scholarly journals Modeling of the chemistry in oxidation flow reactors with high initial NO

2017 ◽  
Author(s):  
Zhe Peng ◽  
Jose L. Jimenez
Keyword(s):  
Atmospheric Chemistry ◽  
Vehicle Emissions ◽  
High Efficiency ◽  
Input Parameter ◽  
High Water ◽  
Peroxy Radicals ◽  
Aerosol Formation ◽  
Experimental Conditions ◽  
Flow Reactors ◽  
Chemistry Research

Abstract. Oxidation flow reactors (OFRs) are increasingly employed in atmospheric chemistry research because of their high efficiency of OH radical production from low-pressure Hg lamp emissions at both 185 and 254 nm (OFR185) or 254 nm only (OFR254). OFRs have been thought to be limited to studying low-NO chemistry (where peroxy radicals (RO2) react preferentially with HO2) because NO is very rapidly oxidized by the high concentrations of O3, HO2, and OH in OFRs. However, many groups are performing experiments aging combustion exhaust with high NO levels, or adding NO in the hopes of simulating high-NO chemistry (where RO2 + NO dominates). This work systematically explores the chemistry in OFRs with high initial NO. Using box modeling, we investigate the interconversion of N-containing species and the uncertainties due to kinetic parameters. Simple initial injection of NO in OFR185 can result in more RO2 reacted with NO than with HO2 and minor non-tropospheric photolysis, but only under a very narrow set of conditions (high water mixing ratio, low UV intensity, low external OH reactivity (OHRext), and initial NO concentration (NOin) of tens to hundreds of ppb) that account for a very small fraction of the input parameter space. These conditions are generally far away from experimental conditions of published OFR studies with high initial NO. In particular, studies of aerosol formation from vehicle emissions in OFR often used OHRext and NOin several orders of magnitude higher. Due to extremely high OHRext and NOin, some studies may have resulted in substantial non-tropospheric photolysis, strong delay to RO2 chemistry due to peroxynitrate formation, VOC reactions with NO3 dominating over those with OH, and faster reactions of OH-aromatic adducts with NO2 than those with O2, all of which are irrelevant to ambient VOC photooxidation chemistry. Some of the negative effects are worst for alkene and aromatic precursors. To avoid undesired chemistry, vehicle emissions generally need to be diluted by a factor of > 100 before being injected into OFR. However, sufficiently diluted vehicle emissions generally do not lead to high-NO chemistry in OFR, but are rather dominated by the low-NO RO2 + HO2 pathway. To ensure high-NO conditions without substantial atmospherically irrelevant chemistry in a more controlled fashion, new techniques are needed.

scholarly journals Modeling of the chemistry in oxidation flow reactors with high initial NO

2017 ◽  
Vol 17 (19) ◽  
pp. 11991-12010 ◽  
Author(s):  
Zhe Peng ◽  
Jose L. Jimenez
Keyword(s):  
Atmospheric Chemistry ◽  
Vehicle Emissions ◽  
High Efficiency ◽  
Input Parameter ◽  
High Water ◽  
Peroxy Radicals ◽  
Aerosol Formation ◽  
Experimental Conditions ◽  
Flow Reactors ◽  
Chemistry Research

Abstract. Oxidation flow reactors (OFRs) are increasingly employed in atmospheric chemistry research because of their high efficiency of OH radical production from low-pressure Hg lamp emissions at both 185 and 254 nm (OFR185) or 254 nm only (OFR254). OFRs have been thought to be limited to studying low-NO chemistry (in which peroxy radicals (RO2) react preferentially with HO2) because NO is very rapidly oxidized by the high concentrations of O3, HO2, and OH in OFRs. However, many groups are performing experiments by aging combustion exhaust with high NO levels or adding NO in the hopes of simulating high-NO chemistry (in which RO2 + NO dominates). This work systematically explores the chemistry in OFRs with high initial NO. Using box modeling, we investigate the interconversion of N-containing species and the uncertainties due to kinetic parameters. Simple initial injection of NO in OFR185 can result in more RO2 reacted with NO than with HO2 and minor non-tropospheric photolysis, but only under a very narrow set of conditions (high water mixing ratio, low UV intensity, low external OH reactivity (OHRext), and initial NO concentration (NOin) of tens to hundreds of ppb) that account for a very small fraction of the input parameter space. These conditions are generally far away from experimental conditions of published OFR studies with high initial NO. In particular, studies of aerosol formation from vehicle emissions in OFRs often used OHRext and NOin several orders of magnitude higher. Due to extremely high OHRext and NOin, some studies may have resulted in substantial non-tropospheric photolysis, strong delay to RO2 chemistry due to peroxynitrate formation, VOC reactions with NO3 dominating over those with OH, and faster reactions of OH–aromatic adducts with NO2 than those with O2, all of which are irrelevant to ambient VOC photooxidation chemistry. Some of the negative effects are the worst for alkene and aromatic precursors. To avoid undesired chemistry, vehicle emissions generally need to be diluted by a factor of > 100 before being injected into an OFR. However, sufficiently diluted vehicle emissions generally do not lead to high-NO chemistry in OFRs but are rather dominated by the low-NO RO2 + HO2 pathway. To ensure high-NO conditions without substantial atmospherically irrelevant chemistry in a more controlled fashion, new techniques are needed.

scholarly journals Rapid formation of isoprene photo-oxidation products observed in Amazonia

2009 ◽  
Vol 9 (3) ◽  
pp. 13629-13653 ◽  
Author(s):  
T. Karl ◽  
A. Guenther ◽  
A. Turnipseed ◽  
P. Artaxo ◽  
S. Martin
Keyword(s):  
Atmospheric Chemistry ◽  
Global Climate ◽  
Oxidative Capacity ◽  
Oxidation Products ◽  
Lower Atmosphere ◽  
Peroxy Radicals ◽  
Aerosol Formation ◽  
Photo Oxidation ◽  
Voc Oxidation ◽  
Rapid Formation

Abstract. Isoprene represents the single most important reactive hydrocarbon for atmospheric chemistry in the tropical atmosphere. It plays a central role in global and regional atmospheric chemistry and possible climate feedbacks. Photo-oxidation of primary hydrocarbons (e.g. isoprene) leads to the formation of oxygenated VOCs (OVOCs). The evolution of these intermediates affects the oxidative capacity of the atmosphere (by reacting with OH) and can contribute to secondary aerosol formation, a poorly understood process. An accurate and quantitative understanding of VOC oxidation processes is needed for model simulations of regional air quality and global climate. Based on field measurements conducted during the Amazonian aerosol characterization experiment (AMAZE-08) we show that the production of certain OVOCs (e.g. hydroxyacetone) from isoprene photo-oxidation in the lower atmosphere is significantly underpredicted by standard chemistry schemes. A recently suggested novel pathway for isoprene peroxy radicals could explain the observed discrepancy and reconcile the rapid formation of these VOCs. Furthermore, if generalized our observations suggest that prompt photochemical formation of OVOCs and other uncertainties in VOC oxidation schemes could result in substantial underestimates of modelled OH reactivity that could explain a major fraction of the missing OH sink over forests which has previously been attributed to a missing source of primary biogenic VOCs.

scholarly journals Rapid formation of isoprene photo-oxidation products observed in Amazonia

2009 ◽  
Vol 9 (20) ◽  
pp. 7753-7767 ◽  
Author(s):  
T. Karl ◽  
A. Guenther ◽  
A. Turnipseed ◽  
G. Tyndall ◽  
P. Artaxo ◽  
...  
Keyword(s):  
Atmospheric Chemistry ◽  
Global Climate ◽  
Field Measurements ◽  
Oxidative Capacity ◽  
Oxidation Products ◽  
Lower Atmosphere ◽  
Peroxy Radicals ◽  
Aerosol Formation ◽  
Photo Oxidation ◽  
Voc Oxidation

Abstract. Isoprene represents the single most important reactive hydrocarbon for atmospheric chemistry in the tropical atmosphere. It plays a central role in global and regional atmospheric chemistry and possible climate feedbacks. Photo-oxidation of primary hydrocarbons (e.g. isoprene) leads to the formation of oxygenated VOCs (OVOCs). The evolution of these intermediates affects the oxidative capacity of the atmosphere (by reacting with OH) and can contribute to secondary aerosol formation, a poorly understood process. An accurate and quantitative understanding of VOC oxidation processes is needed for model simulations of regional air quality and global climate. Based on field measurements conducted during the Amazonian Aerosol Characterization Experiment (AMAZE-08) we show that the production of certain OVOCs (e.g. hydroxyacetone) from isoprene photo-oxidation in the lower atmosphere is significantly underpredicted by standard chemistry schemes. Recently reported fast secondary production could explain 50% of the observed discrepancy with the remaining part possibly produced via a novel primary production channel, which has been proposed theoretically. The observations of OVOCs are also used to test a recently proposed HOx recycling mechanism via degradation of isoprene peroxy radicals. If generalized our observations suggest that prompt photochemical formation of OVOCs and other uncertainties in VOC oxidation schemes could result in uncertainties of modelled OH reactivity, potentially explaining a fraction of the missing OH sink over forests which has previously been largely attributed to a missing source of primary biogenic VOCs.

scholarly journals Organic peroxy radical chemistry in oxidation flow reactors and environmental chambers and their atmospheric relevance

2018 ◽  
Author(s):  
Zhe Peng ◽  
Julia Lee-Taylor ◽  
John J. Orlando ◽  
Geoffrey S. Tyndall ◽  
Jose L. Jimenez
Keyword(s):  
Flow Reactor ◽  
Operating Conditions ◽  
Peroxy Radicals ◽  
Relative Importance ◽  
Atmospheric Conditions ◽  
Aerosol Formation ◽  
Ambient Conditions ◽  
Flow Reactors ◽  
Environmental Chambers ◽  
Atmospherically Relevant

Abstract. Oxidation flow reactors (OFR) are a promising complement to environmental chambers for investigating atmospheric oxidation processes and secondary aerosol formation. However, questions have been raised about how representative the chemistry within OFRs is of that in the troposphere. We investigate the fates of organic peroxy radicals (RO2), which play a central role in atmospheric organic chemistry, in OFRs and environmental chambers by chemical kinetic modeling, and compare to a variety of ambient conditions to help define a range of atmospherically relevant OFR operating conditions. For most types of RO2, their bimolecular fates in OFRs are mainly RO2+HO2 and RO2+NO, similar to chambers and atmospheric studies. For substituted primary RO2 and acyl RO2, RO2+RO2 can make a significant contribution to the fate of RO2 in OFRs, chambers and the atmosphere, but RO2+RO2 in OFRs is in general somewhat less important than in the atmosphere. At high NO, RO2+NO dominates RO2 fate in OFRs, as in the atmosphere. At high UV lamp setting in OFRs, RO2+OH can be a major RO2 fate and RO2 isomerization can be negligible for common multifunctional RO2, both of which deviate from common atmospheric conditions. In the OFR254 operation mode (where OH is generated only from photolysis of added O3), we cannot identify any conditions that can simultaneously avoid significant organic photolysis at 254 nm and lead to RO2 lifetimes long enough (~ 10 s) to allow atmospherically relevant RO2 isomerization. In the OFR185 mode (where OH is generated from reactions initiated by 185 nm photons), high relative humidity, low UV intensity and low precursor concentrations are recommended for atmospherically relevant gas-phase chemistry of both stable species and RO2. These conditions ensure minor or negligible RO2+OH and a relative importance of RO2 isomerization in RO2 fate in OFRs within ~ x2 of that in the atmosphere. Under these conditions, the photochemical age within OFR185 systems can reach a few equivalent days at most, encompassing the typical ages for maximum secondary organic aerosol (SOA) production. A small increase in OFR temperature may allow the relative importance of RO2 isomerization to approach the ambient values. To study heterogeneous oxidation of SOA formed under atmospherically-relevant OFR conditions, a different UV source with higher intensity is needed after the SOA formation stage, which can be done with another reactor in series. Finally, we recommend evaluating the atmospheric relevance of RO2 chemistry by always reporting measured and/or estimated OH, HO2, NO, NO2 and OH reactivity (or at least precursor composition and concentration) in all chamber and flow reactor experiments. An easy-to-use RO2 fate estimator program is included with this paper to facilitate investigation of this topic in future studies.

scholarly journals Reducing secondary organic aerosol formation from gasoline vehicle exhaust

2017 ◽  
Vol 114 (27) ◽  
pp. 6984-6989 ◽  
Author(s):  
Yunliang Zhao ◽  
Rawad Saleh ◽  
Georges Saliba ◽  
Albert A. Presto ◽  
Timothy D. Gordon ◽  
...  
Keyword(s):  
Los Angeles ◽  
Atmospheric Chemistry ◽  
Urban Areas ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Peroxy Radicals ◽  
Oxides Of Nitrogen ◽  
Aerosol Formation ◽  
Vehicle Exhaust ◽  
Gasoline Vehicles

On-road gasoline vehicles are a major source of secondary organic aerosol (SOA) in urban areas. We investigated SOA formation by oxidizing dilute, ambient-level exhaust concentrations from a fleet of on-road gasoline vehicles in a smog chamber. We measured less SOA formation from newer vehicles meeting more stringent emissions standards. This suggests that the natural replacement of older vehicles with newer ones that meet more stringent emissions standards should reduce SOA levels in urban environments. However, SOA production depends on both precursor concentrations (emissions) and atmospheric chemistry (SOA yields). We found a strongly nonlinear relationship between SOA formation and the ratio of nonmethane organic gas to oxides of nitrogen (NOx) (NMOG:NOx), which affects the fate of peroxy radicals. For example, changing the NMOG:NOxfrom 4 to 10 ppbC/ppbNOxincreased the SOA yield from dilute gasoline vehicle exhaust by a factor of 8. We investigated the implications of this relationship for the Los Angeles area. Although organic gas emissions from gasoline vehicles in Los Angeles are expected to fall by almost 80% over the next two decades, we predict no reduction in SOA production from these emissions due to the effects of rising NMOG:NOxon SOA yields. This highlights the importance of integrated emission control policies for NOxand organic gases.

Radical chemistry in oxidation flow reactors for atmospheric chemistry research

2020 ◽  
Vol 49 (9) ◽  
pp. 2570-2616 ◽  
Author(s):  
Zhe Peng ◽  
Jose L. Jimenez
Keyword(s):  
Atmospheric Chemistry ◽  
Flow Reactor ◽  
Flow Reactors ◽  
Radical Chemistry ◽  
Chemistry Research

We summarize the studies on the chemistry in oxidation flow reactor and discuss its atmospheric relevance.

scholarly journals Impact of the Emission Control of Diesel Vehicles on Black Carbon (BC) Concentrations over China

Atmosphere ◽  
2020 ◽  
Vol 11 (7) ◽  
pp. 696 ◽  
Author(s):  
Jiamao Zhou ◽  
Xuexi Tie ◽  
Yunbo Yu ◽  
Shuyu Zhao ◽  
Guohui Li ◽  
...  
Keyword(s):  
Black Carbon ◽  
Atmospheric Chemistry ◽  
Vehicle Emissions ◽  
High Efficiency ◽  
Model Simulation ◽  
Emission Control ◽  
The Other ◽  
Particulate Filter ◽  
Diesel Vehicles ◽  
Diesel Vehicle

In order to reduce black carbon (BC) emissions from diesel vehicles, a regional atmospheric chemistry model (WRF-Chem) was used to investigate the effects of installing a high-efficiency device for vehicle exhaust control, a diesel particulate filter (DPF), on diesel vehicles in China. To reduce the uncertainty of estimation, three sensitivity experiments were designed and conducted for different emission scenarios. The first experiment uses the standard black carbon emissions of diesel vehicles without engaging in any emission control actions (referred to as CTRL), and the other two experiments were conducted using different DPF devices to reduce BC emissions by 65% (CASE1) and 39% (CASE2), respectively. The results show that the model simulation reasonably represents the measured BC concentrations. The highest BC concentrations occurred in large cities of the North China Plain (NCP) and present important seasonal variations. The results suggest that the reduction in diesel vehicle emissions has great benefits for reducing BC pollution not only in winter but also in other seasons. Sensitivity studies show that in CASE1, the average BC concentrations decreased about ~6% in January and by more than 10% in the other seasons. The greatest reduction exceeded 50%. In CASE2, the average BC concentrations decreased by about ~3.5% in January and by more than 7% in the other seasons. This study suggests that adding DPF to a diesel vehicle can have a significant influence on reducing BC concentrations in China. Thus, this study provides a practical basis by which diesel vehicle emissions can be reduced.

scholarly journals Organic peroxy radical chemistry in oxidation flow reactors and environmental chambers and their atmospheric relevance

2019 ◽  
Vol 19 (2) ◽  
pp. 813-834 ◽  
Author(s):  
Zhe Peng ◽  
Julia Lee-Taylor ◽  
John J. Orlando ◽  
Geoffrey S. Tyndall ◽  
Jose L. Jimenez
Keyword(s):  
Flow Reactor ◽  
Operating Conditions ◽  
Peroxy Radicals ◽  
Relative Importance ◽  
Atmospheric Conditions ◽  
Aerosol Formation ◽  
Ambient Conditions ◽  
Flow Reactors ◽  
Environmental Chambers ◽  
Atmospherically Relevant

Abstract. Oxidation flow reactors (OFRs) are a promising complement to environmental chambers for investigating atmospheric oxidation processes and secondary aerosol formation. However, questions have been raised about how representative the chemistry within OFRs is of that in the troposphere. We investigate the fates of organic peroxy radicals (RO2), which play a central role in atmospheric organic chemistry, in OFRs and environmental chambers by chemical kinetic modeling and compare to a variety of ambient conditions to help define a range of atmospherically relevant OFR operating conditions. For most types of RO2, their bimolecular fates in OFRs are mainly RO2+HO2 and RO2+NO, similar to chambers and atmospheric studies. For substituted primary RO2 and acyl RO2, RO2+RO2 can make a significant contribution to the fate of RO2 in OFRs, chambers and the atmosphere, but RO2+RO2 in OFRs is in general somewhat less important than in the atmosphere. At high NO, RO2+NO dominates RO2 fate in OFRs, as in the atmosphere. At a high UV lamp setting in OFRs, RO2+OH can be a major RO2 fate and RO2 isomerization can be negligible for common multifunctional RO2, both of which deviate from common atmospheric conditions. In the OFR254 operation mode (for which OH is generated only from the photolysis of added O3), we cannot identify any conditions that can simultaneously avoid significant organic photolysis at 254 nm and lead to RO2 lifetimes long enough (∼ 10 s) to allow atmospherically relevant RO2 isomerization. In the OFR185 mode (for which OH is generated from reactions initiated by 185 nm photons), high relative humidity, low UV intensity and low precursor concentrations are recommended for the atmospherically relevant gas-phase chemistry of both stable species and RO2. These conditions ensure minor or negligible RO2+OH and a relative importance of RO2 isomerization in RO2 fate in OFRs within ∼×2 of that in the atmosphere. Under these conditions, the photochemical age within OFR185 systems can reach a few equivalent days at most, encompassing the typical ages for maximum secondary organic aerosol (SOA) production. A small increase in OFR temperature may allow the relative importance of RO2 isomerization to approach the ambient values. To study the heterogeneous oxidation of SOA formed under atmospherically relevant OFR conditions, a different UV source with higher intensity is needed after the SOA formation stage, which can be done with another reactor in series. Finally, we recommend evaluating the atmospheric relevance of RO2 chemistry by always reporting measured and/or estimated OH, HO2, NO, NO2 and OH reactivity (or at least precursor composition and concentration) in all chamber and flow reactor experiments. An easy-to-use RO2 fate estimator program is included with this paper to facilitate the investigation of this topic in future studies.

scholarly journals Oceanic phytoplankton are a potentially important source of benzenoids to the remote marine atmosphere

2021 ◽  
Vol 2 (1) ◽  
Author(s):  
Manon Rocco ◽  
Erin Dunne ◽  
Maija Peltola ◽  
Neill Barr ◽  
Jonathan Williams ◽  
...  
Keyword(s):  
Atmospheric Chemistry ◽  
Dimethyl Sulfide ◽  
Laboratory Culture ◽  
Marine Phytoplankton ◽  
Marine Atmosphere ◽  
Aerosol Formation ◽  
Incubation Experiments ◽  
Phytoplankton Communities ◽  
Anthropogenic Air Pollutants ◽  
Benzene Toluene

AbstractBenzene, toluene, ethylbenzene and xylenes can contribute to hydroxyl reactivity and secondary aerosol formation in the atmosphere. These aromatic hydrocarbons are typically classified as anthropogenic air pollutants, but there is growing evidence of biogenic sources, such as emissions from plants and phytoplankton. Here we use a series of shipborne measurements of the remote marine atmosphere, seawater mesocosm incubation experiments and phytoplankton laboratory cultures to investigate potential marine biogenic sources of these compounds in the oceanic atmosphere. Laboratory culture experiments confirmed marine phytoplankton are a source of benzene, toluene, ethylbenzene, xylenes and in mesocosm experiments their sea-air fluxes varied between seawater samples containing differing phytoplankton communities. These fluxes were of a similar magnitude or greater than the fluxes of dimethyl sulfide, which is considered to be the key reactive organic species in the marine atmosphere. Benzene, toluene, ethylbenzene, xylenes fluxes were observed to increase under elevated headspace ozone concentration in the mesocosm incubation experiments, indicating that phytoplankton produce these compounds in response to oxidative stress. Our findings suggest that biogenic sources of these gases may be sufficiently strong to influence atmospheric chemistry in some remote ocean regions.

High-angle Kikuchi patterns

1954 ◽  
Vol 221 (1145) ◽  
pp. 224-242 ◽  
Keyword(s):  
Lithium Fluoride ◽  
High Efficiency ◽  
Cylindrical Specimen ◽  
Angle Of Incidence ◽  
High Angle ◽  
Lead Sulphide ◽  
Marked Contrast ◽  
Experimental Conditions ◽  
Low Intensity ◽  
Glancing Angle

A cylindrical specimen chamber and camera have been used to study the high-angle Kikuchi patterns obtained by reflexion of electrons, of energy 6 to 50 keV, from the cleavage surfaces of crystals with the sodium chloride structure. Angles of scattering ranging from 0 to 164° were covered. The relative intensity of the pattern at different scattering angles was measured using a photographic technique. The intensity distribution was found to become less steep as the energy of the incident electrons decreased. In photographs taken with a large value of the glancing angle of incidence, defect bands were found, starting near the shadow edge of the pattern; these changed to excess bands at higher angles of scattering. The most striking feature of the results is the remarkable intensity and clarity at the highest scattering angles of the pattern produced by crystals such as lead sulphide and potassium iodide, the constituents of which have a relatively high elastic scattering cross-section. In marked contrast, a relatively low intensity and low clarity was found at these angles for lithium fluoride under the same experimental conditions. An investigation of the width of Kikuchi bands, visible over the whole available angular range, showed that the electrons forming these bands had the same energy as that of the incident electrons within the experimental error of 10%. A possible mechanism is discussed by means of which electrons can be diffused through large angles with high efficiency, relative to small angles, and with relatively little loss of energy.

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