Dry deposition is the second-largest tropospheric ozone (O3) sink and occurs through stomatal and nonstomatal pathways. Current O3 uptake predictions are limited by the simplistic big-leaf schemes commonly used in chemical transport models (CTMs) to parameterize deposition. Such schemes fail to reproduce observed O3 fluxes over terrestrial ecosystems, highlighting the need for more realistic treatment of surface-atmosphere exchange in CTMs. We address this need by linking a resolved canopy model (1D Multi-Layer Canopy CHemistry and Exchange Model, MLC-CHEM) to the GEOS-Chem CTM, and use this new framework to simulate O3 fluxes over three north temperate forests. We compare results with in-situ measurements from four field studies and with standalone, observationally-constrained MLC-CHEM runs to test current knowledge of O3 deposition and its drivers. We show that GEOS-Chem overpredicts observed O3 fluxes across all four studies by up to 2×, whereas the resolved-canopy models capture observed diel profiles of O3 deposition and in-canopy concentrations to within 10%. Relative humidity and solar irradiance are strong O3 flux drivers over these forests, and uncertainties in those fields provide the largest remaining source of model deposition biases. Flux partitioning analysis shows that: 1) nonstomatal loss accounts for 60% of O3 deposition on average; 2) in-canopy chemistry makes only a small contribution to total O3 fluxes; and 3) the CTM big-leaf treatment overestimates O3-driven stomatal loss and plant phytotoxicity in these temperate forests by up to 7×. Results motivate the application of fully-online, vertically explicit canopy schemes in CTMs for improved O3 predictions.

We use observations from dual high-resolution mass spectrometers to characterize ecosystem-atmosphere fluxes of reactive carbon across an extensive range of volatile organic compounds (VOCs) and test how well that exchange is represented in current chemical transport models. Measurements combined proton-transfer reaction mass spectrometry (PTRMS) and iodide chemical ionization mass spectrometry (ICIMS) over a Colorado pine forest; together, these techniques have been shown to capture the majority of ambient VOC abundance and reactivity. Total VOC mass and associated OH reactivity fluxes were dominated by emissions of 2-methyl-3-buten-2-ol, monoterpenes, and small oxygenated VOCs, with a small number of compounds detected by PTRMS driving the majority of both net and upward exchanges. Most of these dominant species are explicitly included in chemical models, and we find here that GEOS-Chem accurately simulates the net and upward VOC mass and OH reactivity fluxes under clear sky conditions. However, large upward terpene fluxes occurred during sustained rainfall, and these are not captured by the model. Far more species contributed to the downward fluxes than are explicitly modeled, leading to a major underestimation of this key sink of atmospheric reactive carbon. This model bias mainly reflects missing and underestimated concentrations of depositing species, though inaccurate deposition velocities also contribute. The deposition underestimate is particularly large for assumed isoprene oxidation products, organic acids, and nitrates—species that are primarily detected by ICIMS. Ecosystem-atmosphere fluxes of ozone reactivity were dominated by sesquiterpenes and monoterpenes, highlighting the importance of these species for predicting near-surface ozone, oxidants, and aerosols.

Small cumulus clouds over the western United States were measured via airborne instruments during the wildfire season in summer of 2018. Statistics of the sampled clouds are presented and compared to smoke aerosol properties. Cloud droplet concentrations were enhanced in regions impacted by biomass burning smoke, at times exceeding 3,000 cm-3. Images and elemental composition of individual smoke particles and cloud droplet residuals are presented and show that most are dominantly organic, internally mixed with some inorganic elements. Despite their high organic content and relatively low hygroscopicity, on average about half of smoke aerosol particles >80 nm diameter formed cloud droplets. This reduced cloud droplet size in small, smoke-impacted clouds. A number of complex and competing climatic impacts may result from wide-spread reductions in cloud droplet size due to wildfires prevalent across the region during summer months.