Oxidation Of Organic Compounds Research Articles

Highly efficient Cu(II) coordination polymer catalyst for the conversion of hazardous volatile organic compounds

Three novel coordination polymers (CPs), namely [Cu(μ-1κO,2κN-L)2]n (1), [Zn (μ-1κO,2κN-L)2(H2O)2]n (2) and [Cd (μ-1κOO’,2κN-L)2]n (3) [where HL = 4-(pyrimidin-5-ylcarbamoyl)benzoic acid], were synthesized and characterized by elemental analysis, ATR-IR, TGA, XPS and single-crystal X-ray diffraction. Despite having the same organic ligand, the various metal cations had an impact in the subsequent frameworks. Hirshfeld surface analysis was performed to investigate the intermolecular interactions and to examine the stability of the crystal structures of the three polymers. Their catalytic performances were screened for the peroxidative oxidation of Volatile Organic Compounds (VOCs), with toluene and p-xylene selected as model substrates. Tert-butyl hydroperoxide (t-BuOOH or TBHP) (aq. 70 %) was employed as the oxidant. The catalytic oxidation of toluene yielded benzyl alcohol, benzaldehyde and benzoic acid. The copper CP 1 exhibited the highest total yield for toluene oxidation, reaching approximately 36% in an aqueous medium. For p-xylene oxidation, tolualdehyde, methylbenzyl alcohol, and toluic acid were produced as the primary products, accompanied by minor ones. The experiments were conducted under diverse conditions, manipulating key parameters such as the choice of solvent (water or acetonitrile), type of oxidant (t-BuOOH or H2O2), the concentration of the oxidant and reaction temperature. In the presence of catalyst 1, a maximum total yield of ca. 80% was achieved for p-xylene oxidation.

MAX-DOAS observations of ship emissions in the North Sea

Shipping emissions were measured in Dunkirk, France. Elevated aerosol extinction coefficients (AEC), nitrogen dioxide (NO2) and sulphur dioxide (SO2) were observed up to 500 m from surface. Formaldehyde (HCHO) did not show an increase every time, which suggests that oxidation of emitted volatile organic compounds (VOCs) took longer than the transport to the observation path and dilution of direct emissions had occurred. Background NO2, HCHO, and SO2 levels were higher when the wind came over land or the surrounding industrial area, indicating that land-based sources contribute significantly; however, clear spikes in NO2 and SO2 were observed whenever ship plumes were sampled. Observations show that the ship emission contribution to pollution is significant, but land-based sources still dominate. The SO2/NO2 ratio was low throughout the campaign, although varying according to the ship type, confirming that the new fuel content regulations are being followed by most ships in this region.

Ozone Formation Sensitivity to Precursors and Lightning in the Tropical Troposphere Based on Airborne Observations

AbstractTropospheric ozone (O3) is an important greenhouse gas that is also hazardous to human health. The formation of O3 is sensitive to the levels of its precursors NOx (≡NO + NO2) and peroxy radicals, for example, generated by the oxidation of volatile organic compounds (VOCs). A better understanding of this sensitivity will show how changes in the levels of these trace gases could affect O3 levels today and in the future, and thus air quality and climate. In this study, we investigate O3 sensitivity in the tropical troposphere based on in situ observations of NO, HO2 and O3 from four research aircraft campaigns between 2015 and 2023. These are OMO (Oxidation Mechanism Observations), ATom (Atmospheric Tomography Mission), CAFE Africa (Chemistry of the Atmosphere Field Experiment in Africa) and CAFE Brazil, in combination with simulations using the EMAC atmospheric chemistry—climate model. We use the metric α(CH3O2) together with NO to investigate the O3 formation sensitivity. We show that O3 formation is generally NOx‐sensitive in the lower and middle tropical troposphere and is in a transition regime in the upper troposphere. By distinguishing observations impacted by lightning or not we show that NO from lightning is the most important driver of O3 sensitivity in the tropics. NOx‐sensitive chemistry predominates in regions without lightning impact, with α(CH3O2) ranging between 0.56 and 0.82 and observed average O3 levels between 35 and 55 ppbv. Areas affected by lightning exhibit strongly VOC‐sensitive O3 chemistry with α(CH3O2) of about 1 and average O3 levels between 55 and 80 ppbv.

Simultaneous Oxidation of Trace Organics and Sorption of Trace Metals by Ferrate (Fe(VI))-Coated Sand in Synthetic Wastewater Effluent.

The increased presence of toxic chemicals in aquatic matrices and their associated health effects raise the need for more effective treatment technologies. The application of Fe(VI), an advanced oxidation treatment agent with disinfecting and coagulating capabilities, is limited by Fe(VI) aqueous instability. Our previous study proposed an Fe(VI)-coated sand media to overcome this constraint and demonstrated that Fe(VI)-coated sand was an effective medium for the treatment of phenolic compounds. In this study, we assessed the potential of the media for treatment of acetaminophen (ACM), benzotriazole (BZT), sulfamethoxazole (SMX), copper (Cu), lead (Pb), and zinc (Zn)-common contaminants found in wastewater effluents-in ultrapure and synthetic wastewater effluent. Fe(VI)-coated sand reactivity was influenced by the solution pH and aqueous chemistry. For example, the removal of Pb improved by 39% in the presence of trace organics, indicating that trace metal removal was enhanced by Fe(III) phases formed during Fe(VI) reactions with trace organics. While oxidation of trace organic compounds increased as pH decreased, trace metal sorption was more favorable at higher pH (i.e., pH 8 and 9). The oxidation efficiency of trace organics by the media was the highest for ACM and SMX while BZT degradation was limited due to formation of Cu-BZT complexes. Batch tests in synthetic wastewater effluent revealed that the presence of divalent cations (i.e., Ca2+ and Mg2+) can catalyze Fe(VI) self-decay and promote Fe(III) production and subsequent trace metal removal; however, oxidation of trace organics was hindered in this matrix. This study highlights the potential for Fe(VI)-coated sand application for the treatment of complex matrices more representative of natural and engineered aquatic systems.

Tetrahydroquinolines as inhibitors of radical chain oxidation of organic compounds: kinetics and mechanism of action

Tetrahydroquinolines as inhibitors of radical chain oxidation of organic compounds: kinetics and mechanism of action

Unveiling the Mechanism and Kinetics of Pollutant Attenuation by Free Radicals Triggered from Goethite in Water Distribution Systems.

Investigating the fate of persistent organic pollutants in water distribution systems (WDSs) is of great significance for preventing human health risks. The role of iron corrosion scales in the migration and transformation of organics in such systems remains unclear. Herein, we determined that hydroxyl (•OH), chlorine, and chlorine oxide radicals are generated by Fenton-like reactions due to the coexistence of oxygen vacancy-related Fe(II) on goethite (a major constituent of iron corrosion scales) and hypochlorous acid (HClO, the main reactive chlorine species of residual chlorine at pH ∼ 7.0). •OH contributed mostly to the decomposition of atrazine (ATZ, model compound) more than other radicals, producing a series of relatively low-toxicity small molecular intermediates. A simplified kinetic model consisting of mass transfer of ATZ and HClO, •OH generation, and ATZ oxidation by •OH on the goethite surface was developed to simulate iron corrosion scale-triggered residual chlorine oxidation of organic compounds in a WDS. The model was validated by comparing the fitting results to the experimental data. Moreover, the model was comprehensively applicable to cases in which various inorganic ions (Ca2+, Na+, HCO3-, and SO42-) and natural organic matter were present. With further optimization, the model may be employed to predict the migration and accumulation of persistent organic pollutants under real environmental conditions in the WDSs.

Refining catalytic oxidation of volatile organic compounds over Gd-Sr-Co perovskite-based oxides fabricated via viscous mixture induction: Unveiling the crucial factors influencing catalytic activity

A series of Gd-Sr-Co perovskite-based oxides have been successfully synthesized by thermally driving viscous mixture, wherein only very trace amounts of water need and the metal salts powders do not need to be thoroughly mixed. By the characterization of XRD, XPS, EPR, and Raman, the levels of oxygen vacancies, lattice oxygen, and adsorbed oxygen in the catalyst are controlled by varying the amount of Sr doping. Unlike traditional conclusions, we found that the catalytic activities of the catalysts did not enhance with the increase in the contents of adsorbed oxygen and oxygen vacancies. H2-TPR and O2-TPD confirmed that the migration of lattice oxygen in catalysts determined their activities. Comparative activity of individual catalysts was evaluated by catalytic oxidation of toluene. The best active catalyst also showed superior catalytic activity for the oxidation of acetone, ethyl acetate, and chlorobenzene. The effects of humidity and weight hourly space velocity on the stability of the catalyst were also evaluated. Catalyst’s surface structural changes in toluene oxidation were also analyzed by in-situ DRIFTS. This study provides a simple approach to tailor perovskite-based oxide structures, crucial for effective catalytic oxidation of VOCs.

Low-Temperature Catalytic Oxidation of Volatile Organic Compounds (VOCs) using Transition Metal Mixed Oxide Catalysts

This paper discusses the modification of MnOx by doping various metals, such as Cu, supported on cordierite honeycomb ceramics, which were easily synthesized by using the impregnation method. The physicochemical properties were comprehensively featured via the BET, XRD, SEM-EDX and H2-TPR techniques. Activity results suggested that the introduction of doping metals significantly enhanced the catalytic performance of Cu1Mn2Ox compared to single metal oxides. Furthermore, in the catalytic oxidation of benzene and toluene, the monolithic Cu1Mn2Ox catalyst demonstrates the best catalytic performance. It was able to completely oxidize the two compounds at 275oC with a reaction velocity (WHSV) of about 18,000 mL/(g•hr) and pollutant concentrations of 7000 ppm and 12000 ppm, respectively. The formation of a Cu-Mn solid solution with spinel Cooper-Manganese structure was thought to be the cause of the excellent catalytic performance of monolithic Cu1Mn2Ox. This resulted in an increase in the amount of adsorbed oxygen species on the surface and a high lattice oxygen mobility. This can improve catalyst reducibility and oxygen species activity, as demonstrated by significantly higher dehydrogenation temperatures of Cu-Mn composite oxides through H2-TPR. Meanwhile, the monolithic Cu1Mn2Ox catalyst showed good stability in 16 hours of testing and cycle ability test and showed great potential in practical application.

Selective electrochemical oxidation of organic compounds in a mass transfer-enhanced electrochemical flow reactor (e[sbnd]NETmix)

eNETmix stands as an electrochemical flow reactor engineered to enhance mass transfer. This study aimed at assessing the performance of the eNETmix reactor in the realm of organic electrosynthesis. Specifically, the research focused on the selective electrochemical oxidation of 4-methoxybenzyl alcohol (4-MBA) to p-anisaldehyde (PAA) using a bare fluorine-doped tin oxide (FTO) anode. The efficiency of the process was assessed for distinct current densities (j), Reynolds numbers (Re), supporting electrolyte contents, and substrate initial contents. The eNETmix reactor was extensively compared to a commercial electrochemical flow reactor (MicroFlowCell from ElectroCell, Denmark). eNETmix facilitated the use of a broader range of j (0.8–2.0 mA cm−2versus 0.8 mA cm−2) together with smaller Re (≥190 versus >1750), supporting electrolyte contents (≥1 mM versus ≥30 mM), and substrate initial contents (≥2.0 mM versus ≥3.0 mM) with no loss of PAA production or energy consumption. These findings underscore a remarkable suitability of eNETmix as a reactor for organic electrosynthesis.

Trace Br- Inhibits Halogenated Byproduct Formation in Saline Wastewater Electrochemical Treatment.

The electrochemical technology provides a practical and viable solution to the global water scarcity issue, but it has an inherent challenge of generating toxic halogenated byproducts in treatment of saline wastewater. Our study reveals an unexpected discovery: the presence of a trace amount of Br- not only enhanced the electrochemical oxidation of organic compounds with electron-rich groups but also significantly reduced the formation of halogenated byproducts. For example, in the presence of 20 μM Br-, the oxidation rate of phenol increased from 0.156 to 0.563 min-1, and the concentration of total organic halogen decreased from 59.2 to 8.6 μM. Through probe experiments, direct electron transfer and HO• were ruled out as major contributors; transient absorption spectroscopy (TAS) and computational kinetic models revealed that trace Br- triggers a shift in the dominant reactive species from Cl2•- to Br2•-, which plays a key role in pollutant removal. Both TAS and electron paramagnetic resonance identified signals unique to the phenoxyl and carbon-centered radicals in the Br2•--dominated system, indicating distinct reaction mechanisms compared to those involving Cl2•-. Kinetic isotope experiments and density functional theory calculations confirmed that the interaction between Br2•- and phenolic pollutants follows a hydrogen atom abstraction pathway, whereas Cl2•- predominantly engages pollutants through radical adduct formation. These insights significantly enhance our understanding of bromine radical-involved oxidation processes and have crucial implications for optimizing electrochemical treatment systems for saline wastewater.

Selective photochemical oxidation of sulfides by Gallium and Sulfur Co-Modified TiO2/g-C3N4 Nanocomposites as catalyst

In this study, with the objective of promoting the oxidation of sulfides, a distinctive photocatalyst was synthesized by incorporating Ga- and S-co-doped TiO2 onto graphitic carbon nitride (g-C3N4). Under visible light irradiation, the composites demonstrated enhanced photocatalytic performance in comparison to g-C3N4 and TiO2/g-C3N4. The nanocomposite catalyst displayed a remarkable enhancement in photocatalytic activity, benefiting from the creation of a Z-scheme heterojunction by combining TiO2 and g-C3N4, as well as the presence of electron trap centers, efficient photogenerated electron transfer, improved charge carrier separation, and extended optical absorption in the visible light range. To optimize the performance, the substitution contents of Ga and S (GaxSy@TiO2-g-C3N4) were varied, where the values of x and y were set at 5 % and 10 %, respectively. Notably, Based on the obtained results, it was observed that the Ga5.0S10.0@TiO2-g-C3N4 sample displayed the highest yield when subjected to visible-light irradiation, making it the most effective and optimal sample. The findings of this study offer a fresh perspective on the synergistic effect of dopant photocatalysts in the oxidation of organic compounds. This work presents a novel approach for the development of highly efficient photocatalysts capable of effectively oxidizing organic compounds.

Synergistic doping and de-doping of Co3O4 catalyst for effortless formaldehyde oxidation

The pursuit of high-performance non-precious metal catalysts for Volatile Organic Compounds (VOCs) abatement is paramount in meeting stringent environmental regulations. In this study, we present a groundbreaking approach by crafting a highly defective Co3O4 catalyst through a strategic process involving Mg doping and subsequent partial de-doping. The catalyst exhibited an exceptional activity in the oxidation of formaldehyde (HCHO), achieving a remarkable conversion rate of 2.92 μmol·m−2·h−1, which is 3.1 times that of the pristine Co3O4 at 100 °C and an HCHO space velocity of 75,000 mL·g−1·h−1. Our methodology involves a dual-action process of doping and de-doping, orchestrating the introduction of significant structural and surface defects. These include surface cracks, lattice distortions, cationic vacancies, oxygen vacancies, lower metal coordination, and more. This orchestrated creation of defects serves to amplify the generation of active oxygen sites, thereby enhancing the intrinsic oxidative ability of the catalyst. The net result is a lowered activation energy barrier for HCHO, further contributing to the catalyst performance enhancement. This study not only establishes a new benchmark for Co3O4 catalysis but also provides insightful paradigms for the role of defects engineering in promoting non-noble metal-catalyzed volatile organic compounds oxidation.

Trivalent Copper Ion-Mediated Dual Oxidation in the Copper-Catalyzed Fenton-Like System in the Presence of Histidine.

The Cu(II)/H2O2 system is recognized for its potential to degrade recalcitrant organic contaminants and inactivate microorganisms in wastewater. We investigated its unique dual oxidation strategy involving the selective oxidation of copper-complexing ligands and enhanced oxidation of nonchelated organic compounds. L-Histidine (His) and benzoic acid (BA) served as model compounds for basic biomolecular ligands and recalcitrant organic contaminants, respectively. In the presence of both His and BA, the Cu(II)/H2O2 system rapidly degraded His complexed with copper ions within 30 s; however, BA degraded gradually with a 2.3-fold efficiency compared with that in the absence of His. The primary oxidant responsible was the trivalent copper ion [Cu(III)], not hydroxyl radical (•OH), as evidenced by •OH scavenging, hydroxylated BA isomer comparison with UV/H2O2 (a •OH generating system), electron paramagnetic resonance, and colorimetric Cu(III) detection via periodate complexation. Cu(III) selectively oxidized His owing to its strong chelation with copper ions, even in the presence of excess tert-butyl alcohol. This selectivity extended to other copper-complexing ligands, including L-asparagine and L-aspartic acid. The presence of His facilitated H2O2-mediated Cu(II) reduction and increased Cu(III) production, thereby enhancing the degradation of BA and pharmaceuticals. Thus, the Cu(II)/H2O2 system is a promising option for dual-target oxidation in diverse applications.

Supported nano-sized precious metal catalysts for oxidation of catalytic volatile organic compounds.

Volatile organic compounds (VOCs) are common contaminants found as indoor as well as outdoor pollutants, which can induce acute or chronic health hazards to the human physiological system. The catalytic oxidation method is widely considered as one of the effective methods for removing VOCs, and the development of highly effective catalysts is highly urgent for booming this interesting field. This review focuses on the recent progress of VOC oxidation catalyzed by supported nano-sized precious metal catalysts, and discusses the effects of metal composition, supports, size, and morphology on the catalytic activity. In addition, the roles played by both nano-sized precious metals and supports in enhancing the performance of catalytic VOCs are also systematically discussed, which will guide the further development of more advanced VOC catalysts.

16S rRNA Analysis of Electrogenic Bacterial Communities from Soil Microbial Fuel Cells

Electrogenic bacteria present in bioelectrical devices such as soil microbial fuel cells (SMFCs) are powered by the oxidation of organic and inorganic compounds due to microbial activity. Fourteen soils randomly selected from Bergen Community College or areas nearby, located in the state of New Jersey, USA, were used to screen for the presence of electrogenic bacteria. SMFCs were incubated at 35–37 °C. Of the 14 samples, 11 generated electricity and enriched electrogenic bacteria. The average optimal electricity production by the top 3 SMFCs was 152 microwatts. The highest electrical production was produced by SMFC-B1C and SMFC-B1B, with 162 and 152 microwatts, respectively. Microbial DNA was extracted from the biofilm grown on the anodes, followed by PCR analysis of the 16S rRNA V3–V4 region. Next-generation sequencing was performed to determine the structure and diversity of the electrogenic microbial community. The top 3 MFCs with the highest electricity production showed a bacterial community predominantly composed of bacteria belonging to the Bacillota and Pseudomonadota phyla with a significant presence of Euryarcheota members of methanogenic archaea. SMFC-B1C showed a more diverse electrogenic community, followed by SMFC-B1B and SMFC-B1. When analyzing the top 10 bacteria in the SMFCs, 67 percent belonged to the class Clostridia, indicating that anaerobic conditions were required to enrich electrogenic bacterial numbers and optimize electrical production. The ongoing optimization of SMFCs will provide better production of electricity and continuous enhancement of microbial activity to sustain longer operational times and higher levels of electrogenesis. The characterization of electrogenic microbial communities will provide valuable information to understand the contribution of different populations to the production of electricity in bioelectrical devices.

Performance and Reaction Mechanisms of Catalytic Combustion of Toluene and Ethyl Acetate Over Fe‐Mn Oxides

AbstractIn this paper, Fe−Mn oxide catalysts were prepared by the co‐precipitation method. (Fe2O3)‐(Mn3O4)‐3 : 1 showed the best catalytic activity in the degradation of toluene and ethyl acetate, with the removal rate reaching 90 % at 166 °C and 156 °C respectively. The XRD, SEM, TEM, and XPS characterizations revealed that the interaction between Fe and Mn and the higher surface adsorption of oxygen in the (Fe2O3)‐(Mn3O4)‐3 : 1 catalyst may be the main factors promoting the catalytic oxidation. (Fe2O3)‐(Mn3O4)‐3 : 1 exhibited a better removal rate in ethyl acetate than toluene at different space velocities, concentrations and water contents. Under the same conditions, the degradation rate of (Fe2O3)‐(Mn3O4)‐3 : 1 in ethyl acetate was also greater than that in xylene and butyl acetate, which was related to their oxidation processes. FT‐IR and GC‐MS characterizations of fresh and used (Fe2O3)‐(Mn3O4)‐3 : 1 catalysts revealed intermediates in the oxidation of volatile organic compounds, and the reaction mechanisms were analyzed: Firstly, VOCs molecules were adsorbed on the catalyst surface, then decomposed into organic intermediates and oxidized to CO2 and H2O finally.

Amorphous Ce-Ti composite as an efficient bifunctional catalyst for deep oxidation of volatile organic compounds and selective catalytic reduction of NO

In this work, a series of Ce-Ti composite oxides with different Ti/Ce molar ratios was prepared by co-precipitation method, and investigated for the catalytic degradation of toluene and selective catalytic reduction of NO. The phase transition process between Ce species and Ti species is limited by modulating the interaction between Ce4+ and Ti4+, while a completely amorphous composite is generated with an appropriate molar ratio of Ti/Ce (1.5/1). The catalyst CeTi1.5Ox exhibits the best catalytic performance, where the values of T90 and T50 for deep degradation of toluene are 297 and 330 °C respectively at high weight hours space velocity (WHSV=120000 mL/(g⋅h)). Compared with CeO2, T90 and T50 decrease by 48 and 34 °C respectively while declining by 67 and 70 °C compared to TiO2. For the SCR reaction, CeTi1.5Ox reaches 100% NO conversion at 250 °C with WHSV=60000 mL/(g⋅h), reduced by 50 °C compared to pure CeO2. The amorphous nanostructure with highly dispersed Ce and Ti species was confirmed by transmission electron microscopy (TEM) and X-ray diffraction (XRD) characterizations. The X-ray photoelectron spectroscopy (XPS) and Raman analyses show that a large number of active Ce-O-Ti species and surface oxygen vacancies are generated due to the strong interaction between Ti4+ and Ce4+ in CeTi1.5Ox. Additionally, H2-TPR and O2-TPD further confirm that the interaction promotes the low-temperature reducibility and mobility of surface-active oxygen species. Meanwhile, in-situ DRIFTS study reveals that CeTi1.5Ox with amorphous nanostructure can dramatically enhance the dissociative and complete oxidation capacity for toluene.

Development of a multiphase chemical mechanism to improve secondary organic aerosol formation in CAABA/MECCA (version 4.7.0)

Abstract. During the last few decades, the impact of multiphase chemistry on secondary organic aerosols (SOAs) has been demonstrated to be the key to explaining laboratory experiments and field measurements. However, global atmospheric models still show large biases when simulating atmospheric observations of organic aerosols (OAs). Major reasons for the model errors are the use of simplified chemistry schemes of the gas-phase oxidation of vapours and the parameterization of heterogeneous surface reactions. The photochemical oxidation of anthropogenic and biogenic volatile organic compounds (VOCs) leads to products that either produce new SOA or are taken up by existing aqueous media like cloud droplets and deliquescent aerosols. After partitioning, aqueous-phase processing results in polyols, organosulfates, and other products with a high molar mass and oxygen content. In this work, we introduce the formation of new low-volatility organic compounds (LVOCs) to the multiphase chemistry box model CAABA/MECCA. Most notable are the additions of the SOA precursors, limonene and n-alkanes (5 to 8 C atoms), and a semi-explicit chemical mechanism for the formation of LVOCs from isoprene oxidation in the gas and aqueous phases. Moreover, Henry's law solubility constants and their temperature dependences are estimated for the partitioning of organic molecules to the aqueous phase. Box model simulations indicate that the new chemical scheme predicts the enhanced formation of LVOCs, which are known for being precursor species to SOAs. As expected, the model predicts that LVOCs are positively correlated to temperature but negatively correlated to NOx levels. However, the aqueous-phase processing of isoprene epoxydiols (IEPOX) displays a more complex dependence on these two key variables. Semi-quantitative comparison with observations from the SOAS campaign suggests that the model may overestimate methylbutane-1,2,3,4-tetrol (MeBuTETROL) from IEPOX. Further application of the mechanism in the modelling of two chamber experiments, one in which limonene is consumed by ozone and one in which isoprene is consumed by NO3 shows a sufficient agreement with experimental results within model limitations. The extensions in CAABA/MECCA are transferred to the 3D atmospheric model MESSy for a comprehensive evaluation of the impact of aqueous- and/or aerosol-phase chemistry on SOA at a global scale in a follow-up study.

Primary Radical Effectiveness: Do the Different Chemical Reactivities of Hydroxyl and Chlorine Radicals Matter for Tropospheric Oxidation?

The atmospheric oxidation of organics occurs primarily via reaction cycles involving gas phase radical species, catalysed by nitric oxide (NO), which result in the production of secondary pollutants such as ozone. For these oxidation cycles to occur, they must be initialized by a primary radical, i.e., a radical formed from non-radical precursors. Once formed, these primary radicals can result in the oxidation of organic compounds to produce peroxy radicals that, providing sufficient NO is present, can re-generate "secondary" radicals which can go on to oxidize further organics. Thus, one primary radical can result in the catalytic oxidation of multiple organics. Although the photolysis of ozone in the presence of water vapor to form two hydroxyl (OH) radicals is accepted as the dominant tropospheric primary radical source, multiple other primary radical sources exist and can dominate in certain environments. The chemical reactivity of different radicals to organic and inorganic compounds can be very different, however, and how these differences in radical chemistry impact atmospheric organic oxidation under different atmospheric conditions has not been previously demonstrated. In this work, we use a series of model simulations to investigate the impact of the chemical reactivity of the primary radical on the effectiveness in initializing organic oxidation and thus the production of the secondary pollutant ozone. We compare the chemistries of the OH and atomic chlorine (Cl) radicals and their effectiveness at initializing organic oxidation under different nitrogen oxide and organic concentrations. The OH radical is the dominant tropospheric radical, with both primary and secondary sources. In contrast, Cl has primary sources that show significant spatial heterogeneity throughout the troposphere but is not typically regenerated in catalytic cycles. Both primary OH and Cl can initiate organic oxidation, but this work shows that the relative effectiveness with which they oxidize organics and produce ozone depends on their balance of propagation vs termination reactions which is in turn determined by the chemical environment in which they are produced. In particular, our work shows that in high NOx radical-limited environments, like those found in many urban areas, Cl will be more efficient at oxidizing organics than OH.

Transpacific Transport of Asian Peroxyacetyl Nitrate (PAN) Observed from Satellite: Implications for Ozone.

Peroxyacetyl nitrate (PAN) is produced in the atmosphere by photochemical oxidation of non-methane volatile organic compounds in the presence of nitrogen oxides (NOx), and it can be transported over long distances at cold temperatures before decomposing thermally to release NOx in the remote troposphere. It is both a tracer and a precursor for transpacific ozone pollution transported from East Asia to North America. Here, we directly demonstrate this transport with PAN satellite observations from the infrared atmospheric sounding interferometer (IASI). We reprocess the IASI PAN retrievals by replacing the constant prior vertical profile with vertical shape factors from the GEOS-Chem model that capture the contrasting shapes observed from aircraft over South Korea (KORUS-AQ) and the North Pacific (ATom). The reprocessed IASI PAN observations show maximum transpacific transport of East Asian pollution in spring, with events over the Northeast Pacific offshore from the Western US associated in GEOS-Chem with elevated ozone in the lower free troposphere. However, these events increase surface ozone in the US by less than 1 ppbv because the East Asian pollution mainly remains offshore as it circulates the Pacific High.