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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.

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.

Semivolatile oxygenated organic compounds (SV-OVOCs) are important atmospheric species, in particular for the production and chemistry of atmospheric particulate matter and related impacts on air quality and climate. In this study, SV-OVOCs were collected in the horizontal plane of the roughness layer over the tropical forest in the central Amazon during the wet season of 2018. A sampler mounted to a coptertype, hovering unmanned aerial vehicle was used. Underlying the collection region, a plateau forest transitioned into a slope forest across several hundred meters. The concentrations of pinonic and pinic acids, which are monoterpene oxidation products, had no statistical difference over the two forests. By comparison, across the study period, differences in the concentration of 2-methyltetrols, which are products of isoprene oxidation, ranged from _70% to +480% over the two forests. The chemical lifetime of 2-methyltetrols in the atmosphere is sufficiently long that heterogeneity in the isoprene emission rate from the two forests followed by atmospheric oxidation does not explain the concentration heterogeneity of 2-methyltetrols. Standing waves and local meteorology also cannot account for the heterogeneity. Of the possibilities considered, the most plausible explanation is the direct emission from the forest of 2-methyltetrols produced through biological processes within the plants. Under this explanation, the rate of direct SV-OVOC emissions should be modulated by forest type and related environmental stressors. Direct emissions of SV-OVOCs should be more broadly considered for constraining and improving models of atmospheric composition, transport, and chemistry over tropical forests.

Dry deposition of ozone is an important sink of ozone in near surface air. When dry deposition occurs through plant stomata, ozone can injure the plant, altering water and carbon cycling and reducing crop yields. Quantifying both stomatal and nonstomatal uptake accurately is relevant for understanding ozone's impact on human health as an air pollutant and on climate as a potent short-lived greenhouse gas and primary control on the removal of several reactive greenhouse gases and air pollutants. Robust ozone dry deposition estimates require knowledge of the relative importance of individual deposition pathways, but spatiotemporal variability in nonstomatal deposition is poorly understood. Here we integrate understanding of ozone deposition processes by synthesizing research from fields such as atmospheric chemistry, ecology, and meteorology. We critically review methods for measurements and modeling, highlighting the empiricism that underpins modeling and thus the interpretation of observations. Our unprecedented synthesis of knowledge on deposition pathways, particularly soil and leaf cuticles, reveals process understanding not yet included in widely-used models. If coordinated with short-term field intensives, laboratory studies, and mechanistic modeling, measurements from a few long-term sites would bridge the molecular to ecosystem scales necessary to establish the relative importance of individual deposition pathways and the extent to which they vary in space and time. Our recommended approaches seek to close knowledge gaps that currently limit quantifying the impact of ozone dry deposition on air quality, ecosystems, and climate.

The emissions, deposition, and chemistry of volatile organic compounds (VOCs) are thought to be influenced by underlying landscape heterogeneity at intermediate horizontal scales of several hundred meters across different forest subtypes within a tropical forest. Quantitative observations and scientific understanding at these scales, however, remain lacking, in large part due to a historical absence of canopy access and suitable observational approaches. Herein, horizontal heterogeneity in VOC concentrations in the near-canopy atmosphere was examined by sampling from an unmanned aerial vehicle (UAV) flown horizontally several hundred meters over the plateau and slope forests in central Amazonia during the morning and early afternoon periods of the wet season of 2018. Unlike terpene concentrations, the isoprene concentrations in the near-canopy atmosphere over the plateau forest were 60% greater than those over the slope forest. A gradient transport model constrained by the data suggests that isoprene emissions differed by 220 to 330% from these forest subtypes, which is in contrast to a 0% difference implemented in most present-day biosphere emissions models (i.e., homogeneous emissions). Quantifying VOC concentrations, emissions, and other processes at intermediate horizontal scales is essential for understanding the ecological and Earth system roles of VOCs and representing them in climate and air quality models.

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.

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.

In this study, we evaluated three conceptually similar ozone gas deposition models. These dry deposition models are frequently used with chemical transport models for calculations over large spatial domains. However, large scale applications of surface-atmosphere exchange of reactive gases require modeling results as accurate as possible to avoid nonlinear accumulation of errors in the spatially representative results. In this paper, model evaluation and comparison against measured data over a coniferous forest at Niwot Ridge AmeriFlux site (Colorado, USA) is carried out. At this site, no previous model calibration took place for any of the models, therefore, we can test and compare their performances under similar conditions as they would perform in a spatial application. Our results show systematic model errors in all the three cases, model performance varies with time of the day, and the errors show a pronounced seasonal pattern as well. The introduction of soil moisture content stress in the model improved model performance regarding the magnitude of fluxes, but the correlation between measured and modeled ozone deposition values remains low. Our results suggest that ozone dry deposition model results should be interpreted carefully in large scale applications, where the accuracy can vary with land cover sometimes are biased.

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.

Alkenes are reactive hydrocarbons that influence local and regional atmospheric chemistry by playing important roles in the photochemical production of tropospheric ozone and in the formation of secondary organic aerosols. The simplest alkene, ethene (ethylene), is a major plant hormone and ripening agent for agricultural commodities. The group of light alkenes (C2-C4) originates from both biogenic and anthropogenic sources, but their biogenic sources are poorly characterized, with limited field-based flux observations. Here we report net ecosystem fluxes of light alkenes and isoprene from a semiarid ponderosa pine forest in the Rocky Mountains of Colorado, USA using the relaxed eddy accumulation (REA) technique during the summer of 2014. Ethene, propene, butene and isoprene emissions have strong diurnal cycles, with median daytime fluxes of 123, 95, 39 and 17 μg mg-2 hg-1, respectively. The fluxes were correlated with each other, followed general ecosystem trends of CO2 and water vapor, and showed similar sunlight and temperature response curves as other biogenic VOCs. The May through October flux, based on measurements and modeling, averaged 62, 52, 24 and 18 μg mg-2 hg-1 for ethene, propene, butene and isoprene, respectively. The light alkenes contribute significantly to the overall biogenic source of reactive hydrocarbons: roughly 18 % of the dominant biogenic VOC, 2-methyl-3-buten-2-ol. The measured ecosystem scale fluxes are 40-80 % larger than estimates used for global emissions models for this type of ecosystem.

Emissions of Biogenic Volatile Organic Compounds (BVOCs) observed during 2007 from an experimental Pinus taeda plantation in Central North Carolina are compared with model estimates from the Model of Emissions of Gases and Aerosols from Nature (MEGAN) version 2.1. Relaxed eddy accumulation (REA) estimates of 2-methyl-3-buten-2-ol (MBO) fluxes are a factor of 3-4 higher than MEGAN estimates. MEGAN monoterpene emission estimates were a factor of approximately two higher than REA flux measurements. MEGAN β-caryophyllene emission estimates were within 60% of growing season REA flux estimates but were several times higher than REA fluxes during cooler, dormant season periods. The sum of other sesquiterpene emissions estimated by MEGAN was several times higher than REA estimates throughout the year. Model components are examined to understand these discrepancies. Measured summertime leaf area index (LAI) (and therefore foliar biomass) is a factor of two higher than assumed in MEGAN for the P. taeda default. Increasing the canopy mean MBO emission factor from 0.35 to 1.0mgm(-2)h(-1) also reduces MEGAN vs. REA flux differences. This increase is within current MBO emission factor uncertainties. The algorithm within MEGAN which adjusts isoprene emission estimates as a function of the temperature and light of the previous 24h seems also to improve the seasonal MEGAN MBO correlation with REA fluxes. Including the effects of the previous 240h, however, seems to degrade temporal model correlation with fluxes. Monoterpene and sesquiterpene composition data from the REA are compared with MEGAN2.1 estimates and also branch enclosure and needle extract data collected at this site. To our knowledge, the flux data presented here are the first reported for MBO and sesquiterpenes from a P. taeda ecosystem.

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 (

The effect of an increase in atmospheric aerosol concentrations on the distribution and radiative properties of Earth's clouds is the most uncertain component of the overall global radiative forcing from preindustrial time. General circulation models (GCMs) are the tool for predicting future climate, but the treatment of aerosols, clouds, and aerosol-cloud radiative effects carries large uncertainties that directly affect GCM predictions, such as climate sensitivity. Predictions are hampered by the large range of scales of interaction between various components that need to be captured. Observation systems (remote sensing, in situ) are increasingly being used to constrain predictions, but significant challenges exist, to some extent because of the large range of scales and the fact that the various measuring systems tend to address different scales. Fine-scale models represent clouds, aerosols, and aerosol-cloud interactions with high fidelity but do not include interactions with the larger scale and are therefore limited from a climatic point of view. We suggest strategies for improving estimates of aerosol-cloud relationships in climate models, for new remote sensing and in situ measurements, and for quantifying and reducing model uncertainty.

The effect of an increase in atmospheric aerosol concentrations on the distribution and radiative properties of Earth's clouds is the most uncertain component of the overall global radiative forcing from preindustrial time. General circulation models (GCMs) are the tool for predicting future climate, but the treatment of aerosols, clouds, and aerosol-cloud radiative effects carries large uncertainties that directly affect GCM predictions, such as climate sensitivity. Predictions are hampered by the large range of scales of interaction between various components that need to be captured. Observation systems (remote sensing, in situ) are increasingly being used to constrain predictions, but significant challenges exist, to some extent because of the large range of scales and the fact that the various measuring systems tend to address different scales. Fine-scale models represent clouds, aerosols, and aerosol-cloud interactions with high fidelity but do not include interactions with the larger scale and are therefore limited from a climatic point of view. We suggest strategies for improving estimates of aerosol-cloud relationships in climate models, for new remote sensing and in situ measurements, and for quantifying and reducing model uncertainty.

The biogenic emissions of isoprene and monoterpenes are one of the main drivers of atmospheric photochemistry, including oxidant and secondary organic aerosol production. In this paper, the emission rates of isoprene and monoterpenes from Australian vegetation are investigated for the first time using the Model of Emissions of Gases and Aerosols from Nature version 2.1 (MEGANv2.1); the CSIRO chemical transport model; and atmospheric observations of isoprene, monoterpenes and isoprene oxidation products (methacrolein and methyl vinyl ketone). Observations from four field campaigns during three different seasons are used, covering urban, coastal suburban and inland forest areas. The observed concentrations of isoprene and monoterpenes were of a broadly similar magnitude, which may indicate that southeast Australia holds an unusual position where neither chemical species dominates. The model results overestimate the observed atmospheric concentrations of isoprene (up to a factor of 6) and underestimate the monoterpene concentrations (up to a factor of 4). This may occur because the emission rates currently used in MEGANv2.1 for Australia are drawn mainly from young eucalypt trees (

The emission, dispersion, and photochemistry of isoprene (C5H8) and related chemical species in the convective boundary layer (CBL) during sunlit daytime were studied over a mixed forest in the southeastern United States by combining ground-based and aircraft observations. Fluxes of isoprene and monoterpenes were quantified at the top of the forest canopy using a high-resolution proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS). Snapshot (2 min sampling duration) vertical profiles of isoprene, methyl vinyl ketone (MVK)Cmethacrolein (MACR), and monoterpenes were collected from aircraft every hour in the CBL (100-1000 m). Both ground-based and airborne collected volatile organic compound (VOC) data are used to constrain the initial conditions of a mixed-layer chemistry model (MXLCH), which is applied to examine the chemical evolution of the O3-NOx-HOx-VOC system and how it is affected by boundary layer dynamics in the CBL. The chemical loss rate of isoprene (1 h) is similar to the turbulent mixing timescale (0.1-0.5 h), which indicates that isoprene concentrations are equally dependent on both photooxidation and boundary layer dynamics. Analysis of a modelderived concentration budget suggests that diurnal evolution of isoprene inside the CBL is mainly controlled by surface emissions and chemical loss; the diurnal evolution of O3 is dominated by entrainment. The NO to HO2 ratio (NO :HO2) is used as an indicator of anthropogenic impact on the CBL chemical composition and spans a wide range (1-163). The fate of hydroxyl-substituted isoprene peroxyl radical (HOC5H8OO q; ISOPOO) is strongly affected by NO:HO2, shifting from NO-dominant to NO-HO2-balanced conditions from early morning to noontime. This chemical regime change is reflected in the diurnal evolution of isoprene hydroxynitrates (ISOPN) and isoprene hydroxy hydroperoxides (ISOPOOH).

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.

Accurately modeled biogenic volatile organic compound (BVOC) emissions are an essential input to atmospheric chemistry simulations of ozone and particle formation. BVOC emission models rely on basal emission factor (BEF) distribution maps based on emission measurements and vegetation land-cover data but these critical input components of the models as well as model simulations lack validation by regional scale measurements. We directly assess isoprene emission-factor distribution databases for BVOC emission models by deriving BEFs from direct airborne eddy covariance (AEC) fluxes (Misztal et al., 2014) scaled to the surface and normalized by the activity factor of the Guenther et al. (2006) algorithm. The available airborne BEF data from approx. 10000km of flight tracks over California were averaged spatially over 48 defined ecological zones called ecoregions. Consistently, BEFs used by three different emission models were averaged over the same ecoregions for quantitative evaluation. Ecoregion-averaged BEFs from the most current land cover used by the Model of Emissions of Gases and Aerosols from Nature (MEGAN) v.2.1 resulted in the best agreement among the tested land covers and agreed within 10% with BEFs inferred from measurement. However, the correlation was sensitive to a few discrepancies (either overestimation or underestimation) in those ecoregions where land-cover BEFs are less accurate or less representative for the flight track. The two other land covers demonstrated similar agreement (within 30% of measurements) for total average BEF across all tested ecoregions but there were a larger number of specific ecoregions that had poor agreement with the observations. Independently, we performed evaluation of the new California Air Resources Board (CARB) hybrid model by directly comparing its simulated isoprene area emissions averaged for the same flight times and flux footprints as actual measured area emissions. The model simulation and the observed surface area emissions agreed on average within 20%. We show that the choice of model land-cover input data has the most critical influence on model-measurement agreement and the uncertainty in meteorology inputs has a lesser impact at scales relevant to regional air quality modeling.

Emissions of methane (CH4) and volatile organic compounds (VOCs) from oil and gas production may have large impacts on air quality and climate change. Methane and VOCs were measured over the Haynesville and Marcellus shale gas plays on board the National Center for Atmospheric Research C-130 and NOAA WP-3D research aircraft in June–July of 2013. We used an eddy covariance technique to measure in situ fluxes of CH4 and benzene from both C-130 flights with high-resolution data (10 Hz) and WP-3D flights with low-resolution data (1 Hz). Correlation (R = 0.65) between CH4 and benzene fluxes was observed when flying over shale gas operations, and the enhancement ratio of fluxes was consistent with the corresponding concentration observations. Fluxes calculated by the eddy covariance method show agreement with a mass balance approach within their combined uncertainties. In general, CH4 fluxes in the shale gas regions follow a lognormal distribution, with some deviations for relatively large fluxes (>10 μgm-2 s-1). Statistical analysis of the fluxes shows that a small number of facilities (i.e., ~10%) are responsible for up to ~40% of the total CH4 emissions in the two regions. We show that the airborne eddy covariance method can also be applied in some circumstances when meteorological conditions do not favor application of the mass balance method. We suggest that the airborne eddy covariance method is a reliable alternative and complementary analysis method to estimate emissions from oil and gas extraction.

Oxidation products of monoterpenes and isoprene have a major influence on the global secondary organic aerosol (SOA) burden and the production of atmospheric nanoparticles and cloud condensation nuclei (CCN). Here, we investigate the formation of extremely low volatility organic compounds (ELVOC) from O3 and OH radical oxidation of several monoterpenes and isoprene in a series of laboratory experiments. We show that ELVOC from all precursors are formed within the first minute after the initial attack of an oxidant. We demonstrate that under atmospherically relevant concentrations, species with an endocyclic double bond efficiently produce ELVOC from ozonolysis, whereas the yields from OH radical-initiated reactions are smaller. If the double bond is exocyclic or the compound itself is acyclic, ozonolysis produces less ELVOC and the role of the OH radical-initiated ELVOC formation is increased. Isoprene oxidation produces marginal quantities of ELVOC regardless of the oxidant. Implementing our laboratory findings into a global modeling framework shows that biogenic SOA formation in general, and ELVOC in particular, play crucial roles in atmospheric CCN production. Monoterpene oxidation products enhance atmospheric new particle formation and growth in most continental regions, thereby increasing CCN concentrations, especially at high values of cloud supersaturation. Isoprene-derived SOA tends to suppress atmospheric new particle formation, yet it assists the growth of sub-CCN-size primary particles to CCN. Taking into account compound specific monoterpene emissions has a moderate effect on the modeled global CCN budget.

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.

Ecosystem fluxes of isoprene emissions were measured during the majority of the 2011 growing season at the University of Missouri's Baskett Wildlife Research and Education Area in central Missouri, USA (38.7° N, 92.2° W). This broadleaf deciduous forest is typical of forests common in the Ozarks region of the central United States. The goal of the isoprene flux measurements was to test our understanding of the controls on isoprene emission from the hourly to the seasonal timescale using a state-of-the-art emission model, MEGAN (Model of Emissions of Gases and Aerosols from Nature). Isoprene emission rates from the forest were very high with a maximum of 53.3mgm-2h-1 (217nmolm-2s-1), which to our knowledge exceeds all other reports of canopy-scale isoprene emission. The fluxes showed a clear dependence on the previous temperature and light regimes, which was successfully captured by the existing algorithms in MEGAN. During a period of drought, MEGAN was unable to reproduce the time-dependent response of isoprene emission to water stress. Overall, the performance of MEGAN was robust and could explain 90% of the observed variance in the measured fluxes, but the response of isoprene emission to drought stress is a major source of uncertainty. © 2013 Elsevier Ltd.

Monoterpene emissions from the dominant understory species Pteridium aquilinum (Bracken fern) in a mixed temperate forest were measured in the field during the summers of 2006, 2007 and 2008. The results showed that Bracken fern emitted monoterpenes at different rates depending if the plants were located in the understory or in open areas. Understory plants emitted monoterpene levels ranging from 0.002 to 13 μgC g dw-1 h -1. Open area plants emitted monoterpene levels ranging from 0.005 to 2.21 μgC g dw-1 h -1. During the summer of 2008 greenhouse studies were performed to complement the field studies. Only 3% of the greenhouse Bracken fern plants emitted substantial amounts of monoterpenes. The average emission, 0.15 μgC g dw-1 h -1 ± 0.9 μgC g dw-1 h -1, was much lower than that observed in the field. The factors controlling monoterpene emissions are not clear, but this study provides evidence of the potential importance of understory vegetation to ecosystem total hydrocarbon emissions and emphasizes the need for longer-term field studies. © 2012 Elsevier Ltd.

Dry deposition velocities (Vd) for peroxyacetyl nitrate (PAN) calculated using two community dry deposition models with different treatments of both stomatal and nonstomatal uptakes were evaluated using measurements of PAN eddy covariance fluxes over a Loblolly pine forest in July 2003. The observed daytime maximum of Vd(PAN) was ∼1.0 cm s-1 on average, while the estimates by the WRF-Chem dry deposition module (WDDM) and the Noah land surface model coupled with a photosynthesis-based Gas Exchange Model (Noah-GEM) were only 0.2 cm s-1 and 0.6 cm s-1, respectively. The observations also showed considerable PAN deposition at night with typical Vd values of 0.2-0.6 cm s-1, while the estimated values from both models were less than 0.1 cm s-1. Noah-GEM modeled more realistic stomatal resistance (Rs) than WDDM, as compared with observations of water vapor exchange fluxes. The poor performance of WDDM for stomatal uptake is mainly due to its lack of dependence on leaf area index. Thermal decomposition was found to be relatively unimportant for measured PAN fluxes as shown by the lack of a relationship between measured total surface conductance and temperature. Thus, a large part of the underprediction in Vd from both models should be caused by the underestimation of nonstomatal uptake, in particular, the cuticle uptake. Sensitivity tests on both stomatal and nonstomatal resistances terms were conducted and some recommendations were provided. Copyright 2012 by the American Geophysical Union.

Hourly measurements of O3, NO, NO2, PAN, HNO3 and NOy concentrations, and eddy-covariance fluxes of O3 and NOy over a temperate deciduous forest from June to November, 2000 were used to evaluate the dry deposition velocities (Vd) estimated by the WRF-Chem dry deposition module (WDDM), which adopted Wesely (1989) scheme for surface resistance (Rc), and the Noah land surface model coupled with a photosynthesis-based Gas-exchange Evapotranspiration Model (Noah-GEM). Noah-GEM produced better Vd(O3) variations due to its more realistically simulated stomatal resistance (Rs) than WDDM. Vd(O3) is very sensitive to the minimum canopy stomatal resistance (Ri) which is specified for each seasonal category assigned in WDDM. Treating Sep-Oct as autumn in WDDM for this deciduous forest site caused a large underprediction of Vd(O3) due to the leafless assumption in 'autumn' seasonal category for which an infinite Ri was assigned. Reducing Ri to a value of 70sm-1, the same as the default value for the summer season category, the modeled and measured Vd(O3) agreed reasonably well. HNO3 was found to dominate the NOy flux during the measurement period; thus the modeled Vd(NOy) was mainly controlled by the aerodynamic and quasi-laminar sublayer resistances (Ra and Rb), both being sensitive to the surface roughness length (z0). Using an appropriate value for z0 (10% of canopy height), WDDM and Noah-GEM agreed well with the observed daytime Vd(NOy). The differences in Vd(HNO3) between WDDM and Noah-GEM were small due to the small differences in the calculated Ra and Rb between the two models; however, the differences in Rc of NO2 and PAN between the two models reached a factor of 1.1-1.5, which in turn caused a factor of 1.1-1.3 differences for Vd. Combining the measured concentrations and modeled Vd, NOx, PAN and HNO3 accounted for 19%, 4%, and 70% of the measured NOy fluxes, respectively. © 2011 Elsevier Ltd.

The Canopy Horizontal Array Turbulence Study (CHATS) experimental study was conducted at a Cilker Orchards's walnut blocks in Dixon, California, before and after leaves emerged, to help improve understanding, simulation capabilities, and modeling of coupled vegetation-atmosphere-land surface interactions. The campaign took place over 12 weeks in the spring of 2007 and was broken into three 4-week phases. Canopy-induced mechanical and thermodynamical vertical variation of turbulence transport characteristics and the linkages between canopy-scale motions and the larger scale planetary boundary layer (PBL) turbulence were measured. The observations focused on measurements characterizing stratification influences on the spatial structure of canopy-induced turbulence, the trace gas source/sink distribution associated with vegetation, and the overall impact of canopy-induced processes on trace gas transport.

A three-part study was conducted to quantify the impact of landscaped vegetation on air quality in a rapidly expanding urban area in the arid southeastern United States. The study combines in situ, plant-level measurements, a spatial emissions inventory, and a photochemical box model. Maximum plant-level basal emission rates were moderate: 18.1 μgC gdw-1 h-1 (Washingtonia spp., palms) for isoprene and 9.56 μgC gdw-1 h-1 (Fraxinus velutina, Arizona ash) for monoterpenes. Sesquiterpene emission rates were low for plant species selected in this study, with no measurement exceeding 0.1 μgC gdw-1 h-1. The high ambient temperatures combined with moderate plant-level emission factors resulted in landscape emission factors that were low (250-640 μgC m-2 h-1) compared to more mesic environments (e.g., the southeastern United States). The Regional Atmospheric Chemistry Mechanism (RACM) was modified to include a new reaction pathway for ocimene. Using measured concentrations of anthropogenic hydrocarbons and other reactive air pollutants (NOx, ozone), the box model employing the RACM mechanism revealed that these modest emissions could have a significant impact on air quality. For a suburban location that was downwind of the urban core (high NOx; low anthropogenic hydrocarbons), biogenic terpenes increased time-dependent ozone production rates by a factor of 50. Our study demonstrates that low-biomass density landscapes emit sufficient biogenic terpenes to have a significant impact on regional air quality. © 2009 Elsevier Ltd. All rights reserved.

Ecosystem level ozone (O₃) fluxes during four different years were examined at a subalpine forest site in the Colorado Rocky Mountains. The local mountain-valley wind system and the proximity of the Denver Metropolitan area leads to high summertime ozone episodes on many afternoons. The timing between these episodes and the ecosystem processes controlling photosynthesis during the growing season plays a critical role in determining the amount of ozone deposition. Light and vapor pressure deficit (VPD) were the most dominant environmental drivers controlling the deposition of O₃ at this site through their influence on stomatal conductance. 81% of the daytime O₃ uptake was predicted to occur through the stomata. Stomatal uptake decreased at high VPD and temperatures leading to an overall decrease in O₃ flux; however, we did observe a non-stomatal conductance for O₃ that increased slightly with temperature before leveling off at higher values. During the growing season, O₃ deposition fluxes were enhanced after midday precipitation events and continued at elevated levels throughout the following night, implying a role for surface wetness. From nighttime data, evidence for both the presence of water films on the needles and non-closure of the plant stomata were observed. During the winter (non-growing) season, the ozone deposition velocity showed a consistent dependency on the latent heat flux. Although the mechanism is unclear, it is apparent that precipitation events play a role here through their influence on latent heat flux.

Biogenic emission of sesquiterpene (SQT) and oxygenated SQT (OSQT) were measured from the dominant vegetation in a desert shrubland and urban area (Las Vegas, Nevada, U.S.A.), and at temperate forest sites at Niwot Ridge, Colorado, U.S.A., Tomakomai, Hokkaido, Japan and Tumbarumba, New South Wales, Australia. Additional measurements were conducted using greenhouse grown plants. The sampling technique, based on solid adsorbent preconcentration and liquid extraction, is suitable for measuring high molecular weight and low volatility compounds such as OSQTs. Fourteen SQT and OSQT (10 SQT and 4 OSQT) were identified in the field experiments. Total emission rates of SQTs and OSQTs varied from the detection limit to 7.6 μgC g-1h-1 (average: 0.74) and 3.7 μgC g-1h-1 (average: 0.31), respectively, and varied with plant species and location. Environmental conditions, including temperature and precipitation, appeared to influence emission rates. Canopy level emission of SQT and OSQT in Tomakomai were also estimated using an emission model. The emission rate of SQT and OSQT ranged from 72 to 710 μgC m-2h-1 (average, 460 in daytime) and from 38 to 370 μgC m-2h-1 (average, 240 in daytime), respectively. Their contributions can be very high in specific regions and seasons. Given the relatively high reactivity and secondary organic aerosol yields of SQTs and OSQTs, it is likely that these compounds influence atmospheric constituents in at least some areas. Copyright © 2009 by The Geochemical Society of Japan.

Until now, micrometeorological measurements of surface/ atmosphere exchange fluxes of submicron aerosol chemical components such as nitrate, sulfate or organics could only be made with gradient techniques. This article describes a novel setup to measure speciated aerosol fluxes by the more direct eddy covariance technique. The system is based on the Aerodyne quadrupole-based Aerosol Mass Spectrometer (Q-AMS), providing a quantitative measurement of aerosol constituents of environmental concern at a time resolution sufficient for eddy-covariance. The Q-AMS control software was modified to maximize duty cycle and statistics and enable fast data acquisition, synchronized with that of an ultrasonic anemometer. The detection limit of the Q-AMS based system for flux measurements ranges from 0.2 for NO3- to 15 ng m-2 s-1 for hydrocarbon-like organic aerosol (HOA), with an estimated precision of around 6 ng m-2 s-1, depending on aerosol loading. At common ambient concentrations the system is capable of resolving deposition velocity values < 1 mm s-1, sufficient for measurements of dry deposition to vegetation. First tests of the system in the urban environment (6 to 20 June 2003) in Boulder, CO, USA, reveal clear diurnal, presumably traffic related, patterns in the emission of HOA and NO3-, with indication of fast production of moderately oxygenated organic aerosol below the measurement height, averaging about 15% of the HOA emission. The average emission factor for HOA was 0.5 g (kg fuel)-1, similar to those found in previous studies. For NO3- an emission factor of 0.09 g (kg fuel)-1 was estimated, implying oxidation of 0.5% of the traffic derived NOx below the measurement height of 45 m. By contrast, SO42- fluxes were on average downward, with deposition velocities that increase with friction velocity from 0.4 to 4 mm s-1. Copyright © American Association for Aerosol Research.

The focus of the studies presented in the preceding companion paper (Part A: Review) and here (Part B: Applications) is on defining representative emission rates from vegetation for determining the roles of biogenic volatile organic compound (BVOC) emissions in atmospheric chemistry and aerosol processes. The review of previously published procedures for identifying and quantifying BVOC emissions has revealed a wide variety of experimental methods used by various researchers. Experimental details become increasingly critical for quantitative emission measurements of low volatility monoterpenes (MT) and sesquiterpenes (SQT). These compounds are prone to be lost inadvertently by uptake to materials in contact with the sample air or by reactions with atmospheric oxidants. These losses become more prominent with higher molecular weight compounds, potentially leading to an underestimation of their emission rates. We present MT and SQT emission rate data from numerous experiments that include 23 deciduous tree species, 14 coniferous tree species, 8 crops, and 2 shrubs. These data indicate total, normalized (30 degrees C) basal emission rates from

Most work on methane (CH(4)) emissions from natural ecosystems has focused on wetlands because they are hotspots of CH(4) production. Less attention has been directed toward upland ecosystems that cover far larger areas, but are assumed to be too dry to emit CH(4). Here we review CH(4) production and emissions in upland ecosystems, with attention to the influence of plant physiology on these processes in forests. Upland ecosystems are normally net sinks for atmospheric CH(4) because rates of CH(4) consumption exceed CH(4) production. Production of CH(4) in upland soils occurs in microsites and may be common in upland forest soils. Some forests switch from being CH(4) sinks to CH(4) sources depending on soil water content. Plant physiology influences CH(4) cycling by modifying the availability of electron donors and acceptors in forest soils. Plants are the ultimate source of organic carbon (electron donor) that microbes process into CH(4). The availability of O(2) (electron acceptor) is sensitive to changes in soil water content, and therefore, to transpiration rates. Recently, abiotic production of CH(4) from aerobic plant tissue was proposed, but has not yet been verified with independent data. If confirmed, this new source is likely to be a minor term in the global CH(4) budget, but important to quantify for purposes of greenhouse gas accounting. A variety of observations suggest that our understanding of CH(4) sources in upland systems is incomplete, particularly in tropical forests which are stronger sources then expected.

Airborne trace gas measurements from Transport and Chemical Evolution over the Pacific (TRACE-P), Pacific Exploratory Mission (PEM)-Tropics B, and Intercontinental Chemical Transport Experiment-North America (INTEX-NA) experiments are analyzed to examine the major source factors contributing to the observed variabilities of oxygenated volatile organic compounds and cyanides. The positive matrix factorization method is applied to coincident measurements of 11 chemicals including CH3OH, CH3COCH3, CH3CHO, C2H2, C2H6, i-C5H12, CO, CH3Cl, and CHBr3. Measurements of HCN and CH3CN are available for TRACE-P and INTEX-NA. We identify major source contributions from the terrestrial biosphere, biomass burning, industry/urban regions, and oceans. Spatial and back trajectory characteristics of these factors are examined. On the basis of TRACE-P and PEM-Tropics B data, we find a factor that explains 80-88% of the CH3OH variability, 20-40% of CH3COCH3, 7-35% of CH3CHO, and 41% of HCN, most likely representing the emissions from terrestrial biosphere. Our analysis suggested that biogenic emissions of HCN may be significant. Cyanogenesis in plants is likely a major emission process for HCN, which was not fully accounted for previously. Larger contributions than previous global estimations to CH3COCH3 and CH3CHO by biomass burning and industry/urban sources likely reflect significant secondary production from volatile organic compound oxidation. No evidence was found for large emissions of CH3COCH3 from the ocean. The oceanic CH3CHO contribution implies large regional variations. Copyright 2007 by the American Geophysical Union.

Measurements of aerosol size distribution, chemical composition, and cloud condensation nuclei (CCN) concentration were performed during the Chemical Emission, Loss, Transformation, and Interactions with Canopies (CELTIC) field program at Duke Forest in North Carolina. A kinetic model of the cloud activation of ambient aerosol in the chamber of the CCN instrument was used to perform an aerosol-CCN closure study. This study advances prior investigations by employing a novel fitting algorithm that was used to integrate scanning mobility particle sizer (SMPS) measurements of aerosol number size distribution and aerosol mass spectrometer (AMS) measurements of the mass size distribution for sulfate, nitrate, ammonium, and organics into a single, coherent description of the ambient aerosol in the size range critical to aerosol activation (around 100-nm diameter). Three lognormal aerosol size modes, each with a unique internally mixed composition, were used as input into the kinetic model. For the two smaller size modes, which control CCN number concentration, organic aerosol mass fractions for the defined cases were between 58% and 77%. This study is also unique in that the water vapor accommodation coefficient was estimated based on comparing the initial timing for CCN activation in the instrument chamber with the activation predicted by the kinetic model. The kinetic model overestimated measured CCN concentrations, especially under polluted conditions. Prior studies have attributed a positive model bias to an incomplete understanding of the aerosol composition, especially the role of organics in the activation process. This study shows that including measured organic mass fractions with an assumed organic aerosol speciation profile (pinic acid, fulvic acid, and levoglucosan) and an assumed organic aerosol solubility of 0.02 kg kg-1 still resulted in a significant model positive bias for polluted case study periods. The slope and y intercept for the CCN predicted versus CCN observed regression was found to be 1.9 and -180 cm-3, respectively. The overprediction generally does not exceed uncertainty limits but is indicative that a bias exists in the measurements or application of model. From this study, uncertainties in the particle number and mass size distributions as the cause for the model bias can be ruled out. The authors are also confident that the model is including the effects of growth kinetics on predicted activated number. However, one cannot rule out uncertainties associated with poorly characterized CCN measurement biases, uncertainties in assumed organic solubility, and uncertainties in aerosol mixing state. Sensitivity simulations suggest that assuming either an insoluble organic fraction or external aerosol mixing were both sufficient to reconcile the model bias. © 2007 American Meteorological Society.

Carbonyl compounds exist in the atmosphere as either gases or aerosols. Some of them are water soluble and known as oxidation products of biogenic and/or anthropogenic hydrocarbons. Five carbonyl compounds, glyoxal (GO), 4-oxopentanal (4-OPA), glycolaldehyde (GA), hydroxyacetone (HA) and methylglyoxal (MG) have been identified in a temporal series of 12 rain samples. The concentrations of the compounds in the samples were high at the beginning of the rain event and decreased with time to relatively low and fairly constant levels, indicating that the compounds were washed out from the atmosphere at the start of the rain event. Possibly, these compounds also existed in the cloud condensation nuclei (CCN). Wet deposition rates of the carbonyl compounds were calculated for nine samples collected during a 20 h period. The deposition rates ranged from 0 (4-OPA) to 1.2×10-1 mg C m-2 h-1 (MG) with the average of 2.9×10-2 mg C m-2 h-1. Production rates of isoprene oxidation products (GA, HA and MG) in the area surrounding the sampling site were estimated with a chemical box model. The deposition rates exceeded the production rates in most samples. This indicates that the rainfall causes a large net flux of the water soluble compounds from the atmosphere to the ground. Insoluble carbonyl compounds such as n-nonanal and n-decanal were expected to be present in the atmosphere, but were not detected in the rain during the sampling period, suggesting that an aerosol containing these insoluble compounds does not effectively act as a CCN. © 2006 Elsevier Ltd. All rights reserved.

This study applies a regional Earth system model (NASA-Unified Weather Research and Forecasting with online chemistry) with updated parameterizations for selected land-air exchange processes and multi-platform observations, to first estimate reactive nitrogen (Nr = oxidized NOy + reduced NHx) emissions from anthropogenic and natural sources, nitrogen dioxide (NO2) column densities and surface concentrations, total and speciated Nr dry or/and wet deposition fluxes during 2018-2023 over the northeastern and Mid-Atlantic US most of which belong to nitrogen oxides-limited or transitional chemical regimes. The estimated multi-year Nr concentrations and deposition fluxes are then compared with and related to ozone (O3), in terms of their spatiotemporal variability and key drivers as well as possible ecosystem impacts. Finally, through three sets of case studies, we identify and discuss about 1) the capability of land data assimilation (DA) to reduce the uncertainty in modeled land surface states at daily-to-interannual timescales, that can propagate into atmospheric chemistry fields; 2) the impacts of irrigation on land surface and atmospheric fields as well as pollutants' ecosystem uptake and impacts; and 3) the impacts of transboundary air pollution during selected extreme events on pollutants' budgets and ecosystem impacts. With the updated model parameterizations and anthropogenic emission inputs, the eastern US surface O3 modeled by this tool persistently agrees better with observations (i.e., with root-mean-square errors staying within 4-7 ppbv for the individual years' May-June-July) than those in literature where model errors often exceed 20 ppbv. Based on model calculations, surface O3 correlates more strongly with early afternoon NO2 columns than formaldehyde columns (r=0.54 and 0.40, respectively). The O3 vegetative uptake overall dropped by ~10% from 2018 to 2023, displaying clearer downward temporal changes than the total Nr deposition due to the declining NOy emission and deposition fluxes competing with the increasing NHx fluxes. It is highlighted that, temporal variability of Nr and O3 concentrations and fluxes on subregional-to-local scales respond to hydrological variability that can be influenced by precipitation and controllable human activities such as irrigation. Deposition processes and biogenic emissions that are highly sensitive to interconnected environmental and plants' physiological conditions, as well as extra-regional sources (e.g., O3-rich stratospheric air and dense wildfire plumes from upwind regions), have been playing increasingly important roles in controlling pollutants' budgets in this area as local emissions go down owing to effective emission regulations and COVID lockdowns. To better inform the design of mitigation and adaptation strategies, it is recommended to continue evaluating and improving the model parameterizations and inputs relevant to these processes in seamlessly coupled multiscale Earth system models using laboratory and field experiments in combination with satellite DA which would in turn benefit remote sensing communities. [ABSTRACT FROM AUTHOR]

This study applies a regional Earth system model (NASA-Unified Weather Research and Forecasting with online chemistry) with updated parameterizations for selected land-air exchange processes and multi-platform observations, to first estimate reactive nitrogen (Nr = oxidized NOy + reduced NHx) emissions from anthropogenic and natural sources, nitrogen dioxide (NO2) column densities and surface concentrations, total and speciated Nr dry or/and wet deposition fluxes during 2018–2023 over the northeastern and Mid-Atlantic US most of which belong to nitrogen oxides-limited or transitional chemical regimes. The estimated multi-year Nr concentrations and deposition fluxes are then compared with and related to ozone (O3), in terms of their spatiotemporal variability and key drivers as well as possible ecosystem impacts. Finally, through three sets of case studies, we identify and discuss about 1) the capability of land data assimilation (DA) to reduce the uncertainty in modeled land surface states at daily-to-interannual timescales, that can propagate into atmospheric chemistry fields; 2) the impacts of irrigation on land surface and atmospheric fields as well as pollutants' ecosystem uptake and impacts; and 3) the impacts of transboundary air pollution during selected extreme events on pollutants' budgets and ecosystem impacts. With the updated model parameterizations and anthropogenic emission inputs, the eastern US surface O3 modeled by this tool persistently agrees better with observations (i.e., with root-mean-square errors staying within 4–7 ppbv for the individual years' May-June-July) than those in literature where model errors often exceed 20 ppbv. Based on model calculations, surface O3 correlates more strongly with early afternoon NO2 columns than formaldehyde columns (r =0.54 and 0.40, respectively). The O3 vegetative uptake overall dropped by ~10 % from 2018 to 2023, displaying clearer downward temporal changes than the total Nr deposition due to the declining NOy emission and deposition fluxes competing with the increasing NHx fluxes. It is highlighted that, temporal variability of Nr and O3 concentrations and fluxes on subregional-to-local scales respond to hydrological variability that can be influenced by precipitation and controllable human activities such as irrigation. Deposition processes and biogenic emissions that are highly sensitive to interconnected environmental and plants' physiological conditions, as well as extra-regional sources (e.g., O3-rich stratospheric air and dense wildfire plumes from upwind regions), have been playing increasingly important roles in controlling pollutants' budgets in this area as local emissions go down owing to effective emission regulations and COVID lockdowns. To better inform the design of mitigation and adaptation strategies, it is recommended to continue evaluating and improving the model parameterizations and inputs relevant to these processes in seamlessly coupled multiscale Earth system models using laboratory and field experiments in combination with satellite DA which would in turn benefit remote sensing communities. [ABSTRACT FROM AUTHOR]

Gaseous and particulate semi volatile carbonyls have been measured in urban air using an annular denuder sampling system. Three dicarbonyls, five aliphatic aldehydes and two hydroxy carbonyls were observed. Concentrations of other biogenic and anthropogenic volatile organic compounds (VOCs), SO2, CO, NO2 and particle concentration were also measured. Estimated gasaerosol equilibrium constants for the carbonyls showed an inverse correlation with the concentrations of anthropogenic pollutants such as benzene, isopentane and SO2. This suggests that the increase in the fraction of non-polar anthropogenic particles in the atmosphere could change the average property of the ambient aerosols and drive the gas particle equilibrium of the carbonyls to the gas phase. This trend is uncommon in remote forest air. In this study, we examined the factors controlling the equilibrium in the polluted atmosphere and show that there is a difference in gas-aerosol partition between polluted and clean air. Copyright 2005 by the American Geophysical Union.