Abstract. Atmospheric aerosols are a significant public health hazard and have substantial impacts on the climate. Secondary organic aerosols (SOAs) have been shown to phase separate into a highly viscous organic outer layer surrounding an aqueous core. This phase separation can decrease the partitioning of semi-volatile and low-volatile species to the organic phase and alter the extent of acid-catalyzed reactions in the aqueous core. A new algorithm that can determine SOA phase separation based on their glass transition temperature (Tg), oxygen to carbon (O:C) ratio and organic mass to sulfate ratio, and meteorological conditions was implemented into the Community Multiscale Air Quality Modeling (CMAQ) system version 5.2.1 and was used to simulate the conditions in the continental United States for the summer of 2013. SOA formed at the ground/surface level was predicted to be phase separated with core–shell morphology, i.e., aqueous inorganic core surrounded by organic coating 65.4 % of the time during the 2013 Southern Oxidant and Aerosol Study (SOAS) on average in the isoprene-rich southeastern United States. Our estimate is in proximity to the previously reported ∼70 % in literature. The phase states of organic coatings switched between semi-solid and liquid states, depending on the environmental conditions. The semi-solid shell occurring with lower aerosol liquid water content (western United States and at higher altitudes) has a viscosity that was predicted to be 102–1012 Pa s, which resulted in organic mass being decreased due to diffusion limitation. Organic aerosol was primarily liquid where aerosol liquid water was dominant (eastern United States and at the surface), with a viscosity <102 Pa s. Phase separation while in a liquid phase state, i.e., liquid–liquid phase separation (LLPS), also reduces reactive uptake rates relative to homogeneous internally mixed liquid morphology but was lower than aerosols with a thick viscous organic shell. The sensitivity cases performed with different phase-separation parameterization and dissolution rate of isoprene epoxydiol (IEPOX) into the particle phase in CMAQ can have varying impact on fine particulate matter (PM2.5) organic mass, in terms of bias and error compared to field data collected during the 2013 SOAS. This highlights the need to better constrain the parameters that govern phase state and morphology of SOA, as well as expand mechanistic representation of multiphase chemistry for non-IEPOX SOA formation in models aided by novel experimental insights.

Combining unique high-altitude aircraft measurements and detailed regional model simulations, we show that inplant biochemistry plays a central but previously unidentified role in fine particulate-forming processes and atmosphere−biosphere− climate interactions over the Amazon rainforest. Isoprene epoxydiol secondary organic aerosols (IEPOX-SOA) are key components of sub-micrometer aerosol particle mass throughout the troposphere over the Amazon rainforest and are traditionally thought to form by multiphase chemical pathways. Here, we show that these pathways are strongly inhibited by the solid thermodynamic phase state of aerosol particles and lack of particle and cloud liquid water in the upper troposphere. Strong diffusion limitations within organic aerosol coatings prevailing at low temperatures and low relative humidity in the upper troposphere strongly inhibit the reactive uptake of IEPOX to inorganic aerosols. We find that direct emissions of 2-methyltetrol gases formed by in-plant biochemical oxidation and/or oxidation of deposited IEPOX gases on the surfaces of soils and leaves and their transport by cloud updrafts followed by their condensation at low temperatures could explain over 90% of the IEPOX-SOA mass concentrations in the upper troposphere. Our simulations indicate that even near the surface, direct emissions of 2-methyltetrol gases represent a ubiquitous, but previously unaccounted for, source of IEPOX-SOA. Our results provide compelling evidence for new pathways related to land surface−aerosol−cloud interactions that have not been considered previously.

Abstract. Modeling of soil nitric oxide (NO) emissions is highly uncertain and may misrepresent its spatial and temporal distribution. This study builds upon a recently introduced parameterization to improve the timing and spatial distribution of soil NO emission estimates in the Community Multiscale Air Quality (CMAQ) model. The parameterization considers soil parameters, meteorology, land use, and mineral nitrogen (N) availability to estimate NO emissions. We incorporate daily year-specific fertilizer data from the Environmental Policy Integrated Climate (EPIC) agricultural model to replace the annual generic data of the initial parameterization, and use a 12 km resolution soil biome map over the continental USA. CMAQ modeling for July 2011 shows slight differences in model performance in simulating fine particulate matter and ozone from Interagency Monitoring of Protected Visual Environments (IMPROVE) and Clean Air Status and Trends Network (CASTNET) sites and NO2 columns from Ozone Monitoring Instrument (OMI) satellite retrievals. We also simulate how the change in soil NO emissions scheme affects the expected O3 response to projected emissions reductions.

Abstract. Soils are important sources of emissions of nitrogen-containing (N-containing) gases such as nitric oxide (NO), nitrous acid (HONO), nitrous oxide (N2O), and ammonia (NH3). However, most contemporary air quality models lack a mechanistic representation of the biogeochemical processes that form these gases. They typically use heavily parameterized equations to simulate emissions of NO independently from NH3 and do not quantify emissions of HONO or N2O. This study introduces a mechanistic, process-oriented representation of soil emissions of N species (NO, HONO, N2O, and NH3) that we have recently implemented in the Community Multiscale Air Quality (CMAQ) model. The mechanistic scheme accounts for biogeochemical processes for soil N transformations such as mineralization, volatilization, nitrification, and denitrification. The rates of these processes are influenced by soil parameters, meteorology, land use, and mineral N availability. We account for spatial heterogeneity in soil conditions and biome types by using a global dataset for soil carbon (C) and N across terrestrial ecosystems to estimate daily mineral N availability in nonagricultural soils, which was not accounted for in earlier parameterizations for soil NO. Our mechanistic scheme also uses daily year-specific fertilizer use estimates from the Environmental Policy Integrated Climate (EPIC v0509) agricultural model. A soil map with sub-grid biome definitions was used to represent conditions over the continental United States. CMAQ modeling for May and July 2011 shows improvement in model performance in simulated NO2 columns compared to Ozone Monitoring Instrument (OMI) satellite retrievals for regions where soils are the dominant source of NO emissions. We also assess how the new scheme affects model performance for NOx (NO+NO2), fine nitrate (NO3) particulate matter, and ozone observed by various ground-based monitoring networks. Soil NO emissions in the new mechanistic scheme tend to fall between the magnitudes of the previous parametric schemes and display much more spatial heterogeneity. The new mechanistic scheme also accounts for soil HONO, which had been ignored by parametric schemes.