An emergent constraint on the thermal sensitivity of photosynthesis and greenness in the high latitude northern forests.

Despite the general consensus that the warming over the high latitudes northern forests (HLNF) has led to enhanced photosynthetic activity and contributed to the greening trend, isolating the impact of temperature increase on photosynthesis and greenness has been difficult due to the concurring influence of the CO2 fertilization effect. Here, using an ensemble of simulations from biogeochemical models that have contributed to the Trends in Net Land Atmosphere Carbon Exchange project (TRENDY), we identify an emergent relationship between the simulation of the climate-driven temporal changes in both gross primary productivity (GPP) and greenness (Leaf Area Index, LAI) and the model's spatial sensitivity of these quantities to growing-season (GS) temperature. Combined with spatially-resolved observations of LAI and GPP, we estimate that GS-LAI and GS-GPP increase by 17.0 ± 2.4% and 24.0 ± 3.0% per degree of warming, respectively. The observationally-derived sensitivities of LAI and GPP to temperature are about 40% and 71% higher, respectively, than the mean of the ensemble of simulations from TRENDY, primarily due to the model underestimation of the sensitivity of light use efficiency to temperature. We estimate that the regional mean GS-GPP increased 28.2 ± 5.1% between 1983-1986 and 2013-2016, much larger than the 5.8 ± 1.4% increase from the CO2 fertilization effect implied by Wenzel et al. This suggests that warming, not CO2 fertilization, is primarily responsible for the observed dramatic changes in the HLNF biosphere over the last century.

Particle-phase accretion forms dimer esters in pinene secondary organic aerosol.

Secondary organic aerosol (SOA) is ubiquitous in the atmosphere and plays a pivotal role in climate, air quality, and health. The production of low-volatility dimeric compounds through accretion reactions is a key aspect of SOA formation. However, despite extensive study, the structures and thus the formation mechanisms of dimers in SOA remain largely uncharacterized. In this work, we elucidate the structures of several major dimer esters in SOA from ozonolysis of α-pinene and ß-pinene-substantial global SOA sources-through independent synthesis of authentic standards. We show that these dimer esters are formed in the particle phase and propose a mechanism of nucleophilic addition of alcohols to a cyclic acylperoxyhemiacetal. This chemistry likely represents a general pathway to dimeric compounds in ambient SOA.

Methane Emissions from Dairy Operations in California's San Joaquin Valley Evaluated Using Airborne Flux Measurements.

State inventories indicate that dairy operations account for nearly half of California's methane budget. Recent analyses suggest, however, that these emissions may be underestimated, complicating efforts to develop emission reduction strategies. Here, we report estimates of dairy methane emissions in the southern San Joaquin Valley (SJV) of California in June 2021 using airborne flux measurements. We find average dairy methane fluxes of 512 ± 178 mg m-2 h-1 from a region of 300+ dairies near Visalia, CA using a combination of eddy covariance and mass balance-based techniques, corresponding to 118 ± 41 kg dairy-1 h-1. These values estimated during our June campaign are 39 ± 48% larger than annual average estimates from the recently developed VISTA-CA inventory. We observed notable increases in emissions with temperature. Our estimates align well with inventory predictions when parametrizations for the temperature dependence of emissions are applied. Our measurements further demonstrate that the VISTA-CA emission inventory is considerably more accurate than the EPA GHG-I inventory in this region. Source apportionment analyses confirm that dairy operations produce the majority of methane emissions in the southern SJV (∼65%). Fugitive oil and gas (O&G) sources account for the remaining ∼35%. Our results support the accuracy of the process-based models used to develop dairy emission inventories and highlight the need for additional investigation of the meteorological dependence of these emissions.

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.

Elucidating climatic drivers of photosynthesis by tropical forests.

Tropical forests play a pivotal role in regulating the global carbon cycle. However, the response of these forests to changes in absorbed solar energy and water supply under the changing climate is highly uncertain. Three-year (2018-2021) spaceborne high-resolution measurements of solar-induced chlorophyll fluorescence (SIF) from the TROPOspheric Monitoring Instrument (TROPOMI) provide a new opportunity to study the response of gross primary production (GPP) and more broadly tropical forest carbon dynamics to differences in climate. SIF has been shown to be a good proxy for GPP on monthly and regional scales. Combining tropical climate reanalysis records and other contemporary satellite products, we find that on the seasonal timescale, the dependence of GPP on climate variables is highly heterogeneous. Following the principal component analyses and correlation comparisons, two regimes are identified: water limited and energy limited. GPP variations over tropical Africa are more correlated with water-related factors such as vapor pressure deficit (VPD) and soil moisture, while in tropical Southeast Asia, GPP is more correlated with energy-related factors such as photosynthetically active radiation (PAR) and surface temperature. Amazonia is itself heterogeneous: with an energy-limited regime in the north and water-limited regime in the south. The correlations of GPP with climate variables are supported by other observation-based products, such as Orbiting Carbon Observatory-2 (OCO2) SIF and FluxSat GPP. In each tropical continent, the coupling between SIF and VPD increases with the mean VPD. Even on the interannual timescale, the correlation of GPP with VPD is still discernable, but the sensitivity is smaller than the intra-annual correlation. By and large, the dynamic global vegetation models in the TRENDY v8 project do not capture the high GPP seasonal sensitivity to VPD in dry tropics. The complex interactions between carbon and water cycles in the tropics illustrated in this study and the poor representation of this coupling in the current suite of vegetation models suggest that projections of future changes in carbon dynamics based on these models may not be robust.

Unequal exposure to heatwaves in Los Angeles: Impact of uneven green spaces.

Cities worldwide are experiencing record-breaking summer temperatures. Urban environments exacerbate extreme heat, resulting in not only the urban heat island but also intracity variations in heat exposure. Understanding these disparities is crucial to support equitable climate mitigation and adaptation efforts. We found persistent negative correlations between daytime land surface temperature (LST) and median household income across the Los Angeles metropolitan area based on Ecosystem Spaceborne Thermal Radiometer Experiment on Space Station observations from 2018 to 2021. Lower evapotranspiration resulting from the unequal distribution of vegetation cover is a major factor leading to higher LST in low-income neighborhoods. Disparities worsen with higher regional mean surface temperature, with a $10,000 decrease in income leading to ~0.2°C LST increase at 20°C and up to ~0.7°C at 45°C. With more frequent and intense heat waves projected in the future, equitable mitigation measures, such as increasing surface albedo and tree cover in low-income neighborhoods, are necessary to address these disparities.

Hydrocarbon Tracers Suggest Methane Emissions from Fossil Sources Occur Predominately Before Gas Processing and That Petroleum Plays Are a Significant Source.

We use global airborne observations of propane (C3H8) and ethane (C2H6) from the Atmospheric Tomography (ATom) and HIAPER Pole-to-Pole Observations (HIPPO), as well as U.S.-based aircraft and tower observations by NOAA and from the NCAR FRAPPE campaign as tracers for emissions from oil and gas operations. To simulate global mole fraction fields for these gases, we update the default emissions' configuration of C3H8 used by the global chemical transport model, GEOS-Chem v13.0.0, using a scaled C2H6 spatial proxy. With the updated emissions, simulations of both C3H8 and C2H6 using GEOS-Chem are in reasonable agreement with ATom and HIPPO observations, though the updated emission fields underestimate C3H8 accumulation in the arctic wintertime, pointing to additional sources of this gas in the high latitudes (e.g., Europe). Using a Bayesian hierarchical model, we estimate global emissions of C2H6 and C3H8 from fossil fuel production in 2016-2018 to be 13.3 ± 0.7 (95% CI) and 14.7 ± 0.8 (95% CI) Tg/year, respectively. We calculate bottom-up hydrocarbon emission ratios using basin composition measurements weighted by gas production and find their magnitude is higher than expected and is similar to ratios informed by our revised alkane emissions. This suggests that emissions are dominated by pre-processing activities in oil-producing basins.

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.

Societal shifts due to COVID-19 reveal large-scale complexities and feedbacks between atmospheric chemistry and climate change.

The COVID-19 global pandemic and associated government lockdowns dramatically altered human activity, providing a window into how changes in individual behavior, enacted en masse, impact atmospheric composition. The resulting reductions in anthropogenic activity represent an unprecedented event that yields a glimpse into a future where emissions to the atmosphere are reduced. Furthermore, the abrupt reduction in emissions during the lockdown periods led to clearly observable changes in atmospheric composition, which provide direct insight into feedbacks between the Earth system and human activity. While air pollutants and greenhouse gases share many common anthropogenic sources, there is a sharp difference in the response of their atmospheric concentrations to COVID-19 emissions changes, due in large part to their different lifetimes. Here, we discuss several key takeaways from modeling and observational studies. First, despite dramatic declines in mobility and associated vehicular emissions, the atmospheric growth rates of greenhouse gases were not slowed, in part due to decreased ocean uptake of CO2 and a likely increase in CH4 lifetime from reduced NO x emissions. Second, the response of O3 to decreased NO x emissions showed significant spatial and temporal variability, due to differing chemical regimes around the world. Finally, the overall response of atmospheric composition to emissions changes is heavily modulated by factors including carbon-cycle feedbacks to CH4 and CO2, background pollutant levels, the timing and location of emissions changes, and climate feedbacks on air quality, such as wildfires and the ozone climate penalty.

Unimolecular Reactions Following Indoor and Outdoor Limonene Ozonolysis.

Limonene is one of the monoterpenes with the largest biogenic emissions and is also widely used as an additive in cleaning products, leading to significant indoor emissions. Studies have found that the formation of secondary organic aerosols (SOAs) from limonene oxidation has important implications for indoor air quality. Although ozonolysis is considered the major limonene oxidation pathway under most indoor conditions, little is known about the mechanisms for SOA formation from limonene ozonolysis. Here, we calculate the rate coefficients of the possible unimolecular reactions of the first-generation peroxy radicals formed by limonene ozonolysis using a high-level multiconformer transition state theory approach. We find that all of the peroxy radicals formed initially in the ozonolysis of limonene react unimolecularly with rates that are competitive both indoors and outdoors, except under highly polluted conditions. Differences in reactivity between the peroxy radicals from ozonolysis and those formed by OH, NO3, and Cl oxidation are discussed. Finally, we sketch possible oxidation mechanisms for the different peroxy radicals under both indoor and pristine atmospheric conditions and in more polluted environments. In environments with low concentrations of HO2 and NO, efficient autoxidation will lead to the formation of highly oxygenated organic compounds and thus likely aid in the growth of SOA.

Boundary layer versus free tropospheric submicron particle formation: A case study from NASA DC-8 observations in the Asian continental outflow during the KORUS-AQ campaign.

In this study, we contrasted major secondary inorganic species and processes responsible for submicron particle formation (SPF) events in the boundary layer (BL) and free troposphere (FT) over the Korean Peninsula during Korea-United States Air Quality (KORUS-AQ) campaign (May-June, 2016) using aircraft observations. The number concentration of ultrafine particles with diameters between 3 nm and 10 nm (NCN3-10) during the entire KORUS-AQ period reached a peak (7,606 ± 12,003 cm -3) at below 1 km altitude, implying that the particle formation around the Korean Peninsula primarily occurred in the daytime BL. During the BL SPF case (7 May, 2016), the SPF over Seoul metropolitan area was more attributable to oxidation of NO2 rather than SO2-to-sulfate conversion. From the analysis of the relationship between nitrogen oxidation ratio (NOR) and temperature or relative humidity (RH), NOR showed a positive correlation only with temperature. This suggests that homogeneous gas-phase reactions of NO2 with OH or O3 contributed to nitrate formation. From the relationship between NCN3-10 (> 10,000 cm-3) and the NOR (or sulfur oxidation ratio) at Olympic Park in Seoul during the entire KORUS-AQ period, it was regarded that the relative importance of nitrogen oxidation was grown as the NCN3-10 increased. During the FT SPF case (31 May, 2016) over the yellow sea, the SO2-to-sulfate conversion seemed to influence SPF highly. The sulfate/CO ratio had a positive correlation with both the temperature and RH, suggesting that aqueous-phase pathways as well as gas-phase reactions might be attributable to sulfate formation in the FT. In particular, FT SPF event on 31 May was possibly caused by the direct transport of SO2 precursors from the continent above the shallow marine boundary layer under favorable conditions for FT SPF events, such as decreased aerosol surface area and increased solar radiation.

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.

Correcting model biases of CO in East Asia: impact on oxidant distributions during KORUS-AQ.

Global coupled chemistry-climate models underestimate carbon monoxide (CO) in the Northern Hemisphere, exhibiting a pervasive negative bias against measurements peaking in late winter and early spring. While this bias has been commonly attributed to underestimation of direct anthropogenic and biomass burning emissions, chemical production and loss via OH reaction from emissions of anthropogenic and biogenic volatile organic compounds (VOCs) play an important role. Here we investigate the reasons for this underestimation using aircraft measurements taken in May and June 2016 from the Korea-United States Air Quality (KORUS-AQ) experiment in South Korea and the Air Chemistry Research in Asia (ARIAs) in the North China Plain (NCP). For reference, multispectral CO retrievals (V8J) from the Measurements of Pollution in the Troposphere (MOPITT) are jointly assimilated with meteorological observations using an ensemble adjustment Kalman filter (EAKF) within the global Community Atmosphere Model with Chemistry (CAM-Chem) and the Data Assimilation Research Testbed (DART). With regard to KORUS-AQ data, CO is underestimated by 42% in the control run and by 12% with the MOPITT assimilation run. The inversion suggests an underestimation of anthropogenic CO sources in many regions, by up to 80% for northern China, with large increments over the Liaoning Province and the North China Plain (NCP). Yet, an often-overlooked aspect of these inversions is that correcting the underestimation in anthropogenic CO emissions also improves the comparison with observational O3 datasets and observationally constrained box model simulations of OH and HO2. Running a CAM-Chem simulation with the updated emissions of anthropogenic CO reduces the bias by 29% for CO, 18% for ozone, 11% for HO2, and 27% for OH. Longer-lived anthropogenic VOCs whose model errors are correlated with CO are also improved, while short-lived VOCs, including formaldehyde, are difficult to constrain solely by assimilating satellite retrievals of CO. During an anticyclonic episode, better simulation of O3, with an average underestimation of 5.5 ppbv, and a reduction in the bias of surface formaldehyde and oxygenated VOCs can be achieved by separately increasing by a factor of 2 the modeled biogenic emissions for the plant functional types found in Korea. Results also suggest that controlling VOC and CO emissions, in addition to widespread NO x controls, can improve ozone pollution over East Asia.

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.

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.

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.