hellebust ◽  
John Wenger
Keyword(s):  
Air Pollution ◽  
Organic Compounds ◽  
Solid Fuel ◽  
Urban Areas ◽  
Phase Transfer ◽  
Anthropogenic Sources ◽  
Particulate Phase ◽  
Night Time ◽  
Field Campaign ◽  
Pollution Event

&lt;p&gt;&lt;strong&gt;&amp;#160;Abstract&lt;/strong&gt;&lt;/p&gt;&lt;p&gt;Atmospheric particles are known to cause adverse health effects and premature deaths in European cities. To improve air quality, a detailed understanding of particle sources is thus essential in order to reduce their emissions. Secondary organic aerosols (SOA) produced from the oxidation of volatile organic compounds emitted by anthropogenic sources such as road vehicles and solid fuel combustion is an important air pollution source in urban areas. It is demonstrated that SOA contribute significantly to the atmospheric particle loading, and could even be the major contributor at specific locations. Yet, state of the art models are still not able to reproduce SOA formation despite recent advances. Clearly, further work is needed to improve our understanding of the processes related to SOA formation.&lt;/p&gt;&lt;p&gt;In this context, a field campaign has been conducted at a monitoring station in Cork City, Ireland during winter 2019 (26&lt;sup&gt;th&lt;/sup&gt; January to 8&lt;sup&gt;th&lt;/sup&gt; February). The chemical composition of organic compounds in both gas and particle phases was investigated online using a Time-of-Flight Chemical Ionisation Mass Spectrometer (ToF-CIMS) coupled with a Filter Inlet for Gases and Aerosols (FIGAERO). PM&lt;sub&gt;2.5&lt;/sub&gt; concentration, ozone and nitrogen oxides (NO&lt;sub&gt;x&lt;/sub&gt;) were also monitored during the campaign, as well as meteorological parameters. Finally, air mass backward trajectories were computed using the HYSPLIT model.&lt;/p&gt;&lt;p&gt;A strong night-time air pollution event was observed during the field campaign, characterized by PM&lt;sub&gt;2.5&lt;/sub&gt; concentrations up to 180 &amp;#181;g m&lt;sup&gt;-3&lt;/sup&gt;. Using iodide as reagent, the FIGAERO-ToF-CIMS detected hundreds of ions simultaneously in gas and particulate phases. Among the identified compounds were a range of well-known atmospheric tracers of solid fuel burning, including phenolic compounds such as guaiacol and catechol, and numerous oxygenated polycyclic aromatic hydrocarbons (OPAHs). A number of nitrated aromatic compounds were also detected. In this work, the gas/particle partitioning of some of these key compounds has been investigated to provide information on phase transfer of solid fuel emissions over time. The thermograms produced by the FIGAERO analysis are also used to determine the volatility of the species detected. Finally, the FIGAERO-ToF-CIMS data is used to explore the extent to which oxidation of the gaseous emissions by the nitrate radical (NO&lt;sub&gt;3&lt;/sub&gt;) leads to the formation of nitrated compounds in the particulate phase. This work thus provides unique insights into the night-time oxidation processes that can lead to SOA formation from anthropogenic sources.&lt;/p&gt;&lt;p&gt;&amp;#160;&lt;/p&gt;&lt;p&gt;&lt;strong&gt;Acknowledgments&lt;/strong&gt;&lt;/p&gt;&lt;p&gt;This work was supported by the Irish Research Council (GOIPG/2017/1364) and by the European Union&amp;#8217;s Horizon 2020 research and innovation programme (EUROCHAMP-2020, grant no.&amp;#160;730997; Marie Sk&amp;#322;odowska-Curie grant agreement No. 751527).&lt;/p&gt;

scholarly journals Peroxy radical chemistry and the control of ozone photochemistry at Mace Head, Ireland during the summer of 2002

2005 ◽  
Vol 5 (6) ◽  
pp. 12313-12371 ◽  
Author(s):  
Z. L. Fleming ◽  
P. S. Monks ◽  
A. R. Rickard ◽  
D. E. Heard ◽  
W. J. Bloss ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Production Rate ◽  
Marine Boundary Layer ◽  
Strong Dependence ◽  
Peroxy Radical ◽  
Chemical Mechanism ◽  
Ozone Production ◽  
Peroxy Radicals ◽  
Night Time ◽  
Model Measurement

Abstract. Peroxy radical (HO2+ΣRO2) measurements, using the PEroxy Radical Chemical Amplification (PERCA) technique at the North Atlantic Marine Boundary Layer EXperiment (NAMBLEX) at Mace Head in summer 2002, are presented and put into the context of marine, boundary-layer chemistry. A suite of other chemical parameters (NO, NO2, NO3, CO, CH4, O3, VOCs, peroxides), photolysis frequencies and meteorological measurements, are used to present a detailed analysis of the role of peroxy radicals in tropospheric oxidation cycles and ozone formation. Under the range of conditions encountered the peroxy radical daily maxima varied from 10 to 40 pptv. The diurnal cycles showed an asymmetric shape typically shifted to the afternoon. Using a box model based on the master chemical mechanism the average model measurement agreement was 2.5 across the campaign. The addition of halogen oxides to the model increases the level of model/measurement agreement, apparently by respeciation of HOx. A good correlation exists between j(HCHO).[HCHO] and the peroxy radicals indicative of the importance of HCHO in the remote atmosphere as a HOx source, particularly in the afternoon. The peroxy radicals showed a strong dependence on [NOx] with a break point at 0.1 ppbv, where the radicals increased concomitantly with the reactive VOC loading, this is a lower value than seen at representative urban campaigns. The HO2/(HO2+ΣRO2) ratios are dependent on [NOx] ranging between 0.2 and 0.6, with the ratio increasing linearly with NOx. Significant night-time levels of peroxy radicals were measured up to 25 pptv. The contribution of ozone-alkenes and NO3-alkene chemistry to night-time peroxy radical production was shown to be on average 59 and 41%. The campaign mean net ozone production rate was 0.11±0.3 ppbv h−1. The ozone production rate was strongly dependent on [NO] having linear sensitivity (dln(P(O3))/dln(NO)=1.0). The results imply that the N(O3) (the in-situ net photochemical rate of ozone production/destruction) will be strongly sensitive in the marine boundary layer to small changes in [NO] which has ramifications for changing NOx loadings in the European continental boundary layer.

scholarly journals Oxygenated products formed from OH-initiated reactions of trimethylbenzene: autoxidation and accretion

2020 ◽  
Vol 20 (15) ◽  
pp. 9563-9579
Author(s):  
Yuwei Wang ◽  
Archit Mehra ◽  
Jordan E. Krechmer ◽  
Gan Yang ◽  
Xiaoyu Hu ◽  
...  
Keyword(s):  
Organic Compounds ◽  
Mass Spectrometer ◽  
Chemical Ionization ◽  
Flow Reactor ◽  
Time Of Flight ◽  
Oxidation Products ◽  
Urban Atmosphere ◽  
Reaction Pathways ◽  
Peroxy Radicals ◽  
Flight Mass Spectrometer

Abstract. Gas-phase oxidation pathways and products of anthropogenic volatile organic compounds (VOCs), mainly aromatics, are the subject of intensive research, with attention paid to their contributions to secondary organic aerosol (SOA) formation and potentially new particle formation (NPF) in the urban atmosphere. In this study, a series of OH-initiated oxidation experiments of trimethylbenzene (TMB, C9H12) including 1,2,4-TMB, 1,3,5-TMB, 1,2,3-TMB, and 1,2,4-(methyl-D3)-TMBs (C9H9D3) were investigated in an oxidation flow reactor (OFR) in the absence and presence of NOx. Products were measured using a suite of state-of-the-art instruments, i.e. a nitrate-based chemical ionization–atmospheric pressure interface time-of-flight mass spectrometer (nitrate CI-APi-TOF), an iodide-adduct chemical ionization time-of-flight mass spectrometer (iodide CI-TOF) equipped with a Filter Inlet for Gases and AEROsols (FIGAERO), and a Vocus proton-transfer-reaction mass spectrometer (Vocus PTR). A large number of C9 products with 1–11 oxygen atoms and C18 products presumably formed from dimerization of C9 peroxy radicals were observed, hinting at the extensive existence of autoxidation and accretion reaction pathways in the OH-initiated oxidation reactions of TMBs. Oxidation products of 1,2,4-(methyl-D3)-TMBs with deuterium atoms in different methyl substituents were then used as a molecular basis to propose potential autoxidation reaction pathways. Accretion of C9 peroxy radicals is the most significant for aromatics with meta-substituents and the least for aromatics with ortho-substituents if the number and size of substituted groups are identical. The presence of NOx would suppress the formation of highly oxygenated molecules (HOMs) of C18 and enhance the formation of organonitrates and even dinitrate organic compounds. Our results show that the oxidation products of TMB are much more diverse and could be more oxygenated than the current mechanisms predict.

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