Atmospheric Photo-Oxidation of 2-Ethoxyethanol: Autoxidation Chemistry of Glycol Ethers.

We investigate the gas-phase photo-oxidation of 2-ethoxyethanol (2-EE) initiated by the OH radical with a focus on its autoxidation pathways. Gas-phase autoxidation─intramolecular H-shifts followed by O2 addition─has recently been recognized as a major atmospheric chemical pathway that leads to the formation of highly oxygenated organic molecules (HOMs), which are important precursors for secondary organic aerosols (SOAs). Here, we examine the gas-phase oxidation pathways of 2-EE, a model compound for glycol ethers, an important class of volatile organic compounds (VOCs) used in volatile chemical products (VCPs). Both experimental and computational techniques are applied to analyze the photochemistry of the compound. We identify oxidation products from both bimolecular and autoxidation reactions from chamber experiments at varied HO2 levels and provide estimations of rate coefficients and product branching ratios for key reaction pathways. The H-shift processes of 2-EE peroxy radicals (RO2) are found to be sufficiently fast to compete with bimolecular reactions under modest NO/HO2 conditions. More than 30% of the produced RO2 are expected to undergo at least one H-shift for conditions typical of modern summer urban atmosphere, where RO2 bimolecular lifetime is becoming >10 s, which implies the potential for glycol ether oxidation to produce considerable amounts of HOMs at reduced NOx levels and elevated temperature. Understanding the gas-phase autoxidation of glycol ethers can help fill the knowledge gap in the formation of SOA derived from oxygenated VOCs emitted from VCP sources.

Hydrotrioxide (ROOOH) formation in the atmosphere.

Organic hydrotrioxides (ROOOH) are known to be strong oxidants used in organic synthesis. Previously, it has been speculated that they are formed in the atmosphere through the gas-phase reaction of organic peroxy radicals (RO2) with hydroxyl radicals (OH). Here, we report direct observation of ROOOH formation from several atmospherically relevant RO2 radicals. Kinetic analysis confirmed rapid RO2 + OH reactions forming ROOOH, with rate coefficients close to the collision limit. For the OH-initiated degradation of isoprene, global modeling predicts molar hydrotrioxide formation yields of up to 1%, which represents an annual ROOOH formation of about 10 million metric tons. The atmospheric lifetime of ROOOH is estimated to be minutes to hours. Hydrotrioxides represent a previously omitted substance class in the atmosphere, the impact of which needs to be examined.

Ozone chemistry in western U.S. wildfire plumes.

Wildfires are a substantial but poorly quantified source of tropospheric ozone (O3). Here, to investigate the highly variable O3 chemistry in wildfire plumes, we exploit the in situ chemical characterization of western wildfires during the FIREX-AQ flight campaign and show that O3 production can be predicted as a function of experimentally constrained OH exposure, volatile organic compound (VOC) reactivity, and the fate of peroxy radicals. The O3 chemistry exhibits rapid transition in chemical regimes. Within a few daylight hours, the O3 formation substantially slows and is largely limited by the abundance of nitrogen oxides (NOx). This finding supports previous observations that O3 formation is enhanced when VOC-rich wildfire smoke mixes into NOx-rich urban plumes, thereby deteriorating urban air quality. Last, we relate O3 chemistry to the underlying fire characteristics, enabling a more accurate representation of wildfire chemistry in atmospheric models that are used to study air quality and predict climate.

Large contribution of biomass burning emissions to ozone throughout the global remote troposphere.

Ozone is the third most important anthropogenic greenhouse gas after carbon dioxide and methane but has a larger uncertainty in its radiative forcing, in part because of uncertainty in the source characteristics of ozone precursors, nitrogen oxides, and volatile organic carbon that directly affect ozone formation chemistry. Tropospheric ozone also negatively affects human and ecosystem health. Biomass burning (BB) and urban emissions are significant but uncertain sources of ozone precursors. Here, we report global-scale, in situ airborne measurements of ozone and precursor source tracers from the NASA Atmospheric Tomography mission. Measurements from the remote troposphere showed that tropospheric ozone is regularly enhanced above background in polluted air masses in all regions of the globe. Ozone enhancements in air with high BB and urban emission tracers (2.1 to 23.8 ppbv [parts per billion by volume]) were generally similar to those in BB-influenced air (2.2 to 21.0 ppbv) but larger than those in urban-influenced air (-7.7 to 6.9 ppbv). Ozone attributed to BB was 2 to 10 times higher than that from urban sources in the Southern Hemisphere and the tropical Atlantic and roughly equal to that from urban sources in the Northern Hemisphere and the tropical Pacific. Three independent global chemical transport models systematically underpredict the observed influence of BB on tropospheric ozone. Potential reasons include uncertainties in modeled BB injection heights and emission inventories, export efficiency of BB emissions to the free troposphere, and chemical mechanisms of ozone production in smoke. Accurately accounting for intermittent but large and widespread BB emissions is required to understand the global tropospheric ozone burden.

HCOOH in the remote atmosphere: Constraints from Atmospheric Tomography (ATom) airborne observations.

Formic acid (HCOOH) is an important component of atmospheric acidity but its budget is poorly understood, with prior observations implying substantial missing sources. Here we combine pole-to-pole airborne observations from the Atmospheric Tomography Mission (ATom) with chemical transport model (GEOS-Chem CTM) and back trajectory analyses to provide the first global in-situ characterization of HCOOH in the remote atmosphere. ATom reveals sub-100 ppt HCOOH concentrations over most of the remote oceans, punctuated by large enhancements associated with continental outflow. Enhancements correlate with known combustion tracers and trajectory-based fire influences. The GEOS-Chem model underpredicts these in-plume HCOOH enhancements, but elsewhere we find no broad indication of a missing HCOOH source in the background free troposphere. We conclude that missing non-fire HCOOH precursors inferred previously are predominantly short-lived. We find indications of a wet scavenging underestimate in the model consistent with a positive HCOOH bias in the tropical upper troposphere. Observations reveal episodic evidence of ocean HCOOH uptake, which is well-captured by GEOS-Chem; however, despite its strong seawater undersaturation HCOOH is not consistently depleted in the remote marine boundary layer. Over fifty fire and mixed plumes were intercepted during ATom with widely varying transit times and source regions. HCOOH:CO normalized excess mixing ratios in these plumes range from 3.4 to >50 ppt/ppb CO and are often over an order of magnitude higher than expected primary emission ratios. HCOOH is thus a major reactive organic carbon reservoir in the aged plumes sampled during ATom, implying important missing pathways for in-plume HCOOH production.

Rapid hydrolysis of tertiary isoprene nitrate efficiently removes NOx from the atmosphere.

The formation of a suite of isoprene-derived hydroxy nitrate (IHN) isomers during the OH-initiated oxidation of isoprene affects both the concentration and distribution of nitrogen oxide free radicals (NOx). Experiments performed in an atmospheric simulation chamber suggest that the lifetime of the most abundant isomer, 1,2-IHN, is shortened significantly by a water-mediated process (leading to nitric acid formation), while the lifetime of a similar isomer, 4,3-IHN, is not. Consistent with these chamber studies, NMR kinetic experiments constrain the 1,2-IHN hydrolysis lifetime to less than 10 s in deuterium oxide (D2O) at 298 K, whereas the 4,3-IHN isomer has been observed to hydrolyze much less efficiently. These laboratory findings are used to interpret observations of the IHN isomer distribution in ambient air. The IHN isomer ratio (1,2-IHN to 4,3-IHN) in a high NOx environment decreases rapidly in the afternoon, which is not explained using known gas-phase chemistry. When simulated with an observationally constrained model, we find that an additional loss process for the 1,2-IHN isomer with a time constant of about 6 h best explains our atmospheric measurements. Using estimates for 1,2-IHN Henry's law constant and atmospheric liquid water volume, we show that condensed-phase hydrolysis of 1,2-IHN can account for this loss process. Simulations from a global chemistry transport model show that the hydrolysis of 1,2-IHN accounts for a substantial fraction of NOx lost (and HNO3 produced), resulting in large impacts on oxidant formation, especially over forested regions.

New Insights into the Radical Chemistry and Product Distribution in the OH-Initiated Oxidation of Benzene.

Emissions of aromatic compounds cause air pollution and detrimental health effects. Here, we explore the reaction kinetics and products of key radicals in benzene photo-oxidation. After initial OH addition and reaction with O2, the effective production rates of phenol and bicyclic peroxy radical (BCP-peroxy) are experimentally constrained at 295 K to be 420 ± 80 and 370 ± 70 s-1, respectively. These rates lead to approximately 53% yield for phenol and 47% yield for BCP-peroxy under atmospheric conditions. The reaction of BCP-peroxy with NO produces bicyclic hydroxy nitrate with a branching ratio <0.2%, indicating efficient NOx recycling. Similarly, the reaction of BCP-peroxy with HO2 largely recycles HOx, producing the corresponding bicyclic alkoxy radical (BCP-oxy). Because of the presence of C-C double bonds and multiple functional groups, the chemistry of BCP-oxy and other alkoxy radicals in the system is diverse. Experimental results suggest the aldehydic H-shift and ring-closure to produce an epoxide functionality could be competitive with classic decomposition of alkoxy radicals. These reactions are potential sources of highly oxygenated molecules. Finally, despite the large number of compounds observed in our study, we are unable to account for ∼20% of the carbon flow.

Constraining remote oxidation capacity with ATom observations.

The global oxidation capacity, defined as the tropospheric mean concentration of the hydroxyl radical (OH), controls the lifetime of reactive trace gases in the atmosphere such as methane and carbon monoxide (CO). Models tend to underestimate the methane lifetime and CO concentrations throughout the troposphere, which is consistent with excessive OH. Approximately half of the oxidation of methane and non-methane volatile organic compounds (VOCs) is thought to occur over the oceans where oxidant chemistry has received little validation due to a lack of observational constraints. We use observations from the first two deployments of the NASA ATom aircraft campaign during July-August 2016 and January-February 2017 to evaluate the oxidation capacity over the remote oceans and its representation by the GEOS-Chem chemical transport model. The model successfully simulates the magnitude and vertical profile of remote OH within the measurement uncertainties. Comparisons against the drivers of OH production (water vapor, ozone, and NO y concentrations, ozone photolysis frequencies) also show minimal bias, with the exception of wintertime NO y . The severe model overestimate of NO y during this period may indicate insufficient wet scavenging and/or missing loss on sea-salt aerosols. Large uncertainties in these processes require further study to improve simulated NO y partitioning and removal in the troposphere, but preliminary tests suggest that their overall impact could marginally reduce the model bias in tropospheric OH. During the ATom-1 deployment, OH reactivity (OHR) below 3 km is significantly enhanced, and this is not captured by the sum of its measured components (cOHRobs) or by the model (cOHRmod). This enhancement could suggest missing reactive VOCs but cannot be explained by a comprehensive simulation of both biotic and abiotic ocean sources of VOCs. Additional sources of VOC reactivity in this region are difficult to reconcile with the full suite of ATom measurement constraints. The model generally reproduces the magnitude and seasonality of cOHRobs but underestimates the contribution of oxygenated VOCs, mainly acetaldehyde, which is severely underestimated throughout the troposphere despite its calculated lifetime of less than a day. Missing model acetaldehyde in previous studies was attributed to measurement uncertainties that have been largely resolved. Observations of peroxyacetic acid (PAA) provide new support for remote levels of acetaldehyde. The underestimate in both model acetaldehyde and PAA is present throughout the year in both hemispheres and peaks during Northern Hemisphere summer. The addition of ocean sources of VOCs in the model increases cOHRmod by 3% to 9% and improves model-measurement agreement for acetaldehyde, particularly in winter, but cannot resolve the model summertime bias. Doing so would require 100 Tg yr-1 of a long-lived unknown precursor throughout the year with significant additional emissions in the Northern Hemisphere summer. Improving the model bias for remote acetaldehyde and PAA is unlikely to fully resolve previously reported model global biases in OH and methane lifetime, suggesting that future work should examine the sources and sinks of OH over land.

Stereoselectivity in Atmospheric Autoxidation.

We show that the diastereomers of hydroxy peroxy radicals formed from OH and O2 addition to C2 and C3, respectively, of crotonaldehyde (CH3CHCHCHO) undergo gas-phase unimolecular aldehydic hydrogen shift (H-shift) chemistry with rate coefficients that differ by an order of magnitude. The stereospecificity observed here for crotonaldehyde is general and will lead to a significant diastereomeric-specific chemistry in the atmosphere. This enhancement of specific stereoisomers by stereoselective gas-phase reactions could have widespread implications given the ubiquity of chirality in nature. The H-shift rate coefficients calculated using multiconformer transition state theory (MC-TST) agree with those determined experimentally using stereoisomer-specific gas-chromatography chemical ionization mass spectroscopy (GC-CIMS) measurements.

Mapping hydroxyl variability throughout the global remote troposphere via synthesis of airborne and satellite formaldehyde observations.

The hydroxyl radical (OH) fuels tropospheric ozone production and governs the lifetime of methane and many other gases. Existing methods to quantify global OH are limited to annual and global-to-hemispheric averages. Finer resolution is essential for isolating model deficiencies and building process-level understanding. In situ observations from the Atmospheric Tomography (ATom) mission demonstrate that remote tropospheric OH is tightly coupled to the production and loss of formaldehyde (HCHO), a major hydrocarbon oxidation product. Synthesis of this relationship with satellite-based HCHO retrievals and model-derived HCHO loss frequencies yields a map of total-column OH abundance throughout the remote troposphere (up to 70% of tropospheric mass) over the first two ATom missions (August 2016 and February 2017). This dataset offers unique insights on near-global oxidizing capacity. OH exhibits significant seasonality within individual hemispheres, but the domain mean concentration is nearly identical for both seasons (1.03 ± 0.25 × 106 cm-3), and the biseasonal average North/South Hemisphere ratio is 0.89 ± 0.06, consistent with a balance of OH sources and sinks across the remote troposphere. Regional phenomena are also highlighted, such as a 10-fold OH depression in the Tropical West Pacific and enhancements in the East Pacific and South Atlantic. This method is complementary to budget-based global OH constraints and can help elucidate the spatial and temporal variability of OH production and methane loss.

Highly Oxygenated Organic Molecules (HOM) from Gas-Phase Autoxidation Involving Peroxy Radicals: A Key Contributor to Atmospheric Aerosol.

Highly oxygenated organic molecules (HOM) are formed in the atmosphere via autoxidation involving peroxy radicals arising from volatile organic compounds (VOC). HOM condense on pre-existing particles and can be involved in new particle formation. HOM thus contribute to the formation of secondary organic aerosol (SOA), a significant and ubiquitous component of atmospheric aerosol known to affect the Earth's radiation balance. HOM were discovered only very recently, but the interest in these compounds has grown rapidly. In this Review, we define HOM and describe the currently available techniques for their identification/quantification, followed by a summary of the current knowledge on their formation mechanisms and physicochemical properties. A main aim is to provide a common frame for the currently quite fragmented literature on HOM studies. Finally, we highlight the existing gaps in our understanding and suggest directions for future HOM research.

Unimolecular Reactions of Peroxy Radicals Formed in the Oxidation of α-Pinene and ß-Pinene by Hydroxyl Radicals.

Atmospheric oxidation of monoterpenes (emitted primarily by evergreen trees) is known to contribute to the formation and growth of aerosol particles. While recent research has tied the formation of organic aerosol to unimolecular chemistry of the organic peroxy radicals (RO2) formed in the oxidation of monoterpenes, the fundamental physical chemistry of these RO2 remains obscure. Here we use isomer-specific measurements and ab initio calculations to determine the unimolecular reaction rates and products of RO2 derived from the hydroxyl radical (OH) oxidation of α-pinene and ß-pinene. Among all of the structural isomers of the first-generation RO2 from both monoterpenes, we find that the first-generation RO2 produced following opening of the four-membered ring undergo fast unimolecular reactions (4 ± 2 and 16 ± 5 s-1 for α-pinene and ß-pinene, respectively) at 296 K, in agreement with high-level ab initio calculations. The presence of the hydroxy group and carbon-carbon double bond in the ring-opened RO2 enhances the rates of these unimolecular reactions, including endo-cyclization and H-shift via transition states involving six- and seven-membered rings. These reaction rate coefficients are sufficiently large that unimolecular chemistry is the dominant fate of these monoterpene-derived RO2 in the atmosphere. In addition, the overall yields of first-generation α-pinene and ß-pinene hydroxy nitrates, C10H17NO4, at 296 K and 745 Torr are measured to be 3.3 ± 1.5% and 6.4 ± 2.1%, respectively, for conditions where all RO2 are expected to react with NO ([NO] > 1000 ppbv). These yields are lower than anticipated.

On the sources and sinks of atmospheric VOCs: an integrated analysis of recent aircraft campaigns over North America.

We apply a high-resolution chemical transport model (GEOS-Chem CTM) with updated treatment of volatile organic compounds (VOCs) and a comprehensive suite of airborne datasets over North America to (i) characterize the VOC budget and (ii) test the ability of current models to capture the distribution and reactivity of atmospheric VOCs over this region. Biogenic emissions dominate the North American VOC budget in the model, accounting for 70 % and 95 % of annually emitted VOC carbon and reactivity, respectively. Based on current inventories anthropogenic emissions have declined to the point where biogenic emissions are the dominant summertime source of VOC reactivity even in most major North American cities. Methane oxidation is a 2x larger source of nonmethane VOCs (via production of formaldehyde and methyl hydroperoxide) over North America in the model than are anthropogenic emissions. However, anthropogenic VOCs account for over half of the ambient VOC loading over the majority of the region owing to their longer aggregate lifetime. Fires can be a significant VOC source episodically but are small on average. In the planetary boundary layer (PBL), the model exhibits skill in capturing observed variability in total VOC abundance (R 2 = 0:36) and reactivity (R 2 = 0:54). The same is not true in the free troposphere (FT), where skill is low and there is a persistent low model bias (~ 60 %), with most (27 of 34) model VOCs underestimated by more than a factor of 2. A comparison of PBL: FT concentration ratios over the southeastern US points to a misrepresentation of PBL ventilation as a contributor to these model FT biases. We also find that a relatively small number of VOCs (acetone, methanol, ethane, acetaldehyde, formaldehyde, isoprene C oxidation products, methyl hydroperoxide) drive a large fraction of total ambient VOC reactivity and associated model biases; research to improve understanding of their budgets is thus warranted. A source tracer analysis suggests a current overestimate of biogenic sources for hydroxyacetone, methyl ethyl ketone and glyoxal, an underestimate of biogenic formic acid sources, and an underestimate of peroxyacetic acid production across biogenic and anthropogenic precursors. Future work to improve model representations of vertical transport and to address the VOC biases discussed are needed to advance predictions of ozone and SOA formation.

Atmospheric Acetaldehyde: Importance of Air-Sea Exchange and a Missing Source in the Remote Troposphere.

We report airborne measurements of acetaldehyde (CH3CHO) during the first and second deployments of the National Aeronautics and Space Administration (NASA) Atmospheric Tomography Mission (ATom). The budget of CH3CHO is examined using the Community Atmospheric Model with chemistry (CAM-chem), with a newly-developed online air-sea exchange module. The upper limit of the global ocean net emission of CH3CHO is estimated to be 34 Tg a-1 (42 Tg a-1 if considering bubble-mediated transfer), and the ocean impacts on tropospheric CH3CHO are mostly confined to the marine boundary layer. Our analysis suggests that there is an unaccounted CH3CHO source in the remote troposphere and that organic aerosols can only provide a fraction of this missing source. We propose that peroxyacetic acid (PAA) is an ideal indicator of the rapid CH3CHO production in the remote troposphere. The higher-than-expected CH3CHO measurements represent a missing sink of hydroxyl radicals (and halogen radical) in current chemistry-climate models.

Intramolecular Hydrogen Shift Chemistry of Hydroperoxy-Substituted Peroxy Radicals.

Gas-phase autoxidation - the sequential regeneration of peroxy radicals (RO2) via intramolecular hydrogen shifts (H-shifts) followed by oxygen addition - leads to the formation of organic hydroperoxides. The atmospheric fate of these peroxides remains unclear, including the potential for further H-shift chemistry. Here, we report H-shift rate coefficients for a system of RO2 with hydroperoxide functionality produced in the OH-initiated oxidation of 2-hydroperoxy-2-methylpentane. The initial RO2 formed in this chemistry are unable to undergo α-OOH H-shift (HOOC-H) reactions. However, these RO2 rapidly isomerize (>100 s-1 at 296 K) by H-shift of the hydroperoxy hydrogen (ROO-H) to produce a hydroperoxy-substituted RO2 with an accessible α-OOH hydrogen. First order rate coefficients for the 1,5 H-shift of the α-OOH hydrogen are measured to be ∼0.04 s-1 (296 K) and ∼0.1 s-1 (318 K), within 50% of the rate coefficients calculated using multiconformer transition state theory. Reaction of the RO2 with NO produces alkoxy radicals which also undergo rapid isomerization via 1,6 and 1,5 H-shift of the hydroperoxy hydrogen (ROO-H) to produce RO2 with alcohol functionality. One of these hydroxy-substituted RO2 exhibits a 1,5 α-OH (HOC-H) H-shift, measured to be ∼0.2 s-1 (296 K) and ∼0.6 s-1 (318 K), again in agreement with the calculated rates. Thus, the rapid shift of hydroperoxy hydrogens in alkoxy and peroxy radicals enables intramolecular reactions that would otherwise be inaccessible.

Constraints on Aerosol Nitrate Photolysis as a Potential Source of HONO and NO x.

The concentration of nitrogen oxides (NO x) plays a central role in controlling air quality. On a global scale, the primary sink of NO x is oxidation to form HNO3. Gas-phase HNO3 photolyses slowly with a lifetime in the troposphere of 10 days or more. However, several recent studies examining HONO chemistry have proposed that particle-phase HNO3 undergoes photolysis 10-300 times more rapidly than gas-phase HNO3. We present here constraints on the rate of particle-phase HNO3 photolysis based on observations of NO x and HNO3 collected over the Yellow Sea during the KORUS-AQ study in summer 2016. The fastest proposed photolysis rates are inconsistent with the observed NO x to HNO3 ratios. Negligible to moderate enhancements of the HNO3 photolysis rate in particles, 1-30 times faster than in the gas phase, are most consistent with the observations. Small or moderate enhancement of particle-phase HNO3 photolysis would not significantly affect the HNO3 budget but could help explain observations of HONO and NO x in highly aged air.

Kinetics and Product Yields of the OH Initiated Oxidation of Hydroxymethyl Hydroperoxide.

Hydroxymethyl hydroperoxide (HMHP), formed in the reaction of the C1 Criegee intermediate with water, is among the most abundant organic peroxides in the atmosphere. Although reaction with OH is thought to represent one of the most important atmospheric removal processes for HMHP, this reaction has been largely unstudied in the laboratory. Here, we present measurements of the kinetics and products formed in the reaction of HMHP with OH. HMHP was oxidized by OH in an environmental chamber; the decay of the hydroperoxide and the formation of formic acid and formaldehyde were monitored over time using CF3O- chemical ionization mass spectrometry (CIMS) and laser-induced fluorescence (LIF). The loss of HMHP by reaction with OH is measured relative to the loss of 1,2-butanediol [ k1,2-butanediol+OH = (27.0 ± 5.6) × 10-12 cm3 molecule-1s-1]. We find that HMHP reacts with OH at 295 K with a rate coefficient of (7.1 ± 1.5) × 10-12 cm3 molecule-1s-1, with the formic acid to formaldehyde yield in a ratio of 0.88 ± 0.21 and independent of NO concentration (3 × 1010 - 1.5 × 1013 molecules cm-3). We suggest that, exclusively, abstraction of the methyl hydrogen of HMHP results in formic acid, while abstraction of the hydroperoxy hydrogen results in formaldehyde. We further evaluate the relative importance of HMHP sinks and use global simulations from GEOS-Chem to estimate that HMHP oxidation by OH contributes 1.7 Tg yr-1 (1-3%) of global annual formic acid production.

Gas-Phase Reactions of Isoprene and Its Major Oxidation Products.

Isoprene carries approximately half of the flux of non-methane volatile organic carbon emitted to the atmosphere by the biosphere. Accurate representation of its oxidation rate and products is essential for quantifying its influence on the abundance of the hydroxyl radical (OH), nitrogen oxide free radicals (NO x), ozone (O3), and, via the formation of highly oxygenated compounds, aerosol. We present a review of recent laboratory and theoretical studies of the oxidation pathways of isoprene initiated by addition of OH, O3, the nitrate radical (NO3), and the chlorine atom. From this review, a recommendation for a nearly complete gas-phase oxidation mechanism of isoprene and its major products is developed. The mechanism is compiled with the aims of providing an accurate representation of the flow of carbon while allowing quantification of the impact of isoprene emissions on HO x and NO x free radical concentrations and of the yields of products known to be involved in condensed-phase processes. Finally, a simplified (reduced) mechanism is developed for use in chemical transport models that retains the essential chemistry required to accurately simulate isoprene oxidation under conditions where it occurs in the atmosphere-above forested regions remote from large NO x emissions.

Atmospheric autoxidation is increasingly important in urban and suburban North America.

Gas-phase autoxidation-regenerative peroxy radical formation following intramolecular hydrogen shifts-is known to be important in the combustion of organic materials. The relevance of this chemistry in the oxidation of organics in the atmosphere has received less attention due, in part, to the lack of kinetic data at relevant temperatures. Here, we combine computational and experimental approaches to investigate the rate of autoxidation for organic peroxy radicals (RO2) produced in the oxidation of a prototypical atmospheric pollutant, n-hexane. We find that the reaction rate depends critically on the molecular configuration of the RO2 radical undergoing hydrogen transfer (H-shift). RO2 H-shift rate coefficients via transition states involving six- and seven-membered rings (1,5 and 1,6 H-shifts, respectively) of α-OH hydrogens (HOC-H) formed in this system are of order 0.1 s-1 at 296 K, while the 1,4 H-shift is calculated to be orders of magnitude slower. Consistent with H-shift reactions over a substantial energetic barrier, we find that the rate coefficients of these reactions increase rapidly with temperature and exhibit a large, primary, kinetic isotope effect. The observed H-shift rate coefficients are sufficiently fast that, as a result of ongoing NO x emission reductions, autoxidation is now competing with bimolecular chemistry even in the most polluted North American cities, particularly during summer afternoons when NO levels are low and temperatures are elevated.

Isoprene Peroxy Radical Dynamics.

Approximately 500 Tg of 2-methyl-1,3-butadiene (isoprene) is emitted by deciduous trees each year. Isoprene oxidation in the atmosphere is initiated primarily by addition of hydroxyl radicals (OH) to C4 or C1 in a ratio 0.57 ± 0.03 (1σ) to produce two sets of distinct allylic radicals. Oxygen (O2) adds to these allylic radicals either δ (Z or E depending on whether the allylic radical is cis or trans) or ß to the OH group forming six distinct peroxy radical isomers. Due to the enhanced stability of the allylic radical, however, these peroxy radicals lose O2 in competition with bimolecular reactions. In addition, the Z-δ hydroxy peroxy radical isomers undergo unimolecular 1,6 H-shift isomerization. Here, we use isomer-resolved measurements of the reaction products of the peroxy radicals to diagnose this complex chemistry. We find that the ratio of δ to ß hydroxy peroxy radicals depends on their bimolecular lifetime (τbimolecular). At τbimolecular ≈ 0.1 s, a transition occurs from a kinetically to a largely thermodynamically controlled distribution at 297 K. Thus, in nature, where τbimolecular > 10 s, the distribution of isoprene hydroxy peroxy radicals will be controlled primarily by the difference in the relative stability of the peroxy radical isomers. In this regime, ß hydroxy peroxy radical isomers comprise ∼95% of the radical pool, a much higher fraction than in the nascent (kinetic) distribution. Intramolecular 1,6 H-shift isomerization of the Z-δ hydroxy peroxy radical isomers produced from OH addition to C4 is estimated to be ∼4 s-1 at 297 K. While the Z-δ isomer is initially produced in low yield, it is continually reformed via decomposition of the ß hydroxy peroxy radicals. As a result, unimolecular chemistry from this isomer contributes about half of the atmospheric fate of the entire pool of peroxy radicals formed via addition of OH at C4 for typical atmospheric conditions (τbimolecular = 100 s and T = 25 C). In contrast, unimolecular chemistry following OH addition at C1 is slower and less important.