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Here we present the UCI Fluxtron, a cost-effective multi-enclosure dynamic gas exchange system that provides an adequate level of control of the experimental conditions for investigating biosphere-atmosphere exchange of trace gases. We focus on the hardware and software used to monitor, control, and record the air flows, temperatures, and valve switching, and on the software that processes the collected data to calculate the exchange flux of trace gases. We provide the detailed list of commercial materials used and also the software code developed for the Fluxtron, so that similar dynamic enclosure systems can be quickly adopted by interested researchers. Furthermore, the two software components -Fluxtron Control and Fluxtron Process- work independently of each other, thus being highly adaptable for other experimental designs. Beyond plants, the same experimental setup can be applied to the study of trace gas exchange by animals, microbes, soil, or any materials that can be enclosed in a suitable container.

It has been widely reported that isoprene emissions from the Arctic ecosystem have a strong temperature response. Here we identify sedges (Carex spp. and Eriophorum spp.) as key contributors to this high sensitivity using plant chamber experiments. We observe that sedges exhibit a markedly stronger temperature response compared to that of other isoprene emitters and predictions by the widely accepted isoprene emission model, the Model of Emissions of Gases and Aerosols from Nature (MEGAN). MEGAN is able to reproduce eddy-covariance flux observations at three high-latitude sites by integrating our findings. Furthermore, the omission of the strong temperature responses of Arctic isoprene emitters causes a 20% underestimation of isoprene emissions for the high-latitude regions of the Northern Hemisphere during 2000-2009 in the Community Land Model with the MEGAN scheme. We also find that the existing model had underestimated the long-term trend of isoprene emissions from 1960 to 2009 by 55% for the high-latitude regions.

Four different plant species, sunflower (Helianthus annuus), western redcedar (Thuja plicata), American sweetgum (Liquidambar styraciflua), and red ironbark (Eucalyptus sideroxylon), were enclosed in glass or Teflon chambers, exposed to different temperatures typically ranging from 30 °C to 43 °C, and their terpenoid emission rates were quantified using gas chromatography techniques. The results show that sunflower, western redcedar, and American sweetgum were not significant constitutive monoterpene emitters at 30 °C. Monoterpene emissions from western redcedar and American sweetgum remained negligibly low up to 35 °C–37 °C, however, at higher temperatures, the emissions began to increase at a much more rapid rate than predicted by current emission models. The monoterpene emissions from sunflower, western redcedar, and American sweetgum increased by an average factor of 22, 98, and 5900 for a temperature increase (ΔT) of 13 °C, 13 °C, and 15 °C, respectively, thereby transforming them from negligible into high monoterpene emitters. The observed emission increase was substantially higher than the model-predicted increase of 3.7-fold (ΔT = 13 °C) and 4.5-fold (ΔT = 15 °C). We demonstrate that current emission algorithms cannot accurately model the emission behavior of these plant species at the high temperatures that are characteristic of severe heatwaves. Furthermore, monoterpene emissions from western redcedar and American sweetgum remained elevated for 1–7 days after the heat stress. In contrast to the other three species, red ironbark was a significant constitutive monoterpene emitter (at 30 °C) and its emission response to temperature was close to model predictions. Each of the four species investigated in this study possesses specialized foliar terpene-storing structures, for example, glandular trichomes and oil glands. The strong monoterpene emission induction observed in some of these species may be attributed to heat-induced damage to these storage structures. However, the wall permeability of these structures may vary by species and could limit the magnitude of the heat-induced emission response.

We introduce two new drought stress algorithms designed to simulate isoprene emission with the Model of Emissions of Gases and Aerosols from Nature (MEGAN) model. The two approaches include the representation of the impact of drought on isoprene emission with a simple empirical approach for offline MEGAN applications and a more process-based approach for online MEGAN in Community Land Model (CLM) simulations. The two versions differ in their implementation of leaf-temperature impacts of mild drought. For the online version of MEGAN that is coupled to CLM, the impact of drought on leaf temperature is simulated directly and the calculated leaf temperature is considered for the estimation of isoprene emission. For the offline version, we apply an empirical algorithm derived from whole-canopy flux measurements for simulating the impact of drought ranging from mild to severe stage. In addition, the offline approach adopts the ratio (f PET) of actual evapotranspiration to potential evapotranspiration to quantify the severity of drought instead of using soil moisture. We applied the two algorithms in the CLM-CAM-chem (the Community Atmosphere Model with Chemistry) model to simulate the impact of drought on isoprene emission and found that drought can decrease isoprene emission globally by 11% in 2012. We further compared the formaldehyde (HCHO) vertical column density simulated by CAM-chem to satellite HCHO observations. We found that the proposed drought algorithm can improve the match with the HCHO observations during droughts, but the performance of the drought algorithm is limited by the capacity of the model to capture the severity of drought.

Emissions of biogenic volatile organic compounds (BVOCs) are a crucial component of biosphere-atmosphere interactions. In northern latitudes, climate change is amplified by feedback processes in which BVOCs have a recognized, yet poorly quantified role, mainly due to a lack of measurements and concomitant modeling gaps. Hence, current Earth system models mostly rely on temperature responses measured on vegetation from lower latitudes, rendering their predictions highly uncertain. Here, we show how tundra isoprene emissions respond vigorously to temperature increases, compared to model results. Our unique dataset of direct eddy covariance ecosystem-level isoprene measurements in two contrasting ecosystems exhibited Q10 (the factor by which the emission rate increases with a 10 °C rise in temperature) temperature coefficients of up to 20.8, that is, 3.5 times the Q10 of 5.9 derived from the equivalent model calculations. Crude estimates using the observed temperature responses indicate that tundra vegetation could enhance their isoprene emissions by up to 41% (87%)-that is, 46% (55%) more than estimated by models-with a 2 °C (4 °C) warming. Our results demonstrate that tundra vegetation possesses the potential to substantially boost its isoprene emissions in response to future rising temperatures, at rates that exceed the current Earth system model predictions.

We present foliar biogenic volatile organic compound (BVOC) emission data from 24-h heat-stressed tomato (Solanum lycopersicum) seedlings including speciated monoterpenes and sesquiterpenes and high time-resolution measurements of methyl salicylate and total monoterpenes. The median total monoterpene and total sesquiterpene emission rates at 30C were 18.5 and 0.172 pmol m–2 s–1, respectively, which falls within the negligible emission category of previous studies. However, initial heat exposure (39C or 42C) increased the emissions of approximately half of the targeted compounds beyond what was predicted by current BVOC emission temperature response algorithms. The enhanced emissions were not always sustained for the entire duration of the heat stress and some plants exhibited a delayed monoterpene response, where emissions peaked toward the end of the heat treatment. Methyl salicylate, a known stress marker, responded differently to the heat stress than most of the other compounds. Heat stress increased methyl salicylate emissions in some plants (at least initially), but in others, emissions declined or did not change significantly. There was no significant correlation between the magnitude of gene expression and emission induction of monoterpenes or methyl salicylate. Furthermore, the emitted monoterpenes did not exhibit any apparent light-dependent behavior, which suggests that these monoterpene stress emissions mostly originated from light-independent foliar storage pools and not from increased de novo production. In contrast, methyl salicylate emissions appear to have contributions from both de novo synthesis and stored pools, as they showed both enzyme-controlled (i.e., light-dependent) and light-independent behaviors. Analyses of the foliar essential oils demonstrate that most of the emitted BVOCs were also present in stored pools. The pool sizes were generally large enough to sustain unstressed emission levels for days to months, and even years for some compounds. However, heat-induced emission enhancement can diminish the pool sizes of some BVOCs, which could decrease subsequent emissions.

We present trace gas vertical profiles observed by instruments on the NASA DC-8 and at a ground site during the Korea-US air quality study (KORUS) field campaign in May to June 2016. We focus on the region near the Seoul metropolitan area and its surroundings where both anthropogenic and natural emission sources play an important role in local photochemistry. Integrating ground and airborne observations is the major research goal of many atmospheric chemistry field campaigns. Although airborne platforms typically aim to sample from near surface to the free troposphere, it is difficult to fly very close to the surface especially in environments with complex terrain or a populated area. A detailed analysis integrating ground and airborne observations associated with specific concentration footprints indicates that reactive trace gases are quickly oxidized below an altitude of 700 m. The total OH reactivity profile has a rapid decay in the lower part of troposphere from surface to the lowest altitude (700 m) sampled by the NASA DC-8. The decay rate is close to that of very reactive biogenic volatile organic compounds such as monoterpenes. Therefore, we argue that photochemical processes in the bottom of the boundary layer, below the typical altitude of aircraft sampling, should be thoroughly investigated to properly assess ozone and secondary aerosol formation.

Floral scent often intensifies during periods of pollinator activity, but the degree of this synchrony may vary among scent compounds depending on their function. Related plant species with the same pollinator may exhibit similar timing and composition of floral scent. We compared timing and composition of floral volatiles for two endemic Hawaiian plant species, Schiedea kaalae and S. hookeri (Caryophyllaceae). For S. kaalae, we also compared the daily timing of emission of floral volatiles to evening visits of their shared pollinator, an endemic Hawaiian moth (Pseudoschrankia brevipalpis; Erebidae). The identity and amount of floral volatiles were measured in the greenhouse during day and evening periods with dynamic headspace sampling and GC-MS (gas chromatography - mass spectrometry). The timing of emissions (daily rise, peak, and fall) was measured by sampling continuously for multiple days in a growth chamber with PTR-MS (proton transfer reaction mass spectrometry). Nearly all volatiles detected underwent strong daily cycles in emission. Timings of floral volatile emissions were similar for S. kaalae and S. hookeri, as expected for two species sharing the same pollinator. For S. kaalae, many volatiles known to attract moths, including several linalool oxides and 2-phenylacetaldehyde, peaked within 2 h of the peak visitation time of the moth which pollinates both species. Floral volatiles of both species that peaked in the evening were also emitted several hours before and after the brief window of pollinator activity. Few volatiles followed a daytime emission pattern, consistent with increased apparency to visitors only at night. The scent blends of the two species differed in their major components and were most distinct from each other in the evening. The qualitative difference in evening scent composition between the two Schiedea species may reflect their distinct evolutionary history and may indicate that the moth species uses several different floral cues to locate rewards.

Biogenic volatile organic compounds (BVOCs) are important drivers of atmospheric chemical composition and accurate model simulations require characterization of the emissions associated with specific vegetation types which is typically determined using enclosure measurements. Static enclosure techniques were used for past BVOC emission measurement studies, especially in the 1960s–1980s, but are no longer widely used because of concerns that the resulting emission rates are not representative. The main advantages of the static approach are the capability for rapid measurements and a lower detection limit that enables the use of less sensitive analytical techniques. We evaluate a version of the static approach which we call the semi-static approach. In order to evaluate the performance of the semi-static approach for BVOCs emission measurements, multiple replicate measurements for different plants were conducted in a laboratory growth chamber using both semi-static and dynamic enclosure techniques. Variability of replicate measurements was calculated and the results from the two techniques were compared. The semi-static technique provided consistent measurements for isoprene but not for α-pinene, β-pinene and other compounds that are stored in leaves. The measured isoprene emission factors were much higher than dynamic measurements. There were a large number of compounds to be detected by dynamic technique that could not be detected by the semi-static technique. But the semi-static technique could still provide qualitative information on categorization of non, low and high emitters for some compounds.

Reports on the composition of ultrafine particles (<100 nm in diameter) in the Amazon are scarce, due in part to the fact that new-particle formation has rarely been observed near ground level. Ultrafine particles near the surface have nevertheless been observed, leaving open questions regarding the sources and chemistry of their formation and growth, particularly as these vary across seasons. Here, we present measurements of the composition of ultrafine particles collected in the Tapajós National Forest (2.857° S, 54.959° W) during three different seasonal periods: 10–30 September 2016 (SEP), 18 November–23 December 2016 (DEC), and 22 May–21 June 2017 (JUN). Size-selected (5–70 nm) particles were collected daily (for 22 h each day) using an offline sampler. Samples collected during the three time periods were compiled and analyzed using liquid chromatography coupled with Orbitrap high-resolution mass spectrometry. Our findings suggest a sustained influence of isoprene organosulfate chemistry on ultrafine particles from the different periods. We present chemical evidence that indicates that biological-spore fragmentation impacted ultrafine-particle composition during the late wet season (JUN), while chemical markers for biomass burning and secondary chemistry peaked during the dry season (SEP and DEC). Higher oxidation states and degrees of unsaturation were observed for organics in the dry season (SEP and DEC), suggesting greater extents of aerosol aging. Finally, applying a volatility parameterization to the observed compounds suggests that organic sulfur species are likely key drivers of new-particle growth in the region due to their low volatility compared to other species. [ABSTRACT FROM AUTHOR]

BTEX (benzene, toluene, ethylbenzene, and m -xylene, p -xylene, and o -xylene) are significant urban air pollutants. This study examines BTEX variability across 7 European countries using data from 22 monitoring sites in different urban settings (urban background, traffic, industry, and suburban background). Results indicate that the relative abundance of BTEX in urban areas follows the order toluene > benzene > m,p -xylene > o -xylene > ethylbenzene, with median mixing ratios of 266 ± 152, 163 ± 74, 129 ± 88, 53 ± 35, and 45 ± 27 ppt during the years 2017–2022, respectively. Seasonal trends show benzene had similar median concentrations across urban background, traffic, and industrial sites, indicating mixed sources. Toluene levels were highest in traffic and industrial areas, highlighting road traffic and industrial emissions. Ethylbenzene and xylenes showed equivalent levels in traffic and industrial areas but were lower in urban backgrounds. Peak BTEX levels occurred during morning and evening rush hours, linked to traffic, heating, and atmospheric stagnation. B/T ratios ranged from 0.29 ± 0.11 to 1.35 ± 0.95, and X/E ratios ranged from 1.75 ± 0.91 to 3.68 ± 0.30, indicating primary pollution from local traffic, followed by solvents, coatings, and biomass burning. Lifetime cancer risk from BTEX exposure was below the definite risk threshold (10−4) but above the permissible risk level (10−6), suggesting moderate risk from benzene and ethylbenzene, particularly in traffic and industrial areas. Additionally, the health index of BTEX at monitoring sites was generally lower than the threshold limit value, suggesting a low non-carcinogenic risk overall. This study offers essential insights into BTEX pollution in urban European environments. [ABSTRACT FROM AUTHOR]

Nitryl chloride (ClNO2) is a radical reservoir species that releases chlorine radicals upon photolysis. An integrated analysis of the impact of ClNO2 on regional photochemistry in the Seoul metropolitan area (SMA) during the Korea-United States Air Quality Study (KORUS-AQ) 2016 field campaign is presented. Comprehensive multiplatform observations were conducted aboard the NASA DC-8 and at two ground sites (Olympic Park, OP; Taehwa Research Forest, TRF), representing an urbanized area and a forested suburban region, respectively. Positive correlations between daytime Cl2 and ClNO2 were observed at both sites, the slope of which was dependent on O3 levels. The possible mechanisms are explored through box model simulations constrained with observations. The overall diurnal variations in ClNO2 at both sites appeared similar but the nighttime variations were systematically different. For about half of the observation days at the OP site the level of ClNO2 increased at sunset but rapidly decreased at around midnight. On the other hand, high levels were observed throughout the night at the TRF site. Significant levels of ClNO2 were observed at both sites for 4-5 h after sunrise. Airborne observations, box model calculations, and back-trajectory analysis consistently show that these high levels of ClNO2 in the morning are likely from vertical or horizontal transport of air masses from the west. Box model results show that chlorine-radical-initiated chemistry can impact the regional photochemistry by elevating net chemical production rates of ozone by 25% in the morning.

Abstract. Nitryl chloride (ClNO2) is a radical reservoir species that releases chlorine radicals upon photolysis. An integrated analysis of the impact of ClNO2 on regional photochemistry in the Seoul Metropolitan Area (SMA) during the Korean-United States-Air Quality (KORUS-AQ) 2016 field campaign is presented. Comprehensive multiplatform observations were conducted aboard the NASA DC-8 and at two ground sites (Olympic Park, OP; Taehwa Research Forest, TRF), representing an urbanized area and a forested region downwind, respectively. The overall diurnal variations of ClNO2 in both sites appeared similar but the night time variation were systematically different. For about half of the observation days at the OP site the level of ClNO2 increased at sunset but rapidly decreased at around midnight. On the other hand, high levels were sustained throughout the night at the TRF site. Significant levels of ClNO2 were sustained at both sites for 4–5 hours after sunrise. Airborne observations, box model calculations, and back trajectory analysis consistently show that this high levels of ClNO2 in the morning is likely due to the transport of air masses within the boundary layer. Box model results show that chlorine radical initiated chemistry can impact the regional photochemistry by elevating net ozone production rate up to ~ 25 % in the morning.

Biogenic isoprene emissions play a very important role in atmospheric chemistry. These emissions are strongly dependent on various environmental conditions, such as temperature, solar radiation, plant water stress, ambient ozone and CO2 concentrations, and soil moisture. Current biogenic emission models (i.e., Model of Emissions of Gases and Aerosols from Nature, MEGAN) can simulate emission responses to some of the major driving variables, such as short-term variations in temperature and solar radiation, but the other factors are either missing or poorly represented. In this paper, we propose a new modeling approach that considers the physiological effects of drought stress on plant photosynthesis and isoprene emissions for use in the MEGAN3 biogenic emission model. We test the MEGAN3 approach by integrating the algorithm into the existing MEGAN2.1 biogenic emission model framework embedded into the global Community Land Model of the Community Earth System Model (CLM4.5/CESM1.2). Single-point simulations are compared against available field measurements at the Missouri Ozarks AmeriFlux (MOFLUX) field site. The modeling results show that the MEGAN3 approach of using of a photosynthesis parameter (Vcmax) and soil wetness factor (βt) to determine the drought activity factor leads to better simulated isoprene emissions in non-drought and drought periods. The global simulation with the MEGAN3 approach predicts a 17% reduction in global annual isoprene emissions, in comparison to the value predicted using the default CLM4.5/MEGAN2.1 without any drought effect. This reduction leads to changes in surface ozone and oxidants in the areas where the reduction of isoprene emissions is observed. Based on the results presented in this study, we conclude that it is important to simulate the drought-induced response of biogenic isoprene emission accurately in the coupled Earth System model.

Nitrogen oxides (NO x ) emitted from human activities are believed to regulate the atmospheric oxidation capacity of the troposphere. However, observational evidence is limited for the low-to-median NO x concentrations prevalent outside of polluted regions. Directly measuring oxidation capacity, represented primarily by hydroxyl radicals (OH), is challenging, and the span in NO x concentrations at a single observation site is often not wide. Concentrations of isoprene and its photo-oxidation products were used to infer the equivalent noontime OH concentrations. The fetch at an observation site in central Amazonia experienced varied contributions from background regional air, urban pollution, and biomass burning. The afternoon concentrations of reactive nitrogen oxides (NO y ), indicative of NO x exposure during the preceding few hours, spanned from 0.3 to 3.5 parts per billion. Accompanying the increase of NO y concentration, the inferred equivalent noontime OH concentrations increased by at least 250% from 0.6 × 106 to 1.6 × 106 cm-3. The conclusion is that, compared to background conditions of low NO x concentrations over the Amazon forest, pollution increased NO x concentrations and amplified OH concentrations, indicating the susceptibility of the atmospheric oxidation capacity over the forest to anthropogenic influence and reinforcing the important role of NO x in sustaining OH concentrations.

We present the ambient ozone and relevant observed trace gas dataset in Seoul, South Korea, during the Megacity Air Pollution Studies (MAPS)-Seoul field campaign from May to June of 2015 (MAPS-Seoul 2015). We observed two distinctive periods, one with higher and the other with lower daytime ozone levels despite mostly clear conditions for both periods. The importance of peroxy radical contributions to excess ozone production is illustrated by the substantial differences in the Leighton constant (Φ) for the two periods. Moreover, higher levels of hydroxyl radical (OH) reactivity (s–1) were observed during the high ozone episode compared to the low ozone episode by as much as ~5 s–1. The contributions of nitrogen oxides (NOx) to OH reactivity become less important than those of volatile organic compounds (VOCs) during the high ozone episode, which suggests the NOx saturated ozone production regime. It was also notable that the biogenic VOC isoprene consistently contributed the most to OH reactivity from among the observed VOCs during the afternoon throughout the whole field campaign. Finally, we ran multiple box model scenarios to evaluate the ozone production rates of three different air mixtures: a high ozone mixture, a low ozone mixture, and a simulation of the regional air quality. The results indicate that the total OH reactivity levels and the relative contributions of VOCs to NOx play critical roles in ozone production rates. The simulated air quality mixture results in lower OH reactivity, causing lower ozone production rates than those calculated for the high ozone mixture, which clearly indicates the need for further improvements in the regional model to accurately simulate ozone precursors in the region. The results of this study suggest that a comprehensive trace gas dataset combined with observations of the OH reactivity enables us to properly diagnose the photochemistry behind ozone pollution, leading to effective ozone abatement policies.

Oxidation flow reactors (OFRs) allow the concentration of a given atmospheric oxidant to be increased beyond ambient levels in order to study secondary organic aerosol (SOA) formation and aging over varying periods of equivalent aging by that oxidant. Previous studies have used these reactors to determine the bulk OA mass and chemical evolution. To our knowledge, no OFR study has focused on the interpretation of the evolving aerosol size distributions. In this study, we use size-distribution measurements of the OFR and an aerosol microphysics model to learn about size-dependent processes in the OFR. Specifically, we use OFR exposures between 0.09 and 0.9 equivalent days of OH aging from the 2011 BEACHON-RoMBAS and GoAmazon2014/5 field campaigns. We use simulations in the TOMAS (TwO-Moment Aerosol Sectional) microphysics box model to constrain the following parameters in the OFR: (1) the rate constant of gas-phase functionalization reactions of organic compounds with OH, (2) the rate constant of gas-phase fragmentation reactions of organic compounds with OH, (3) the reactive uptake coefficient for heterogeneous fragmentation reactions with OH, (4) the nucleation rate constants for three different nucleation schemes, and (5) an effective accommodation coefficient that accounts for possible particle diffusion limitations of particles larger than 60nm in diameter. We find the best model-to-measurement agreement when the accommodation coefficient of the larger particles (Dp>60nm) was 0.1 or lower (with an accommodation coefficient of 1 for smaller particles), which suggests a diffusion limitation in the larger particles. When using these low accommodation-coefficient values, the model agrees with measurements when using a published H2SO4-organics nucleation mechanism and previously published values of rate constants for gas-phase oxidation reactions. Further, gas-phase fragmentation was found to have a significant impact upon the size distribution, and including fragmentation was necessary for accurately simulating the distributions in the OFR. The model was insensitive to the value of the reactive uptake coefficient on these aging timescales. Monoterpenes and isoprene could explain 24%-95% of the observed change in total volume of aerosol in the OFR, with ambient semivolatile and intermediate-volatility organic compounds (S/IVOCs) appearing to explain the remainder of the change in total volume. These results provide support to the mass-based findings of previous OFR studies, give insight to important size-distribution dynamics in the OFR, and enable the design of future OFR studies focused on new particle formation and/or microphysical processes.

Isoprene dominates global non-methane volatile organic compound emissions, and impacts tropospheric chemistry by influencing oxidants and aerosols. Isoprene emission rates vary over several orders of magnitude for different plants, and characterizing this immense biological chemodiversity is a challenge for estimating isoprene emission from tropical forests. Here we present the isoprene emission estimates from aircraft eddy covariance measurements over the Amazonian forest. We report isoprene emission rates that are three times higher than satellite top-down estimates and 35% higher than model predictions. The results reveal strong correlations between observed isoprene emission rates and terrain elevations, which are confirmed by similar correlations between satellite-derived isoprene emissions and terrain elevations. We propose that the elevational gradient in the Amazonian forest isoprene emission capacity is determined by plant species distributions and can substantially explain isoprene emission variability in tropical forests, and use a model to demonstrate the resulting impacts on regional air quality.

The Amazon Basin plays key role in atmospheric chemistry, biodiversity and climate change. In this study we applied nanoelectrospray (nanoESI) ultra-high-resolution mass spectrometry (UHRMS) for the analysis of the organic fraction of PM2.5 aerosol samples collected during dry and wet seasons at a site in central Amazonia receiving background air masses, biomass burning and urban pollution. Comprehensive mass spectral data evaluation methods (e.g. Kendrick mass defect, Van Krevelen diagrams, carbon oxidation state and aromaticity equivalent) were used to identify compound classes and mass distributions of the detected species. Nitrogen-and/or sulfur-containing organic species contributed up to 60% of the total identified number of formulae. A large number of molecular formulae in organic aerosol (OA) were attributed to later-generation nitrogen-and sulfur-containing oxidation products, suggesting that OA composition is affected by biomass burning and other, potentially anthropogenic, sources. Isoprene-derived organosulfate (IEPOX-OS) was found to be the most dominant ion in most of the analysed samples and strongly followed the concentration trends of the gas-phase anthropogenic tracers confirming its mixed anthropogenic-biogenic origin. The presence of oxidised aromatic and nitro-aromatic compounds in the samples suggested a strong influence from biomass burning especially during the dry period. Aerosol samples from the dry period and under enhanced biomass burning conditions contained a large number of molecules with high carbon oxidation state and an increased number of aromatic compounds compared to that from the wet period. The results of this work demonstrate that the studied site is influenced not only by biogenic emissions from the forest but also by biomass burning and potentially other anthropogenic emissions from the neighbouring urban environments.

South Korea has recently achieved developed country status with the second largest megacity in the world, the Seoul Metropolitan Area (SMA). This study provides insights into future changes in air quality for rapidly emerging megacities in the East Asian region. We present total OH reactivity observations in the SMA conducted at an urban Seoul site (May-June, 2015) and a suburban forest site (Sep, 2015). The total OH reactivity in an urban site during the daytime was observed at similar levels (∼15 s(-1)) to those previously reported from other East Asian megacity studies. Trace gas observations indicate that OH reactivity is largely accounted for by NOX (∼50%) followed by volatile organic compounds (VOCs) (∼35%). Isoprene accounts for a substantial fraction of OH reactivity among the comprehensive VOC observational dataset (25-47%). In general, observed total OH reactivity can be accounted for by the observed trace gas dataset. However, observed total OH reactivity in the suburban forest area cannot be largely accounted for (∼70%) by the trace gas measurements. The importance of biogenic VOC (BVOCs) emissions and oxidations used to evaluate the impacts of East Asian megacity outflows for the regional air quality and climate contexts are highlighted in this study.

Isoprene photooxidation is a major driver of atmospheric chemistry over forested regions. Isoprene reacts with hydroxyl radicals (OH) and molecular oxygen to produce isoprene peroxy radicals (ISOPOO). These radicals can react with hydroperoxyl radicals (HO2) to dominantly produce hydroxyhydroperoxides (ISOPOOH). They can also react with nitric oxide (NO) to largely produce methyl vinyl ketone (MVK) and methacrolein (MACR). Unimolecular isomerization and bimolecular reactions with organic peroxy radicals are also possible. There is uncertainty about the relative importance of each of these pathways in the atmosphere and possible changes because of anthropogenic pollution. Herein, measurements of ISOPOOH and MVK + MACR concentrations are reported over the central region of the Amazon basin during the wet season. The research site, downwind of an urban region, intercepted both background and polluted air masses during the GoAmazon2014/5 Experiment. Under background conditions, the confidence interval for the ratio of the ISOPOOH concentration to that of MVK + MACR spanned 0.4-0.6. This result implies a ratio of the reaction rate of ISOPOO with HO2 to that with NO of approximately unity. A value of unity is significantly smaller than simulated at present by global chemical transport models for this important, nominally low-NO, forested region of Earth. Under polluted conditions, when the concentrations of reactive nitrogen compounds were high (>1 ppb), ISOPOOH concentrations dropped below the instrumental detection limit (

Speciated particle-phase organic nitrates (pONs) were quantified using online chemical ionization MS during June and July of 2013 in rural Alabama as part of the Southern Oxidant and Aerosol Study. A large fraction of pONs is highly functionalized, possessing between six and eight oxygen atoms within each carbon number group, and is not the common first generation alkyl nitrates previously reported. Using calibrations for isoprene hydroxynitrates and the measured molecular compositions, we estimate that pONs account for 3% and 8% of total submicrometer organic aerosol mass, on average, during the day and night, respectively. Each of the isoprene- and monoterpenes-derived groups exhibited a strong diel trend consistent with the emission patterns of likely biogenic hydrocarbon precursors. An observationally constrained diel box model can replicate the observed pON assuming that pONs (i) are produced in the gas phase and rapidly establish gas-particle equilibrium and (ii) have a short particle-phase lifetime (∼2-4 h). Such dynamic behavior has significant implications for the production and phase partitioning of pONs, organic aerosol mass, and reactive nitrogen speciation in a forested environment.

Speciated particle-phase organic nitrates (pONs) were quantified using online chemical ionization MS during June and July of 2013 in rural Alabama as part of the Southern Oxidant and Aerosol Study. A large fraction of pONs is highly functionalized, possessing between six and eight oxygen atoms within each carbon number group, and is not the common first generation alkyl nitrates previously reported. Using calibrations for isoprene hydroxynitrates and the measured molecular compositions, we estimate that pONs account for 3% and 8% of total submicrometer organic aerosol mass, on average, during the day and night, respectively. Each of the isoprene- and monoterpenes-derived groups exhibited a strong diel trend consistent with the emission patterns of likely biogenic hydrocarbon precursors. An observationally constrained diel box model can replicate the observed pON assuming that pONs (i) are produced in the gas phase and rapidly establish gas-particle equilibrium and (ii) have a short particle-phase lifetime (∼2-4 h). Such dynamic behavior has significant implications for the production and phase partitioning of pONs, organic aerosol mass, and reactive nitrogen speciation in a forested environment.

The San Joaquin Valley (SJV) in California experiences persistent air-quality problems associated with elevated particulate matter (PM) concentrations due to anthropogenic emissions, topography, and meteorological conditions. Thus it is important to unravel the various sources and processes that affect the physicochemical properties of PM in order to better inform pollution abatement strategies and improve parameterizations in air-quality models. During January and February 2013, a ground supersite was installed at the Fresno-Garland California Air Resources Board (CARB) monitoring station, where comprehensive, real-time measurements of PM and trace gases were performed using instruments including an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and an Ionicon proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS) as part of the NASA Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality (DISCOVER-AQ) campaign. The average submicron aerosol (PM1) concentration was 31.0 μg m-3 and the total mass was dominated by organic aerosols (OA, 55%), followed by ammonium nitrate (35%). High PM pollution events were commonly associated with elevated OA concentrations, mostly from primary sources. Organic aerosols had average atomic oxygen-to-carbon (O / C), hydrogen-to-carbon (H / C), and nitrogen-to-carbon (N / C) ratios of 0.42, 1.70, and 0.017, respectively. Six distinct sources of organic aerosol were identified from positive matrix factorization (PMF) analysis of the AMS data: hydrocarbon-like OA (HOA; 9% of total OA, O / C = 0.09) associated with local traffic, cooking OA (COA; 18% of total OA, O / C = 0.19) associated with food cooking activities, two biomass burning OA (BBOA1: 13% of total OA, O / C = 0.33; BBOA2: 20% of total OA, O / C = 0.60) most likely associated with residential space heating from wood combustion, and semivolatile oxygenated OA (SV-OOA; 16% of total OA, O / C = 0.63) and low-volatility oxygenated OA (LV-OOA; 24% of total OA, O / C = 0.90) formed via chemical reactions in the atmosphere. Large differences in aerosol chemistry at Fresno were observed between the current campaign (winter 2013) and a previous campaign in winter 2010, most notably that PM1 concentrations were nearly 3 times higher in 2013 than in 2010. These variations were attributed to differences in the meteorological conditions, which influenced primary emissions and secondary aerosol formation. In particular, COA and BBOA concentrations were greater in 2013 than 2010, where colder temperatures in 2013 likely resulted in increased biomass burning activities. The influence from a nighttime formed residual layer that mixed down in the morning was found to be much more intense in 2013 than 2010, leading to sharp increases in ground-level concentrations of secondary aerosol species including nitrate, sulfate, and OOA, in the morning between 08:00 and 12:00 PST. This is an indication that nighttime chemical reactions may have played a more important role in 2013. As solar radiation was stronger in 2013 the higher nitrate and OOA concentrations in 2013 could also be partly due to greater photochemical production of secondary aerosol species. The greater solar radiation and larger range in temperature in 2013 also likely led to both SV-OOA and LV-OOA being observed in 2013 whereas only a single OOA factor was identified in 2010.

Isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA) can contribute substantially to organic aerosol (OA) concentrations in forested areas under low NO conditions, hence significantly influencing the regional and global OA budgets, accounting, for example, for 16-36% of the submicron OA in the southeastern United States (SE US) summer. Particle evaporation measurements from a thermodenuder show that the volatility of ambient IEPOX-SOA is lower than that of bulk OA and also much lower than that of known monomer IEPOX-SOA tracer species, indicating that IEPOX-SOA likely exists mostly as oligomers in the aerosol phase. The OH aging process of ambient IEPOX-SOA was investigated with an oxidation flow reactor (OFR). New IEPOX-SOA formation in the reactor was negligible, as the OFR does not accelerate processes such as aerosol uptake and reactions that do not scale with OH. Simulation results indicate that adding ∼ 100μgm-3 of pure H2SO4 to the ambient air allows IEPOX-SOA to be efficiently formed in the reactor. The heterogeneous reaction rate coefficient of ambient IEPOX-SOA with OH radical (kOH) was estimated as 4.0±2.0 × 10-13cm3molec-1s-1, which is equivalent to more than a 2-week lifetime. A similar kOH was found for measurements of OH oxidation of ambient Amazon forest air in an OFR. At higher OH exposures in the reactor (> 1 × 1012molec cm-3s), the mass loss of IEPOX-SOA due to heterogeneous reaction was mainly due to revolatilization of fragmented reaction products. We report, for the first time, OH reactive uptake coefficients (γOH = 0.59±0.33 in SE US and γOH = 0.68±0.38 in Amazon) for SOA under ambient conditions. A relative humidity dependence of kOH and γOH was observed, consistent with surface-area-limited OH uptake. No decrease of kOH was observed as OH concentrations increased. These observations of physicochemical properties of IEPOX-SOA can help to constrain OA impact on air quality and climate.

Considerable amounts and varieties of biogenic volatile organic compounds (BVOCs) are exchanged between vegetation and the surrounding air. These BVOCs play key ecological and atmospheric roles that must be adequately represented for accurately modeling the coupled biosphere-atmosphere-climate earth system. One key uncertainty in existing models is the response of BVOC fluxes to an important global change process: drought. We describe the diurnal and seasonal variation in isoprene, monoterpene, and methanol fluxes from a temperate forest ecosystem before, during, and after an extreme 2012 drought event in the Ozark region of the central USA. BVOC fluxes were dominated by isoprene, which attained high emission rates of up to 35.4 mg m(-2)  h(-1) at midday. Methanol fluxes were characterized by net deposition in the morning, changing to a net emission flux through the rest of the daylight hours. Net flux of CO2 reached its seasonal maximum approximately a month earlier than isoprenoid fluxes, which highlights the differential response of photosynthesis and isoprenoid emissions to progressing drought conditions. Nevertheless, both processes were strongly suppressed under extreme drought, although isoprene fluxes remained relatively high compared to reported fluxes from other ecosystems. Methanol exchange was less affected by drought throughout the season, confirming the complex processes driving biogenic methanol fluxes. The fraction of daytime (7-17 h) assimilated carbon released back to the atmosphere combining the three BVOCs measured was 2% of gross primary productivity (GPP) and 4.9% of net ecosystem exchange (NEE) on average for our whole measurement campaign, while exceeding 5% of GPP and 10% of NEE just before the strongest drought phase. The meganv2.1 model correctly predicted diurnal variations in fluxes driven mainly by light and temperature, although further research is needed to address model BVOC fluxes during drought events.

Particle Investigations at a Northern Ozarks Tower: NOx, Oxidant, Isoprene Research (PINOT NOIR) were conducted in a Missouri forest dominated by isoprene emissions from May to October 2012. This study presents results of new particle formation (NPF) and the growth of new particles to cloud condensation nuclei (CCN)-active sizes (∼100 nm) observed during this field campaign. The measured sub-5 nm particles were up to ∼20,000 cm-3 during a typical NPF event. Nucleation rates J1 were relatively high (11.0 ± 10.6 cm-3 s-1), and one order of magnitude higher than formation rates of 5 nm particles (J5). Sub-5 nm particle formation events were observed during 64% of measurement days, with a high preference in biogenic volatile organic compounds (BVOCs)- and SO2-poor northwesterly (90%) air masses than in BVOCs-rich southerly air masses (13%). About 80% of sub-5 nm particle events led to the further growth. While high temperatures and high aerosol loadings in the southerly air masses were not favorable for nucleation, high BVOCs in the southerly air masses facilitated the growth of new particles to CCN-active sizes. In overall, 0.4-9.4% of the sub-5 nm particles grew to CCN-active sizes within each single NPF event. During a regional NPF event period that took place consecutively over several days, concentrations of CCN size particles increased by a factor of 4.7 in average. This enhanced production of CCN particles from new particles was commonly observed during all 13 regional NPF events during the campaign period.