scholarly journals Investigation of the <i>α</i>-pinene photooxidation by OH in the atmospheric simulation chamber SAPHIR

2019 ◽  
Vol 19 (18) ◽  
pp. 11635-11649
Author(s):  
Michael Rolletter ◽  
Martin Kaminski ◽  
Ismail-Hakki Acir ◽  
Birger Bohn ◽  
Hans-Peter Dorn ◽  
...  
Keyword(s):  
Time Series ◽  
Oxidation Mechanism ◽  
Peroxy Radical ◽  
Chemical Oxidation ◽  
Oxidation Products ◽  
Chemical Mechanism ◽  
Model Calculations ◽  
Mixing Ratios ◽  
Measured Time ◽  
Simulation Chamber

Abstract. The photooxidation of the most abundant monoterpene, α-pinene, by the hydroxyl radical (OH) was investigated at atmospheric concentrations in the atmospheric simulation chamber SAPHIR. Concentrations of nitric oxide (NO) were below 120 pptv. Yields of organic oxidation products are determined from measured time series giving values of 0.11±0.05, 0.19±0.06, and 0.05±0.03 for formaldehyde, acetone, and pinonaldehyde, respectively. The pinonaldehyde yield is at the low side of yields measured in previous laboratory studies, ranging from 0.06 to 0.87. These studies were mostly performed at reactant concentrations much higher than observed in the atmosphere. Time series of measured radical and trace-gas concentrations are compared to results from model calculations applying the Master Chemical Mechanism (MCM) 3.3.1. The model predicts pinonaldehyde mixing ratios that are at least a factor of 4 higher than measured values. At the same time, modeled hydroxyl and hydroperoxy (HO2) radical concentrations are approximately 25 % lower than measured values. Vereecken et al. (2007) suggested a shift of the initial organic peroxy radical (RO2) distribution towards RO2 species that do not yield pinonaldehyde but produce other organic products. Implementing these modifications reduces the model–measurement gap of pinonaldehyde by 20 % and also improves the agreement in modeled and measured radical concentrations by 10 %. However, the chemical oxidation mechanism needs further adjustment to explain observed radical and pinonaldehyde concentrations. This could be achieved by adjusting the initial RO2 distribution, but could also be done by implementing alternative reaction channels of RO2 species that currently lead to the formation of pinonaldehyde in the model.

scholarly journals Investigation of the α-pinene photooxidation by OH in the atmospheric simulation chamber SAPHIR

2019 ◽  
Author(s):  
Michael Rolletter ◽  
Martin Kaminski ◽  
Ismail-Hakki Acir ◽  
Birger Bohn ◽  
Hans-Peter Dorn ◽  
...  
Keyword(s):  
Time Series ◽  
Oxidation Mechanism ◽  
Peroxy Radical ◽  
Chemical Oxidation ◽  
Oxidation Products ◽  
Chemical Mechanism ◽  
Model Calculations ◽  
Mixing Ratios ◽  
Measured Time ◽  
Simulation Chamber

Abstract. The photooxidation of the most abundant monoterpene α-pinene, by the hydroxyl radical (OH) was investigated at atmospheric concentrations in the atmospheric simulation chamber SAPHIR. Concentrations of nitric oxide (NO) were below 120 pptv. Yields of organic oxidation products are determined from measured time series giving values of 0.11 ± 0.05, 0.19 ± 0.06, and 0.05 ± 0.03 for formaldehyde, acetone, and pinonaldehyde, respectively. The pinonaldehyde yield is at the low side of yields measured in previous laboratory studies, ranging from 0.06 to 0.87. These studies were mostly performed at reactant concentrations much higher than observed in the atmosphere. Time series of measured radical and trace gas concentrations are compared to results from model calculations applying the Master Chemical Mechanism (MCM) 3.3.1. The model predicts pinonaldehyde mixing ratios that are at least a factor of 4 higher than measured values. At the same time, modelled hydroxyl and hydroperoxy (HO2) radical concentrations are approximately 25 % lower than measured values. Vereecken et al. (2007) suggested a shift of the initial organic peroxy radical (RO2) distribution towards RO2 species that do not yield pinonaldehyde, but produce other organic products. Implementing these modifications reduces the model-measurement gap of pinonaldehyde by 20 % and also improves the agreement in modelled and measured radical concentrations by 10 %. However, the chemical oxidation mechanism needs further adjustment to explain observed radical and pinonaldehyde concentrations. This could be achieved by adjusting the initial RO2 distribution, but could also be done by implementing alternative reaction channels of RO2 species that currently lead to the formation of pinonaldehyde in the model.

scholarly journals Formation and sink of glyoxal and methylglyoxal in a polluted subtropical environment: observation-based photochemical analysis and impact evaluation

2020 ◽  
Vol 20 (19) ◽  
pp. 11451-11467
Author(s):  
Zhenhao Ling ◽  
Qianqian Xie ◽  
Min Shao ◽  
Zhe Wang ◽  
Tao Wang ◽  
...  
Keyword(s):  
Southern China ◽  
Oxidation Mechanism ◽  
Receptor Site ◽  
Oxidation Products ◽  
Chemical Mechanism ◽  
Major Pathway ◽  
Mixing Ratios ◽  
Heterogeneous Processes ◽  
The Pearl River ◽  
Improved Model

Abstract. The dicarbonyls glyoxal (Gly) and methylglyoxal (Mgly) have been recognized as important precursors of secondary organic aerosols (SOAs) through the atmospheric heterogeneous process. In this study, field measurement was conducted at a receptor site in the Pearl River Delta (PRD) region in southern China, and an observation-based photochemical box model was subsequently applied to investigate the production and evolution of Gly and Mgly as well as their contributions to SOA formation. The model was coupled with a detailed gas-phase oxidation mechanism of volatile organic compounds (VOCs) (i.e., Master Chemical Mechanism, MCM, v3.2), heterogeneous processes of Gly and Mgly (i.e., reversible partitioning in aqueous phase, irreversible volume reactions and irreversible surface uptake processes), and the gas–particle partitioning of oxidation products. The results suggested that without considering the heterogeneous processes of Gly and Mgly on aerosol surfaces, the model would overpredict the mixing ratios of Gly and Mgly by factors of 3.3 and 3.5 compared to the observed levels. The agreement between observation and simulation improved significantly when the irreversible uptake and the reversible partitioning were incorporated into the model, which in total both contributed ∼ 62 % to the destruction of Gly and Mgly during daytime. Further analysis of the photochemical budget of Gly and Mgly showed that the oxidation of aromatics by the OH radical was the major pathway producing Gly and Mgly, followed by degradation of alkynes and alkenes. Furthermore, based on the improved model mechanism, the contributions of VOC oxidation to SOA formed from gas–particle partitioning (SOAgp) and from heterogeneous processes of Gly and Mgly (SOAhet) were also quantified. It was found that o-xylene was the most significant contributor to SOAgp formation (∼ 29 %), while m,p-xylene and toluene made dominant contributions to SOAhet formation. Overall, the heterogeneous processes of Gly and Mgly can explain ∼ 21 % of SOA mass in the PRD region. The results of this study demonstrated the important roles of heterogeneous processes of Gly and Mgly in SOA formation and highlighted the need for a better understanding of the evolution of intermediate oxidation products.

scholarly journals Mainz Isoprene Mechanism 2 (MIM2): an isoprene oxidation mechanism for regional and global atmospheric modelling

2008 ◽  
Vol 8 (4) ◽  
pp. 14033-14085 ◽  
Author(s):  
D. Taraborrelli ◽  
M. G. Lawrence ◽  
T. M. Butler ◽  
R. Sander ◽  
J. Lelieveld
Keyword(s):  
Atmospheric Chemistry ◽  
Oxidation Mechanism ◽  
Tropospheric Chemistry ◽  
Oxidation Products ◽  
Chemical Mechanism ◽  
Good Representation ◽  
Chemical Production ◽  
Global Models ◽  
Mixing Ratios ◽  
Isoprene Oxidation

Abstract. We present an oxidation mechanism of intermediate size for isoprene (2-methyl-1,3-butadiene) suitable for simulations in regional and global atmospheric chemistry models, which we call MIM2. It is a reduction of the corresponding detailed mechanism in the Master Chemical Mechanism (MCM v3.1) and intended as the second version of the well-established Mainz Isoprene Mechanism (MIM). Our aim is to improve the representation of tropospheric chemistry in regional and global models under all NOx regimes. We evaluate MIM2 and re-evaluate MIM through comparisons with MCM v3.1. We find that MIM and MIM2 compute similar O3, OH and isoprene mixing ratios. Unlike MIM, MIM2 produces small relative biases for NOx and organic nitrogen-containing species due to a good representation of the alkyl and peroxy acyl nitrates (RONO2 and RC(O)OONO2). Moreover, MIM2 computes only small relative biases with respect to hydrogen peroxide (H2O2), methyl peroxide (CH3OOH), methanol (CH3OH), formaldehyde (HCHO), peroxy acetyl nitrate (PAN), and formic and acetic acids (HCOOH and CH3C(O)OH), being always below ≈6% in all NOx scenarios studied. Most of the isoprene oxidation products are represented explicitly, including methyl vinyl ketone (MVK), methacrolein (MACR), hydroxyacetone and methyl glyoxal. MIM2 is mass-conserving with respect to carbon, including CO2 as well. Therefore, it is suitable for studies assessing carbon monoxide (CO) from biogenic sources, as well as for studies focused on the carbon cycle. Compared to MIM, MIM2 considers new species like acetaldehyde (CH3CHO), propene (CH2=CHCH3) and glyoxal (CHOCHO) with global chemical production rates for the year 2005 of 7.3, 9.5 and 33.8 Tg/yr, respectively. Our new mechanism is expected to substantially improve the results of atmospheric chemistry models by more accurately representing the interplay between atmospheric chemistry, transport and deposition, especially of nitrogen reservoir species. MIM2 allows regional and global models to easily incorporate new experimental results on the chemistry of organic species.

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 Investigation of the β-pinene photooxidation by OH in the atmosphere simulation chamber SAPHIR

2016 ◽  
Author(s):  
Martin Kaminski ◽  
Hendrik Fuchs ◽  
Ismail-Hakki Acir ◽  
Birger Bohn ◽  
Theo Brauers ◽  
...  
Keyword(s):  
Degradation Mechanism ◽  
Degradation Process ◽  
Product Distribution ◽  
High Reactivity ◽  
Oxidation Products ◽  
Chemical Mechanism ◽  
Emission Rates ◽  
Photochemical Degradation ◽  
Atmosphere Simulation Chamber ◽  
Simulation Chamber

Abstract. Beside isoprene, monoterpenes are the non-methane volatile organic compounds (VOC) with the highest global emission rates. Due to their high reactivity towards OH, monoterpenes can dominate the radical chemistry of the atmosphere in forested areas. In the present study the photochemical degradation mechanism of β-pinene was investigated in the Jülich atmosphere simulation chamber SAPHIR. The focus of this study is on the OH budget in the degradation process. Therefore the SAPHIR chamber was equipped with instrumentation to measure radicals (OH, HO2, RO2), the total OH reactivity, important OH precursors (O3, HONO, HCHO), the parent VOC beta-pinene, its main oxidation products, acetone and nopinone, and photolysis frequencies. All experiments were carried out under low NOx conditions (≤ 2 ppb) and at atmospheric beta-pinene concentrations (≤ 5 ppb) with and without addition of ozone. For the investigation of the OH budget, the OH production and destruction rates were calculated from measured quantities. Within the limits of accuracy of the instruments, the OH budget was balanced in all β-pinene oxidation experiments. However, even though the OH budget was closed, simulation results from the Master Chemical Mechanism 3.2 showed that the OH production and destruction rates were underestimated by the model. The measured OH and HO2 concentrations were underestimated by up to a factor of two whereas the total OH reactivity was slightly overestimated because of the poor reproduction of the measured nopinone by the model by up to a factor of three. A new, theory-derived first-generation product distribution by Vereecken and Peeters was able to reproduce the measured nopinone time series and the total OH reactivity. Nevertheless the measured OH and HO2 concentrations remained underestimated by the numerical simulations. These observations together with the fact that the measured OH budget was closed suggest the existence of unaccounted sources of HO2.

Incorporation and evaluation of the CRI v2.2 chemical mechanism in UKESM1: An alternative mechanism with updated isoprene chemistry for investigating the influence of BVOCs on atmospheric composition and climate. 

2021 ◽  
Author(s):  
James Weber ◽  
Scott Archer-Nicholls ◽  
N. Luke Abraham ◽  
Youngsub M. Shin ◽  
Thomas Bannan ◽  
...  
Keyword(s):  
Peroxy Radical ◽  
Tropospheric Chemistry ◽  
Chemical Mechanism ◽  
Atmospheric Composition ◽  
Radiation Budget ◽  
Alternative Mechanism ◽  
Mixing Ratios ◽  
The United Kingdom ◽  
Surface Mixing ◽  
Phase Chemistry

&lt;p&gt;We present the first incorporation and evaluation of the Common Representative Intermediates version 2.2 chemistry mechanism, CRI v2.2, for use in the United Kingdom Earth System Model (UKESM1). Tuned against the MCM v3.3.1, the CRI v2.2 mechanism builds on the previous CRI version, CRI v2.1, in UKESM1 (Archer-Nicholls et al., 2020) by updating isoprene chemistry and offers a more comprehensive description of tropospheric chemistry than the standard chemistry mechanism STRAT-TROP (ST).&lt;/p&gt;&lt;p&gt;&lt;span&gt;CRI v2.2 adds state-of-the-art isoprene chemistry with the introduction of HO&lt;/span&gt;&lt;sub&gt;&lt;span&gt;x&lt;/span&gt;&lt;/sub&gt;&lt;span&gt;-recycling via the isoprene peroxy radical isomerisation pathway, &lt;/span&gt;&lt;span&gt;making UKESM1 one of the first CMIP6 models to include this important chemistry. &lt;/span&gt;&lt;span&gt;HO&lt;/span&gt;&lt;sub&gt;&lt;span&gt;x&lt;/span&gt;&lt;/sub&gt;&lt;span&gt;-recycling has noticeable effects on oxidants in regions with large emissions of biogenic volatile organic compounds (BVOCs). Low altitude OH in tropical forested regions increases by 75-150% relative to ST, reducing the existing model low bias compared to observations. Consequently, isoprene surface mixing ratios decrease considerably (25-40%), significantly improving the model high bias relative to ST. Methane lifetime decreases by 2% and tropospheric ozone burden increases by 4%. &lt;/span&gt;&lt;/p&gt;&lt;p&gt;Aerosol processes also differ between CRI v2.2 and ST, resulting in changes to the size and number distributions. Relative to ST, CRI v2.2 simulates an 8% decrease in the sulphate aerosol burden with 20% decreases in the nucleation and Aitken modes. By contrast, the secondary organic aerosol (SOA) nucleation mode burden increases by 11%. Globally, the average nucleation and Aitken mode aerosol number concentrations decrease by 20%.&lt;/p&gt;&lt;p&gt;The differences in aerosol and gas phase chemistry between CRI v2.2 and ST are likely to have impacts on the radiation budget. We plan to use CRI v2.2 and ST to investigate the influence that the chemical mechanism has on the simulated chemistry-climate feedbacks from BVOCs. In addition, CRI v2.2 will serve as the basis for the addition of a scheme describing the formation of highly oxygenated organic molecules (HOMs) from BVOCs, facilitating a semi-explicit mechanism for new particle formation from organic species.&lt;/p&gt;

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 Investigation of the <i>β</i>-pinene photooxidation by OH in the atmosphere simulation chamber SAPHIR

2017 ◽  
Vol 17 (11) ◽  
pp. 6631-6650 ◽  
Author(s):  
Martin Kaminski ◽  
Hendrik Fuchs ◽  
Ismail-Hakki Acir ◽  
Birger Bohn ◽  
Theo Brauers ◽  
...  
Keyword(s):  
Degradation Mechanism ◽  
Product Distribution ◽  
Oxidation Products ◽  
Chemical Mechanism ◽  
Emission Rates ◽  
Photochemical Degradation ◽  
Alkoxy Radical ◽  
Radical Intermediate ◽  
Atmosphere Simulation Chamber ◽  
Simulation Chamber

Abstract. Besides isoprene, monoterpenes are the non-methane volatile organic compounds (VOCs) with the highest global emission rates. Due to their high reactivity towards OH, monoterpenes can dominate the radical chemistry of the atmosphere in forested areas. In the present study the photochemical degradation mechanism of β-pinene was investigated in the Jülich atmosphere simulation chamber SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction Chamber). One focus of this study is on the OH budget in the degradation process. Therefore, the SAPHIR chamber was equipped with instrumentation to measure radicals (OH, HO2, RO2), the total OH reactivity, important OH precursors (O3, HONO, HCHO), the parent VOC β-pinene, its main oxidation products, acetone and nopinone and photolysis frequencies. All experiments were carried out under low-NO conditions ( ≤  300 ppt) and at atmospheric β-pinene concentrations ( ≤  5 ppb) with and without addition of ozone. For the investigation of the OH budget, the OH production and destruction rates were calculated from measured quantities. Within the limits of accuracy of the instruments, the OH budget was balanced in all β-pinene oxidation experiments. However, even though the OH budget was closed, simulation results from the Master Chemical Mechanism (MCM) 3.2 showed that the OH production and destruction rates were underestimated by the model. The measured OH and HO2 concentrations were underestimated by up to a factor of 2, whereas the total OH reactivity was slightly overestimated because the model predicted a nopinone mixing ratio which was 3 times higher than measured. A new, theory-derived, first-generation product distribution by Vereecken and Peeters (2012) was able to reproduce the measured nopinone time series and the total OH reactivity. Nevertheless, the measured OH and HO2 concentrations remained underestimated by the numerical simulations. These observations together with the fact that the measured OH budget was closed suggest the existence of unaccounted sources of HO2. Although the mechanism of additional HO2 formation could not be resolved, our model studies suggest that an activated alkoxy radical intermediate proposed in the model of Vereecken and Peeters (2012) generates HO2 in a new pathway, whose importance has been underestimated so far. The proposed reaction path involves unimolecular rearrangement and decomposition reactions and photolysis of dicarbonyl products, yielding additional HO2 and CO. Further experiments and quantum chemical calculations have to be made to completely unravel the pathway of HO2 formation.

scholarly journals Observations of speciated isoprene nitrates in Beijing: implications for isoprene chemistry

2021 ◽  
Vol 21 (8) ◽  
pp. 6315-6330
Author(s):  
Claire E. Reeves ◽  
Graham P. Mills ◽  
Lisa K. Whalley ◽  
W. Joe F. Acton ◽  
William J. Bloss ◽  
...  
Keyword(s):  
Chemical Mechanism ◽  
Organic Nitrates ◽  
Isomer Ratio ◽  
Peroxy Radicals ◽  
Model Calculations ◽  
Mixing Ratios ◽  
Field Evidence ◽  
Isoprene Nitrates ◽  
Field Deployment ◽  
The Impact

Abstract. Isoprene is the most important biogenic volatile organic compound in the atmosphere. Its calculated impact on ozone (O3) is critically dependent on the model isoprene oxidation chemical scheme, in particular the way the isoprene-derived organic nitrates (IN) are treated. By combining gas chromatography with mass spectrometry, we have developed a system capable of separating and unambiguously measuring individual IN isomers. In this paper we use measurements from its first field deployment, which took place in Beijing as part of the Atmospheric Pollution and Human Health in a Chinese Megacity programme, to test understanding of the isoprene chemistry as simulated in the Master Chemical Mechanism (MCM) (v.3.3.1). Seven individual isoprene nitrates were identified and quantified during the campaign: two β-hydroxy nitrates (IHN), four δ-carbonyl nitrates (ICN), and propanone nitrate. Our measurements show that in the summertime conditions experienced in Beijing the ratio of (1-OH, 2-ONO2)-IHN to (4-OH, 3-ONO2)-IHN (the numbers indicate the carbon atom in the isoprene chain to which the radical is added) increases at NO mixing ratios below 2 ppb. This provides observational field evidence of the redistribution of the peroxy radicals derived from OH oxidation of isoprene away from the kinetic ratio towards a new thermodynamic equilibrium consistent with box model calculations. The observed amounts of δ-ICN demonstrate the importance of daytime addition of NO3 to isoprene in Beijing but suggest that the predominant source of the δ-ICN in the model (reaction of NO with δ-nitrooxy peroxy radicals) may be too large. Our speciated measurements of the four δ-ICN exhibit a mean C1 : C4 isomer ratio of 1.4 and a mean trans : cis isomer ratio of 7 and provide insight into the isomeric distribution of the δ-nitrooxy peroxy radicals. Together our measurements and model results indicate that propanone nitrate was formed from the OH oxidation of δ-ICN both during the day and night, as well as from NO3 addition to propene at night. This study demonstrates the value of speciated IN measurements in testing understanding of the isoprene degradation chemistry and shows how more extensive measurements would provide greater constraints. It highlights areas of the isoprene chemistry that warrant further study, in particular the impact of NO on the formation of the IHN and the NO3-initiated isoprene degradation chemistry, as well as the need for further laboratory studies on the formation and the losses of IN, in particular via photolysis of δ-ICN and hydrolysis.

scholarly journals Low-level summertime isoprene observed at a forested mountaintop site in southern China: implications for strong regional atmospheric oxidative capacity

2018 ◽  
Vol 18 (19) ◽  
pp. 14417-14432 ◽  
Author(s):  
Daocheng Gong ◽  
Hao Wang ◽  
Shenyang Zhang ◽  
Yu Wang ◽  
Shaw Chen Liu ◽  
...  
Keyword(s):  
Air Pollution ◽  
Southern China ◽  
Sampling Site ◽  
Oxidative Capacity ◽  
Oxidation Products ◽  
Chemical Mechanism ◽  
High Mountain ◽  
Mountain Areas ◽  
Sequential Reaction ◽  
Mixing Ratios

Abstract. To investigate the atmospheric oxidative capacity (AOC) in forested high mountain areas adjacent to the photochemistry-active Pearl River Delta (PRD) region in southern China, one-month online observations of isoprene and its oxidation products methyl vinyl ketone (MVK) and methacrolein (MACR) were conducted at a national background station in Nanling Mountains in summer 2016. The results showed that the observed daytime isoprene levels (377±46 pptv) were significantly lower in comparison with other forest sites within and outside China, although the sampling site was surrounded with subtropical evergreen broad-leaved trees which are strong isoprene emitters. Also, high daytime (MVK + MACR) ∕ isoprene ratios (1.9±0.5) were observed. Based on the observations, we hypothesized that the lower isoprene levels in the study forest might be attributable to a strong AOC in relation to the elevated regional complex air pollution. In further data analyses, high site-level concentrations of daytime OH (7.3±0.5×106 molecules cm−3) and nighttime NO3 radicals (6.0±0.5×108 molecules cm−3) were estimated by using a photochemical box model incorporating the master chemical mechanism (PBM-MCM), and high regional mixing ratios of OH (19.7±2.3×106 molecules cm−3) during 09:00–15:00 LT were also obtained by applying a parameterization method with measured aromatic hydrocarbons. And besides, high initial mixing ratios (1213±108 pptv) and short atmospheric reaction time (0.27 h) of isoprene during the day were derived by a sequential reaction approach. All these indicate that isoprene was rapidly and highly oxidized in this forest, which supports our hypothesis. The study suggests that the complex air pollution in the PRD may have significantly elevated the background AOC of the adjacent forests, and probably affects the regional air quality and ecological environment in the long term. The feedback of forest ecosystems to the increasing AOC in southern China warrants further studies.

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