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

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.

2019 ◽  
Vol 19 (2) ◽  
pp. 813-834 ◽  
Author(s):  
Zhe Peng ◽  
Julia Lee-Taylor ◽  
John J. Orlando ◽  
Geoffrey S. Tyndall ◽  
Jose L. Jimenez

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.


2017 ◽  
Vol 10 (4) ◽  
pp. 1519-1537 ◽  
Author(s):  
Pauli Simonen ◽  
Erkka Saukko ◽  
Panu Karjalainen ◽  
Hilkka Timonen ◽  
Matthew Bloss ◽  
...  

Abstract. Oxidation flow reactors (OFRs) or environmental chambers can be used to estimate secondary aerosol formation potential of different emission sources. Emissions from anthropogenic sources, such as vehicles, often vary on short timescales. For example, to identify the vehicle driving conditions that lead to high potential secondary aerosol emissions, rapid oxidation of exhaust is needed. However, the residence times in environmental chambers and in most oxidation flow reactors are too long to study these transient effects ( ∼  100 s in flow reactors and several hours in environmental chambers). Here, we present a new oxidation flow reactor, TSAR (TUT Secondary Aerosol Reactor), which has a short residence time ( ∼  40 s) and near-laminar flow conditions. These improvements are achieved by reducing the reactor radius and volume. This allows studying, for example, the effect of vehicle driving conditions on the secondary aerosol formation potential of the exhaust. We show that the flow pattern in TSAR is nearly laminar and particle losses are negligible. The secondary organic aerosol (SOA) produced in TSAR has a similar mass spectrum to the SOA produced in the state-of-the-art reactor, PAM (potential aerosol mass). Both reactors produce the same amount of mass, but TSAR has a higher time resolution. We also show that TSAR is capable of measuring the secondary aerosol formation potential of a vehicle during a transient driving cycle and that the fast response of TSAR reveals how different driving conditions affect the amount of formed secondary aerosol. Thus, TSAR can be used to study rapidly changing emission sources, especially the vehicular emissions during transient driving.


2016 ◽  
Author(s):  
Pauli Simonen ◽  
Erkka Saukko ◽  
Panu Karjalainen ◽  
Hilkka Timonen ◽  
Matthew Bloss ◽  
...  

Abstract. Oxidation flow reactors or environmental chambers can be used to estimate secondary aerosol formation potential of different emission sources. Emissions from anthropogenic sources, such as vehicles, often vary on short timescales. For example, to identify the vehicle driving conditions that lead to high potential secondary aerosol emissions, rapid oxidation of exhaust is needed. However, the residence times in environmental chambers and in most oxidation flow reactors are too long to study these transient effects. Here, we present a new oxidation flow reactor, TSAR (TUT Secondary Aerosol Reactor), which has a short residence time and near-laminar flow conditions. This allows studying e.g. the effect of vehicle driving conditions on secondary aerosol formation potential of the exhaust. We show that the flow pattern in TSAR is nearly laminar and particle losses are negligible. The secondary organic aerosol (SOA) produced in TSAR has a similar mass spectrum as the SOA produced in the state-of-the-art reactor, PAM (Potential Aerosol Mass). Both reactors produce the same amount of mass, but the TSAR has a higher time-resolution. We also show that the TSAR is capable of measuring secondary aerosol formation potential of a vehicle during a transient driving cycle, and that the fast response of the TSAR reveals how different driving conditions affect the amount of formed secondary aerosol. Thus, the TSAR can be used to study rapidly changing emission sources, especially the vehicular emissions during transient driving.


2020 ◽  
Author(s):  
Andrew T. Lambe ◽  
Ezra C. Wood ◽  
Jordan E. Krechmer ◽  
Francesca Majluf ◽  
Leah R. Williams ◽  
...  

Abstract. Oxidation flow reactors (OFRs) are an emerging tool for studying the formation and oxidative aging of organic aerosols and other applications. The majority of OFR studies to date involved generation of the hydroxyl radical (OH) to mimic daytime oxidative aging processes. On the other hand, use of the nitrate radical (NO3) in modern OFRs to mimic nighttime oxidative aging processes has been limited due to the complexity of conventional techniques that are used to generate NO3. Here, we present a new method that uses a laminar flow reactor (LFR) to continuously generate dinitrogen pentoxide (N2O5) in the gas phase at room temperature from the NO2 + O3 and NO2 + NO3 reactions. The N2O5 is then injected into a dark Potential Aerosol Mass OFR and decomposes to generate NO3; hereafter, this method is referred to as OFR-iN2O5 (i = injected). To assess the applicability of the OFR-iN2O5 method towards different chemical systems, we present experimental and model characterization of the integrated NO3 exposure, NO3:O3, NO2:NO3, and NO2:O2 as a function of LFR and OFR conditions. These parameters were used to investigate the fate of representative organic peroxy radicals (RO2) and aromatic alkyl radicals generated from volatile organic compound (VOC) + NO3 reactions, and VOCs that are reactive towards both O3 and NO3. Finally, we demonstrate the OFR-iN2O5 method by generating and characterizing secondary organic aerosol from the β-pinene + NO3 reaction.


2020 ◽  
Vol 10 (3) ◽  
pp. 475-490 ◽  
Author(s):  
Pauline Bianchi ◽  
Jason D. Williams ◽  
C. Oliver Kappe

Abstract Oscillatory flow reactors (OFRs) superimpose an oscillatory flow to the net movement through a flow reactor. OFRs have been engineered to enable improved mixing, excellent heat- and mass transfer and good plug flow character under a broad range of operating conditions. Such features render these reactors appealing, since they are suitable for reactions that require long residence times, improved mass transfer (such as in biphasic liquid-liquid systems) or to homogeneously suspend solid particles. Various OFR configurations, offering specific features, have been developed over the past two decades, with significant progress still being made. This review outlines the principles and recent advances in OFR technology and overviews the synthetic applications of OFRs for liquid-liquid and solid-liquid biphasic systems.


2017 ◽  
Vol 17 (19) ◽  
pp. 11991-12010 ◽  
Author(s):  
Zhe Peng ◽  
Jose L. Jimenez

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.


2014 ◽  
Vol 14 (22) ◽  
pp. 30575-30609 ◽  
Author(s):  
A. T. Lambe ◽  
P. S. Chhabra ◽  
T. B. Onasch ◽  
W. H. Brune ◽  
J. F. Hunter ◽  
...  

Abstract. We performed a systematic intercomparison study of the chemistry and yields of SOA generated from OH oxidation of a common set of gas-phase precursors in a Potential Aerosol Mass (PAM) continuous flow reactor and several environmental chambers. In the flow reactor, SOA precursors were oxidized using OH concentrations ranging from 2.0×108 to 2.2&times1010 molec cm−3 over exposure times of 100 s. In the environmental chambers, precursors were oxidized using OH concentrations ranging from 2×106 to 2×107 molec cm−3 over exposure times of several hours. The OH concentration in the chamber experiments is close to that found in the atmosphere, but the integrated OH exposure in the flow reactor can simulate atmospheric exposure times of multiple days compared to chamber exposure times of only a day or so. A linear correlation analysis of the mass spectra (m=0.91–0.92, r2=0.93–0.94) and carbon oxidation state (m=1.1, r2=0.58) of SOA produced in the flow reactor and environmental chambers for OH exposures of approximately 1011 molec cm−3 s suggests that the composition of SOA produced in the flow reactor and chambers is the same within experimental accuracy as measured with an aerosol mass spectrometer. This similarity in turn suggests that both in the flow reactor and in chambers, SOA chemical composition at low OH exposure is governed primarily by gas-phase OH oxidation of the precursors, rather than heterogeneous oxidation of the condensed particles. In general, SOA yields measured in the flow reactor are lower than measured in chambers for the range of equivalent OH exposures that can be measured in both the flow reactor and chambers. The influence of sulfate seed particles on isoprene SOA yield measurements was examined in the flow reactor. The studies show that seed particles increase the yield of SOA produced in flow reactors by a factor of 3 to 5 and may also account in part for higher SOA yields obtained in the chambers, where seed particles are routinely used.


2020 ◽  
Vol 13 (5) ◽  
pp. 2397-2411
Author(s):  
Andrew T. Lambe ◽  
Ezra C. Wood ◽  
Jordan E. Krechmer ◽  
Francesca Majluf ◽  
Leah R. Williams ◽  
...  

Abstract. Oxidation flow reactors (OFRs) are an emerging tool for studying the formation and oxidative aging of organic aerosols and other applications. The majority of OFR studies to date have involved the generation of the hydroxyl radical (OH) to mimic daytime oxidative aging processes. In contrast, the use of the nitrate radical (NO3) in modern OFRs to mimic nighttime oxidative aging processes has been limited due to the complexity of conventional techniques that are used to generate NO3. Here, we present a new method that uses a laminar flow reactor (LFR) to continuously generate dinitrogen pentoxide (N2O5) in the gas phase at room temperature from the NO2 + O3 and NO2 + NO3 reactions. The N2O5 is then injected into a dark Potential Aerosol Mass (PAM) OFR and decomposes to generate NO3; hereafter, this method is referred to as “OFR-iN2O5” (where “i” stands for “injected”). To assess the applicability of the OFR-iN2O5 method towards different chemical systems, we present experimental and model characterization of the integrated NO3 exposure, NO3:O3, NO2:NO3, and NO2:O2 as a function of LFR and OFR conditions. These parameters were used to investigate the fate of representative organic peroxy radicals (RO2) and aromatic alkyl radicals generated from volatile organic compound (VOC) + NO3 reactions, and VOCs that are reactive towards both O3 and NO3. Finally, we demonstrate the OFR-iN2O5 method by generating and characterizing secondary organic aerosol from the β-pinene + NO3 reaction.


2017 ◽  
Author(s):  
Zhe Peng ◽  
Jose L. Jimenez

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.


2019 ◽  
Author(s):  
Suchanuch Sachdev ◽  
Rhushabh Maugi ◽  
Sam Davis ◽  
Scott Doak ◽  
Zhaoxia Zhou ◽  
...  

<div>The interface between two immiscible liquids represent an ideal substrate for the assembly of nanomaterials. The defect free surface provides a reproducible support for creating densely packed ordered materials. Here a droplet flow reactor is presented for the synthesis and/ or assembly of nanomaterials at the interface of the emulsion. Each droplet acts as microreactor for a reaction between decamethylferrocene (DmFc) within the hexane and metal salts (Ag+/ Pd2+) in the aqueous phase. The hypothesis was that a spontaneous, interfacial reaction would lead to the assembly of nanomaterials creating a Pickering emulsion. The subsequent removal of the solvents showed how the Ag nanoparticles were trapped at the interface and retain the shape of the droplet, however the Pd nanoparticles were dispersed with no tertiary structure. To further exploit this, a one-step process where the particles are synthesised and then assembled into core-shell materials was proposed. The same reactions were performed in the presence of oleic acid stabilise Iron oxide nanoparticles dispersed within the hexane. It was shown that by changing the reaction rate and ratio between palladium and iron oxide a continuous coating of palladium onto iron oxide microspheres can be created. The same reaction with silver, was unsuccessful and resulted in the silver particles being shed into solution, or incorporated within the iron oxide micro particle. These insights offer a new method and chemistry within flow reactors for the creation of palladium and silver nanoparticles. We use the technique to create metal coated iron oxide nanomaterials but the methodology could be easily transferred to the assembly of other materials.</div><div><br></div>


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