scholarly journals Atmospheric photooxidation and ozonolysis of Δ<sup>3</sup>-carene and 3-caronaldehyde: Rate constants and product yields

2021 ◽  
Author(s):  
Luisa Lamberta Hantschke ◽  
Anna Novelli ◽  
Birger Bohn ◽  
Changmin Cho ◽  
David Reimer ◽  
...  
Keyword(s):  
Rate Constants ◽  
Reactive Nitrogen Species ◽  
Oxidation Products ◽  
Organic Nitrate ◽  
Effective Quantum Yield ◽  
Peroxy Radicals ◽  
Atmospheric Conditions ◽  
Mixing Ratios ◽  
Photolysis Frequency ◽  
First Time

Abstract. The oxidation of Δ3-carene and one of its main oxidation products, caronaldehyde, by the OH radical and O3 was investigated in the atmospheric simulation chamber SAPHIR under atmospheric conditions for NOx mixing ratios below 2 ppbv. Within this study, the rate constants of the reaction of Δ3-carene with OH and O3, and of the reaction of caronaldehyde with OH were determined to be (8.0 ± 0.5) × 10−11 cm3 s−1 at 304 K, (4.4 ± 0.2) × 10−17 cm3 s−1 at 300 K and (4.6 ± 1.6) × 10−11 cm3 s−1 at 300 K, respectively, in agreement with previously published values. The yields of caronaldehyde from the reaction of OH and ozone with Δ3-carene were determined to be (0.30 ± 0.05) and (0.06 ± 0.02), respectively. Both values are in reasonably well agreement with reported literature values. An organic nitrate (RONO2) yield from the reaction of NO with RO2 derived from Δ3-carene of (0.25 ± 0.04) was determined from the analysis of the reactive nitrogen species (NOy) in the SAPHIR chamber. The RONO2 yield of the reaction of NO with RO2 derived from the reaction of caronaldehyde with OH was found to be (0.10 ± 0.02). The organic nitrate yields of Δ3-carene and caronaldehyde oxidation with OH are reported here for the first time in the gas phase. An OH yield of (0.65 ± 0.10) was determined from the ozonolysis of Δ3-carene. Calculations of production and destruction rates of the sum of hydroxyl and peroxy radicals (ROx = OH+HO2+RO2) demonstrated that there were no unaccounted production or loss processes of radicals in the oxidation of Δ3-carene for conditions of the the chamber experiments. In an OH free experiment with added OH scavenger, the photolysis frequency of caronaldehyde was obtained from its photolytical decay. The experimental photolysis frequency was a factor of 7 higher than the value calculated from the measured solar acintic flux density, an absorption cross section from the literature and an assumed effective quantum yield of unity for photodissociation.

scholarly journals Atmospheric photooxidation and ozonolysis of Δ<sup>3</sup>-carene and 3-caronaldehyde: rate constants and product yields

2021 ◽  
Vol 21 (16) ◽  
pp. 12665-12685
Author(s):  
Luisa Hantschke ◽  
Anna Novelli ◽  
Birger Bohn ◽  
Changmin Cho ◽  
David Reimer ◽  
...  
Keyword(s):  
Rate Constants ◽  
Oxidation Products ◽  
Organic Nitrate ◽  
Effective Quantum Yield ◽  
Peroxy Radicals ◽  
Atmospheric Conditions ◽  
Mixing Ratios ◽  
Photolysis Frequency ◽  
First Time ◽  
Good Agreement

Abstract. The oxidation of Δ3-carene and one of its main oxidation products, caronaldehyde, by the OH radical and O3 was investigated in the atmospheric simulation chamber SAPHIR under atmospheric conditions for NOx mixing ratios below 2 ppbv. Within this study, the rate constants of the reaction of Δ3-carene with OH and O3 and of the reaction of caronaldehyde with OH were determined to be (8.0±0.5)×10-11 cm3 s−1 at 304 K, (4.4±0.2)×10-17 cm3 s−1 at 300 K and (4.6±1.6)×10-11 cm3 s−1 at 300 K, in agreement with previously published values. The yields of caronaldehyde from the reaction of OH and ozone with Δ3-carene were determined to be 0.30±0.05 and 0.06±0.02, respectively. Both values are in reasonably good agreement with reported literature values. An organic nitrate (RONO2) yield from the reaction of NO with RO2 derived from Δ3-carene of 0.25±0.04 was determined from the analysis of the reactive nitrogen species (NOy) in the SAPHIR chamber. The RONO2 yield of the reaction of NO with RO2 derived from the reaction of caronaldehyde with OH was found to be 0.10±0.02. The organic nitrate yields of Δ3-carene and caronaldehyde oxidation with OH are reported here for the first time in the gas phase. An OH yield of 0.65±0.10 was determined from the ozonolysis of Δ3-carene. Calculations of production and destruction rates of the sum of hydroxyl and peroxy radicals (ROx=OH+HO2+RO2) demonstrated that there were no unaccounted production or loss processes of radicals in the oxidation of Δ3-carene for conditions of the chamber experiments. In an OH-free experiment with added OH scavenger, the photolysis frequency of caronaldehyde was obtained from its photolytical decay. The experimental photolysis frequency was a factor of 7 higher than the value calculated from the measured solar actinic flux density, an absorption cross section from the literature and an assumed effective quantum yield of unity for photodissociation.

Photooxidation and ozonolysis of Δ3-carene and its oxidation product caronaldehyde in the atmospheric simulation chamber SAPHIR

2021 ◽  
Author(s):  
Luisa Hantschke ◽  
Anna Novelli ◽  
Birger Bohn ◽  
Changmin Cho ◽  
David Reimer ◽  
...  
Keyword(s):  
Oxidation Product ◽  
Boreal Forests ◽  
Oxidation Products ◽  
Organic Nitrate ◽  
Organic Nitrates ◽  
Peroxy Radicals ◽  
Atmospheric Conditions ◽  
Oxidation Reactions ◽  
Reaction Rate Constants ◽  
Simulation Chamber

&lt;p&gt;Of the total global annual monoterpene emissions, &amp;#916;&lt;sup&gt;3&lt;/sup&gt;-carene contributes 4.5 %, making it the 7&lt;sup&gt;th&lt;/sup&gt; most abundant monoterpene worldwide. As it is primarily emitted by pine trees, &amp;#916;&lt;sup&gt;3&lt;/sup&gt;-carene can regionally gain in importance, for example in boreal forests and Mediterranean regions.&amp;#160; Oxidation products of monoterpenes such as organic nitrates and aldehydes are known to impact the formation of secondary pollutants such as ozone and particles, so understanding their atmospheric formation and fate is crucial.&lt;/p&gt;&lt;p&gt;The photooxidation and ozonolysis of &amp;#916;&lt;sup&gt;3&lt;/sup&gt;-carene and the photooxidation and photolysis of its main daytime photooxidation product caronaldehyde were investigated in the atmospheric simulation chamber SAPHIR. Oxidation reactions were studied under atmospheric conditions with high (&gt; 8 ppbv) and low (&lt; 2 ppbv) NOx concentrations. Reaction rate constants of the reaction of &amp;#916;&lt;sup&gt;3&lt;/sup&gt;-carene with OH and O&lt;sub&gt;3&lt;/sub&gt;, and of the reaction of caronaldehyde with OH as well as photolysis frequencies of caronaldehyde were determined. Production and destruction rates of the sum of hydroxyl and peroxy radicals (ROx = OH+HO2+RO2) were analysed to determine if there were unaccounted production and loss processes of radicals in the oxidation of &amp;#916;&lt;sup&gt;3&lt;/sup&gt;-carene. The yield of &amp;#916;&lt;sup&gt;3&lt;/sup&gt;-carene&amp;#8217;s oxidation product caronaldehyde was determined from measured timeseries from OH photooxidation and ozonolysis experiments. Additionally, the OH yield from ozonolysis of &amp;#916;&lt;sup&gt;3&lt;/sup&gt;-carene was determined.&lt;/p&gt;&lt;p&gt;Organic nitrate (RONO&lt;sub&gt;2&lt;/sub&gt;) yields of the reaction of RO&lt;sub&gt;2&lt;/sub&gt; + NO, from RO&lt;sub&gt;2&lt;/sub&gt; produced from the reactions of &amp;#916;&lt;sup&gt;3&lt;/sup&gt;-carene and caronaldehyde with OH were determined by analyzing the reactive nitrogen species (NOy) in the chamber.&lt;/p&gt;

Kinetic study on the linalool ozonolysis reaction in the atmosphere

2012 ◽  
Vol 90 (4) ◽  
pp. 353-361 ◽  
Author(s):  
Xiaomin Sun ◽  
Chenxi Zhang ◽  
Yuyang Zhao ◽  
Jing Bai ◽  
Maoxia He
Keyword(s):  
Rate Constants ◽  
Transition State Theory ◽  
State Theory ◽  
Oxidation Products ◽  
Tunneling Effect ◽  
Total Rate ◽  
Variational Transition State Theory ◽  
Atmospheric Lifetime ◽  
Ozone Addition ◽  
First Time

In the atmosphere, linalool ozonolysis will generate a series of oxidation products and then form particles through nucleation. In this study, the linalool ozonolysis mechanisms were studied and some of the main products detected from experiment are verified. The Rice–Ramsperger–Kassel–Marcus (RRKM) theory and the canonical variational transition state theory (CVT) with small curvature tunneling effect (SCT) are used to calculate rate constants over the temperature range of 200∼800 K. The total rate constant for the reaction of ozone with linalool is 4.50 × 10−16 cm3 molecule–l s–l, and the addition of ozone to (CH3)2C=CH– is the main ozone addition position. Furthermore, the Arrhenius formulas are fitted and the lifetimes of reaction species in the troposphere are discussed for the first time. The total atmospheric lifetime of linalool relative to O3 is 2.30 h. The O3-initiated atmospheric lifetimes of P1, P3, and P6 are 2.64 months, 16.67 days, and 15.5 h, respectively.

scholarly journals OH and HO<sub>2</sub> radical chemistry in a midlatitude forest: Measurements and model comparisons

2019 ◽  
Author(s):  
Michelle L. Lew ◽  
Pamela S. Rickly ◽  
Brandon P. Bottorff ◽  
Sofia Sklaveniti ◽  
Thierry Léonardis ◽  
...  
Keyword(s):  
Atmospheric Chemistry ◽  
Global Climate ◽  
Oxidation Products ◽  
Chemical Mechanism ◽  
Ozone Production ◽  
Peroxy Radicals ◽  
Mixing Ratios ◽  
Photolysis Rates ◽  
Model Predictions ◽  
Ho2 Radical

Abstract. Reactions of the hydroxyl (OH) and peroxy radicals (HO2 and RO2) play a central role in the chemistry of the atmosphere. In addition to controlling the lifetimes of many trace gases important to issues of global climate change, OH radical reactions initiate the oxidation of volatile organic compounds (VOCs) which can lead to the production of ozone and secondary organic aerosols in the atmosphere. Previous measurements of these radicals in forest environments characterized by high mixing ratios of isoprene and low mixing ratios of nitrogen oxides (NOx) have shown serious discrepancies with modeled concentrations. These results bring into question our understanding of the atmospheric chemistry of isoprene and other biogenic VOCs under low NOx conditions. During the summer of 2015, OH and HO2 radical concentrations as well as total OH reactivity were measured using Laser-Induced Fluorescence - Fluorescence Assay by Gas Expansion (LIF-FAGE) techniques as part of the Indiana Radical, Reactivity and Ozone Production Intercomparison (IRRONIC). This campaign took place in a forested area near the Indiana University, Bloomington campus characterized by high mixing ratios of isoprene and low mixing ratios of NOx. Supporting measurements of photolysis rates, VOCs, NOx, and other species were used to constrain a zero-dimensional box model based on the Regional Atmospheric Chemistry Mechanism (RACM2) and the Master Chemical Mechanism (MCM). Using an OH chemical scavenger technique, the study revealed the presence of an interference with the LIF-FAGE measurements of OH that increased with both ambient concentrations of ozone and temperature. Subtraction of the interference resulted in measured OH concentrations that were in better agreement with model predictions, although the model still underestimated the measured concentrations, likely due to an underestimation of the concentration of NO at this site. Measurements of HO2 radical concentrations during the campaign included a fraction of isoprene-based peroxy radicals (HO2* = HO2 + αRO2) and were found to agree with model predictions. On average, the measured reactivity was consistent with that calculated from measured OH sinks to within 20 %, with modeled oxidation products accounting for the missing reactivity, although significant missing reactivity (approximately 40 % of the total measured reactivity) was observed on some days.

scholarly journals OH regeneration from methacrolein oxidation investigated in the atmosphere simulation chamber SAPHIR

2014 ◽  
Vol 14 (15) ◽  
pp. 7895-7908 ◽  
Author(s):  
H. Fuchs ◽  
I.-H. Acir ◽  
B. Bohn ◽  
T. Brauers ◽  
H.-P. Dorn ◽  
...  
Keyword(s):  
Reaction Pathway ◽  
Chemical Mechanism ◽  
Isomerization Reaction ◽  
Initial Reaction ◽  
Oh Radicals ◽  
Peroxy Radicals ◽  
Atmospheric Conditions ◽  
Model Calculations ◽  
Mixing Ratios ◽  
Simulation Chamber

Abstract. Hydroxyl radicals (OH) are the most important reagent for the oxidation of trace gases in the atmosphere. OH concentrations measured during recent field campaigns in isoprene-rich environments were unexpectedly large. A number of studies showed that unimolecular reactions of organic peroxy radicals (RO2) formed in the initial reaction step of isoprene with OH play an important role for the OH budget in the atmosphere at low mixing ratios of nitrogen monoxide (NO) of less than 100 pptv. It has also been suggested that similar reactions potentially play an important role for RO2 from other compounds. Here, we investigate the oxidation of methacrolein (MACR), one major oxidation product of isoprene, by OH in experiments in the simulation chamber SAPHIR under controlled atmospheric conditions. The experiments show that measured OH concentrations are approximately 50% larger than calculated by the Master Chemical Mechanism (MCM) for conditions of the experiments (NO mixing ratio of 90 pptv). The analysis of the OH budget reveals an OH source that is not accounted for in MCM, which is correlated with the production rate of RO2 radicals from MACR. In order to balance the measured OH destruction rate, 0.77 OH radicals (1σ error: ± 0.31) need to be additionally reformed from each reaction of OH with MACR. The strong correlation of the missing OH source with the production of RO2 radicals is consistent with the concept of OH formation from unimolecular isomerization and decomposition reactions of RO2. The comparison of observations with model calculations gives a lower limit of 0.03 s−1 for the reaction rate constant if the OH source is attributed to an isomerization reaction of MACR-1-OH-2-OO and MACR-2-OH-2-OO formed in the MACR + OH reaction as suggested in the literature (Crounse et al., 2012). This fast isomerization reaction would be a competitor to the reaction of this RO2 species with a minimum of 150 pptv NO. The isomerization reaction would be the dominant reaction pathway for this specific RO2 radical in forested regions, where NO mixing ratios are typically much smaller.

scholarly journals Ozone production in remote oceanic and industrial areas derived from ship based measurements of peroxy radicals during TexAQS 2006

2011 ◽  
Vol 11 (6) ◽  
pp. 2471-2485 ◽  
Author(s):  
R. Sommariva ◽  
S. S. Brown ◽  
J. M. Roberts ◽  
D. M. Brookes ◽  
A. E. Parker ◽  
...  
Keyword(s):  
Gulf Coast ◽  
Peroxy Radical ◽  
Oxidation Products ◽  
Ozone Production ◽  
Ozone Formation ◽  
Peroxy Radicals ◽  
Industrial Areas ◽  
Mixing Ratios ◽  
Photolysis Rates ◽  
Houston Ship Channel

Abstract. During the Texas Air Quality Study II (TexAQS 2006) campaign, a PEroxy Radical Chemical Amplifier (PERCA) was deployed on the NOAA research vessel R/V Brown to measure total peroxy radicals (HO2+Σ RO2). Day-time mixing ratios of HO2+Σ RO2 between 25 and 110 ppt were observed throughout the study area – the Houston/Galveston region and the Gulf coast of the US – and analyzed in relation to measurements of nitrogen oxides, volatile organic compounds (VOC) and photolysis rates to assess radical sources and sinks in the region. The measurements of HO2+Σ RO2 were used to calculate the in-situ net photochemical formation of ozone. Measured median values ranged from 0.6 ppb/h in clean oceanic air masses up to several tens of ppb/h in the most polluted industrial areas. The results are consistent with previous studies and generally agree with observations made during the previous TexAQS 2000 field campaign. The net photochemical ozone formation rates determined at Barbours Cut, a site immediately south of the Houston Ship Channel, were analyzed in relation to local wind direction and VOC reactivity to understand the relationship between ozone formation and local VOC emissions. The measurements of HO2+Σ RO2 made during the R/V Brown TexAQS 2006 cruise indicate that ozone formation is NOx-limited in the Houston/Galveston region and influenced by highly reactive hydrocarbons, especially alkenes from urban and industrial sources and their photo-oxidation products, such as formaldehyde.

scholarly journals Global tropospheric effects of aromatic chemistry with the SAPRC-11 mechanism implemented in GEOS-Chem

2018 ◽  
Author(s):  
Yingying Yan ◽  
David Cabrera-Perez ◽  
Jintai Lin ◽  
Andrea Pozzer ◽  
Lu Hu ◽  
...  
Keyword(s):  
Production Efficiency ◽  
Chemical Species ◽  
Oxidation Products ◽  
Chemical Mechanism ◽  
Ozone Production ◽  
Peroxy Radicals ◽  
Mixing Ratios ◽  
Regional Effects ◽  
Source Regions ◽  
Remote Troposphere

Abstract. The GEOS-Chem model has been updated with the SAPRC-11 aromatics chemical mechanism, with the purpose of evaluating global and regional effects of the most abundant aromatics (benzene, toluene, xylenes) on the chemical species important for tropospheric oxidation capacity. The model evaluation based on surface and aircraft observations indicates good agreement for aromatics and ozone. A comparison between scenarios in GEOS-Chem with simplified aromatic chemistry (as in the standard setup, with no ozone formation from related peroxy radicals or recycling of NOx) and with the SAPRC-11 scheme reveals relatively slight changes in ozone, hydroxyl radical, and nitrogen oxides on a global mean basis (1–4 %), although remarkable regional differences (5–20 %) exist near the source regions. NOx decreases over the source regions and increases in the remote troposphere, due mainly to more efficient transport of peroxyacetyl nitrate (PAN), which is increased with the SAPRC aromatic chemistry. Model ozone mixing ratios with the updated aromatic chemistry increase by up to 5 ppb (more than 10 %), especially in industrially polluted regions. The ozone change is partly due to the direct influence of aromatic oxidation products on ozone production rates, and in part to the altered spatial distribution of NOx that enhances the tropospheric ozone production efficiency. Improved representation of aromatics is important to simulate the tropospheric oxidation.

scholarly journals Global tropospheric effects of aromatic chemistry with the SAPRC-11 mechanism implemented in GEOS-Chem version 9-02

2019 ◽  
Vol 12 (1) ◽  
pp. 111-130 ◽  
Author(s):  
Yingying Yan ◽  
David Cabrera-Perez ◽  
Jintai Lin ◽  
Andrea Pozzer ◽  
Lu Hu ◽  
...  
Keyword(s):  
Production Efficiency ◽  
Chemical Species ◽  
Oxidation Products ◽  
Chemical Mechanism ◽  
Ozone Production ◽  
Peroxy Radicals ◽  
Mixing Ratios ◽  
Earth Observing System ◽  
Source Regions ◽  
Remote Troposphere

Abstract. The Goddard Earth Observing System with chemistry (GEOS-Chem) model has been updated with the State-wide Air Pollution Research Center version 11 (SAPRC-11) aromatics chemical mechanism, with the purpose of evaluating global and regional effects of the most abundant aromatics (benzene, toluene, xylenes) on the chemical species important for tropospheric oxidation capacity. The model evaluation based on surface and aircraft observations indicates good agreement for aromatics and ozone. A comparison between scenarios in GEOS-Chem with simplified aromatic chemistry (as in the standard setup, with no ozone formation from related peroxy radicals or recycling of NOx) and with the SAPRC-11 scheme reveals relatively slight changes in ozone, the hydroxyl radical, and nitrogen oxides on a global mean basis (1 %–4 %), although remarkable regional differences (5 %–20 %) exist near the source regions. NOx decreases over the source regions and increases in the remote troposphere, due mainly to more efficient transport of peroxyacetyl nitrate (PAN), which is increased with the SAPRC aromatic chemistry. Model ozone mixing ratios with the updated aromatic chemistry increase by up to 5 ppb (more than 10 %), especially in industrially polluted regions. The ozone change is partly due to the direct influence of aromatic oxidation products on ozone production rates, and in part to the altered spatial distribution of NOx that enhances the tropospheric ozone production efficiency. Improved representation of aromatics is important to simulate the tropospheric oxidation.

scholarly journals On the similarities and differences between the products of oxidation of hydrocarbons under simulated atmospheric conditions and cool-flames

2020 ◽  
Author(s):  
Roland Benoit ◽  
Nesrine Belhadj ◽  
Maxence Lailliau ◽  
Philippe Dagaut
Keyword(s):  
Atmospheric Chemistry ◽  
High Resolution Mass Spectrometry ◽  
Direct Injection ◽  
Oxidation Products ◽  
Peroxy Radicals ◽  
Atmospheric Conditions ◽  
Combustion Chemistry ◽  
Stirred Reactor ◽  
Oxidation Of Hydrocarbons ◽  
Reacting Mixtures

Abstract. Whereas the kinetics of oxidation of limonene has been extensively studied and mechanisms for its oxidation by OH and/or ozone have been proposed, more studies are required for better understanding its oxidation pathways. The oxidation of limonene-oxygen-nitrogen mixtures was studied using a jet-stirred reactor at elevated temperature and atmospheric pressure. Samples of the reacting mixtures were collected and analyzed by high resolution mass spectrometry (Orbitrap) after direct injection or after separation by reverse-phase ultra-high-pressure liquid chromatography and soft ionization by (+/−) HESI and (+/−) APCI. The results indicate that among the 1138 detected products, many oxygenates found in earlier studies of limonene oxidation by OH and/or ozone are also produced under the present conditions. Other highly oxygenated products and oligomers were also detected in the present work. The results are discussed in terms of reaction pathways involving the initial formation of peroxy radicals, isomerization reactions yielding keto-hydroperoxides and other oxygenated intermediates and products up to C25H32O17. The possible occurrence of the Waddington mechanism and of the Korcek mechanism are also discussed. The present work demonstrates similarities between the oxidation products and oxidation pathways of limonene under simulated atmospheric conditions and in those encountered during the self-ignition of hydrocarbons at low temperatures, which should stimulate future interactions between communities of atmospheric chemistry and combustion chemistry to improve current chemical models.

scholarly journals OH regeneration from methacrolein oxidation investigated in the atmosphere simulation chamber SAPHIR

2014 ◽  
Vol 14 (4) ◽  
pp. 5197-5231 ◽  
Author(s):  
H. Fuchs ◽  
I.-H. Acir ◽  
B. Bohn ◽  
T. Brauers ◽  
H.-P. Dorn ◽  
...  
Keyword(s):  
Nitrogen Monoxide ◽  
Reaction Rate Constant ◽  
Isomerization Reaction ◽  
Initial Reaction ◽  
Oh Radicals ◽  
Peroxy Radicals ◽  
Atmospheric Conditions ◽  
Model Calculations ◽  
Mixing Ratios ◽  
Simulation Chamber

Abstract. Hydroxyl radicals (OH) are the most important reagent for the oxidation of trace gases in the atmosphere. OH concentrations measured during recent field campaigns in isoprene rich environments were unexpectedly large. A number of studies showed that unimolecular reactions of organic peroxy radicals (RO2) formed in the initial reaction step of isoprene with OH play an important role for the OH budget in the atmosphere at low mixing ratios of nitrogen monoxide (NO) of less than 100 pptv. It has also been suggested that similar reactions potentially play an important role for RO2 from other compounds. Here, we investigate the oxidation of methacrolein (MACR), one major oxidation product of isoprene, by OH in experiments in the simulation chamber SAPHIR under controlled atmospheric conditions. The experiments show that measured OH concentrations are approximately 50% larger than calculated by current chemical models for conditions of the experiments (NO mixing ratio of 90 pptv). The analysis of the OH budget reveals a so far unaccounted OH source, which is correlated with the production rate of RO2 radicals from MACR. In order to balance the measured OH destruction rate, (0.77±0.3) OH radicals need to be additionally reformed from each OH that has reacted with MACR. The strong correlation of the missing OH source with the production of RO2 radicals is consistent with the concept of OH formation from unimolecular isomerization and decomposition reactions of RO2. The comparison of observations with model calculations gives a lower limit of 0.03 s−1 for the reaction rate constant, if the OH source is attributed to an isomerization reaction of one RO2 species formed in the MACR+OH reaction as suggested in literature. This fast isomerization reaction would be competitive to the reaction of this RO2 species with minimum 150 pptv NO.

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