Heterogeneous Oxidation of Terbuthylazine by “Dark” OH Radicals under Simulated Atmospheric Conditions in a Flow Tube

2013 ◽  
Vol 47 (12) ◽  
pp. 6239-6246 ◽  
Author(s):  
Maryline Pflieger ◽  
Anne Monod ◽  
Henri Wortham
Keyword(s):  
Oh Radicals ◽  
Atmospheric Conditions ◽  
Flow Tube ◽  
Heterogeneous Oxidation

scholarly journals Heterogeneous conversion of NO<sub>2</sub> on secondary organic aerosol surfaces: A possible source of nitrous acid (HONO) in the atmosphere?

2003 ◽  
Vol 3 (1) ◽  
pp. 597-613 ◽  
Author(s):  
R. Bröske ◽  
J. Kleffmann ◽  
P. Wiesen
Keyword(s):  
Nitrous Acid ◽  
Secondary Organic Aerosols ◽  
Organic Aerosols ◽  
Oh Radicals ◽  
Atmospheric Conditions ◽  
Flow Tube ◽  
Upper Limits ◽  
Uptake Coefficients ◽  
Heterogeneous Formation ◽  
Organic Particles

Abstract. The heterogeneous conversion of NO2 on different secondary organic aerosols (SOA) was investigated with the focus on a possible formation of nitrous acid (HONO). In one set of experiments different organic aerosols were produced in the reactions of O3 with α-pinene, limonene or catechol and OH radicals with toluene or limonene, respectively. The aerosols were sampled on filters and exposed to humidified NO2 mixtures under atmospheric conditions. The estimated upper limits for the uptake coefficients of NO2 and the reactive uptake coefficients NO2 →HONO are in the range of 10−6 and 10−7, respectively. The integrated HONO formation for 1 h reaction time was <1013 cm−2 geometrical surface and <1017 g−1 particle mass. In a second set of experiments the conversion of NO2 into HONO in the presence of organic particles was carried out in an aerosol flow tube under atmospheric conditions. In this case the aerosols were produced in the reaction of O3 with β-pinene, limonene or catechol, respectively. The upper limits for the reactive uptake coefficients NO2 \\rightarrow HONO were in the range of 7×10−7 −9×10−6. The results from the present study show that heterogeneous formation of nitrous acid on secondary organic aerosols (SOA) is unimportant for the atmosphere.

scholarly journals Heterogeneous loss of OH on NaCl and NH<sub>4</sub>NO<sub>3</sub> at tropospheric temperatures

1996 ◽  
Vol 14 (6) ◽  
pp. 659-664 ◽  
Author(s):  
A. V. Ivanov ◽  
Y. M. Gershenzon ◽  
F. Gratpanche ◽  
P. Devolder ◽  
J.-P. Sawerysyn
Keyword(s):  
Temperature Dependence ◽  
Detection Method ◽  
Tropospheric Chemistry ◽  
Minor Role ◽  
Oh Radicals ◽  
Flow Tube ◽  
Temperature Range ◽  
Uptake Coefficients

Abstract. The uptake coefficients (Γ) for OH radicals on some dry salts of tropospheric interest (NaCl and NH4NO3) have been investigated as a function of temperature using the flow tube technique combined with an EPR spectrometer as a detection method. The temperature dependence of Γ-values measured over the temperature range 245–340 K can be expressed in Arrhenius form: ΓOHNaCl=(1.2±0.7)×10–5exp[(1750±200)/T] and ΓOHNH4NO3=(1.4±0.5)×10–4exp[(1000±100)/T]. These Arrhenius expressions lead to very similar Γ-values (~4×10–3) for both salts studied at 300 K. It is shown that the heterogeneous OH sinks on solids aerosol play a very minor role in tropospheric chemistry in comparison with the homogeneous sinks.

scholarly journals The MCM v3.3 degradation scheme for isoprene

2015 ◽  
Vol 15 (6) ◽  
pp. 9709-9766 ◽  
Author(s):  
M. E. Jenkin ◽  
J. C. Young ◽  
A. R. Rickard
Keyword(s):  
Boundary Layer ◽  
Free Radical ◽  
Degradation Mechanism ◽  
Closed Shell ◽  
Chemical Mechanism ◽  
Formation Mechanisms ◽  
Oh Radicals ◽  
Atmospheric Conditions ◽  
Radical Species ◽  
Master Chemical Mechanism

Abstract. The chemistry of isoprene degradation in the Master Chemical Mechanism (MCM) has been systematically refined and updated to reflect recent advances in understanding, with these updates appearing in the latest version, MCM v3.3. The complete isoprene degradation mechanism in MCM v3.3 consists of 1935 reactions of 605 closed shell and free radical species, which treat the chemistry initiated by reaction with OH radicals, NO3 radicals and ozone (O3). A detailed overview of the updates is provided, within the context of reported kinetic and mechanistic information. The revisions mainly relate to the OH-initiated chemistry, which tends to dominate under atmospheric conditions, although these include updates to the chemistry of some products that are also generated from the O3 - and NO3-initiated oxidation. The revisions have impacts in a number of key areas, including HOx recycling, NOx recycling and the formation of species reported to play a role in SOA-formation mechanisms. The performance of the MCM v3.3 isoprene mechanism has been compared with those of earlier versions (MCM v3.1 and MCM v3.2) over a range of relevant conditions, using a box model of the tropical forested boundary layer. The results of these calculations are presented and discussed, and are used to illustrate the impacts of the mechanistic updates in MCM v3.3.

scholarly journals Heterogeneous oxidation of saturated organic aerosols by hydroxyl radicals: Uptake kinetics and condensed-phase products

2007 ◽  
Vol 7 (3) ◽  
pp. 6803-6842 ◽  
Author(s):  
I. J. George ◽  
A. Vlasenko ◽  
J. G. Slowik ◽  
J. P. D. Abbatt
Keyword(s):  
Hydroxyl Radicals ◽  
Particle Density ◽  
Organic Aerosols ◽  
Oxidation Products ◽  
Photochemical Oxidation ◽  
Mass Spectrometry Analysis ◽  
Oh Radicals ◽  
Ionization Mass ◽  
Phase Reaction ◽  
Heterogeneous Oxidation

Abstract. The kinetics and reaction mechanism for the heterogeneous oxidation of saturated organic aerosols by gas-phase OH radicals were investigated under NOx-free conditions. The reaction of 150 nm diameter Bis(2-ethylhexyl) sebacate (BES) particles with OH was studied as a proxy for chemical aging of atmospheric aerosols containing saturated organic matter. An aerosol reactor flow tube combined with an Aerodyne time-of-flight aerosol mass spectrometer (ToF-AMS) and scanning mobility particle sizer (SMPS) was used to study this system. Hydroxyl radicals were produced by 254 nm photolysis of O3 in the presence of water vapour. The kinetics of the heterogeneous oxidation of the BES particles was studied by monitoring the loss of a mass fragment of BES with the ToF-AMS as a function of OH exposure. We measured an initial OH uptake coefficient of γ0 = 1.26 (±0.04), confirming that this reaction is highly efficient. The density of BES particles increased by up to 20% of the original BES particle density at the highest OH exposure studied, consistent with the particle becoming more oxidized. Electrospray ionization mass spectrometry analysis showed that the major particle-phase reaction products are multifunctional carbonyls and alcohols with higher molecular weights than the starting material. Volatilization of oxidation products accounted for a maximum of 17% decrease of the particle volume at the highest OH exposure studied. Tropospheric organic aerosols will become more oxidized from heterogeneous photochemical oxidation, which may affect not only their physical and chemical properties, but also their hygroscopicity and cloud nucleation activity.

scholarly journals Laboratory study on new particle formation from the reaction OH + SO<sub>2</sub>: influence of experimental conditions, H<sub>2</sub>O vapour, NH<sub>3</sub> and the amine tert-butylamine on the overall process

2010 ◽  
Vol 10 (3) ◽  
pp. 6447-6484 ◽  
Author(s):  
T. Berndt ◽  
F. Stratmann ◽  
M. Sipilä ◽  
J. Vanhanen ◽  
T. Petäjä ◽  
...  
Keyword(s):  
Relative Humidity ◽  
High Sensitivity ◽  
Particle Growth ◽  
Counting Efficiency ◽  
Oh Radicals ◽  
Atmospheric Conditions ◽  
Promoting Effect ◽  
Experimental Conditions ◽  
H2so4 Concentration ◽  
Tert Butylamine

Abstract. Nucleation experiments starting from the reaction of OH radicals with SO2 have been performed in the IfT-LFT flow tube under atmospheric conditions at 293±0.5 K for a relative humidity of 13–61%. The presence of different additives (H2, CO, 1,3,5-trimethylbenzene) for adjusting the OH radical concentration and resulting OH levels in the range (4–300)·105 molecule cm−3 did not influence the nucleation process itself. The number of detected particles as well as the threshold H2SO4 concentration needed for nucleation was found to be strongly dependent on the counting efficiency of the used counting devices. High-sensitivity particle counters allowed the measurement of freshly nucleated particles with diameters down to about 1.5 nm. A parameterization of the experimental data was developed using power law equations for H2SO4 and H2O vapour. The exponent for H2SO4 from different measurement series was in the range of 1.7–2.1 being in good agreement with those arising from analysis of nucleation events in the atmosphere. For increasing relative humidity, an increase of the particle number was observed. The exponent for H2O vapour was found to be 3.1 representing a first estimate. Addition of 1.2·1011 molecule cm−3 or 1.2·1012 molecule cm−3 of NH3 (range of atmospheric NH3 peak concentrations) revealed that NH3 has a measureable, promoting effect on the nucleation rate under these conditions. The promoting effect was found to be more pronounced for relatively dry conditions. NH3 showed a contribution to particle growth. Adding the amine tert-butylamine instead of NH3, the enhancing impact for nucleation and particle growth appears to be stronger.

scholarly journals Flame stability limits of premixed low-swirl combustion

2018 ◽  
Vol 10 (9) ◽  
pp. 168781401879087 ◽  
Author(s):  
Yinli Xiao ◽  
Zhibo Cao ◽  
Changwu Wang
Keyword(s):  
Flow Field ◽  
Vortex Breakdown ◽  
Flame Structure ◽  
Field Measurements ◽  
Operating Conditions ◽  
Oh Radicals ◽  
Flame Stability ◽  
Atmospheric Conditions ◽  
Swirl Burner ◽  
Stability Limits

The objective of this study is to gain a fundamental understanding of the flow-field and flame behaviors associated with a low-swirl burner. A vane-type low-swirl burner with different swirl numbers has been developed. The velocity field measurements are carried out with particle image velocimetry. The basic flame structures are characterized using OH radicals measured by planar laser-induced fluorescence. Three combustion regimes of low-swirl flames are identified depending on the operating conditions. For the same low-swirl injector under atmospheric conditions, attached flame is first observed when the incoming velocity is too low to generate vortex breakdown. Then, W-shaped flame is formed above the burner at moderate incoming velocity. Bowl-shaped flame structure is formed as the mixture velocity increases until it extinct. Local extinction and relight zones are observed in the low-swirl flame. Flow-field features and flame stability limits are obtained for the present burner.

scholarly journals Physicochemical uptake and release of volatile organic compounds by soil in coated-wall flow tube experiments with ambient air

2019 ◽  
Vol 19 (4) ◽  
pp. 2209-2232 ◽  
Author(s):  
Guo Li ◽  
Yafang Cheng ◽  
Uwe Kuhn ◽  
Rongjuan Xu ◽  
Yudong Yang ◽  
...  
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Atmospheric Chemistry ◽  
Soil Surface ◽  
Ambient Air ◽  
Flow Tube ◽  
Heterogeneous Oxidation ◽  
Volatile Organic ◽  
Wall Flow

Abstract. Volatile organic compounds (VOCs) play a key role in atmospheric chemistry. Emission and deposition on soil have been suggested as important sources and sinks of atmospheric trace gases. The exchange characteristics and heterogeneous chemistry of VOCs on soil, however, are not well understood. We used a newly designed differential coated-wall flow tube system to investigate the long-term variability of bidirectional air–soil exchange of 13 VOCs under ambient air conditions of an urban background site in Beijing. Sterilized soil was investigated to address physicochemical processes and heterogeneous/multiphase reactions independently from biological activity. Most VOCs revealed net deposition with average uptake coefficients (γ) in the range of 10−7–10−6 (referring to the geometric soil surface area), corresponding to deposition velocities (Vd) of 0.0013–0.01 cm s−1 and soil surface resistances (Rc) of 98–745 s cm−1, respectively. Formic acid, however, was emitted at a long-term average rate of ∼6×10-3 nmol m−2 s−1, suggesting that it was formed and released upon heterogeneous oxidation of other VOCs. The soil–atmosphere exchange of one individual VOC species can be affected by both its surface degradation/depletion caused by surface reactions and by competitive uptake or heterogeneous formation/accommodation of other VOC species. Overall, the results show that physicochemical processing and heterogeneous oxidation on soil and soil-derived dust can act as a sink or as a source of atmospheric VOCs, depending on molecular properties and environmental conditions.

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