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Abstract. Secondary organic aerosol (SOA) is a dominant contributor of fine particulate matter in the atmosphere, but the complexity of SOA formation chemistry hinders the accurate representation of SOA in models. Volatility-based SOA parameterizations have been adopted in many recent chemistry modeling studies and have shown a reasonable performance compared to observations. However, assumptions made in these empirical parameterizations can lead to substantial errors when applied to future climatic conditions as they do not include the mechanistic understanding of processes but are rather fitted to laboratory studies of SOA formation. This is particularly the case for SOA derived from isoprene epoxydiols (IEPOX SOA), for which we have a higher level of understanding of the fundamental processes than is currently parameterized in most models. We predict future SOA concentrations using an explicit mechanism and compare the predictions with the empirical parameterization based on the volatility basis set (VBS) approach. We then use the Community Earth System Model 2 (CESM2.1.0) with detailed isoprene chemistry and reactive uptake processes for the middle and end of the 21st century under four Shared Socioeconomic Pathways (SSPs): SSP1–2.6, SSP2–4.5, SSP3–7.0, and SSP5–8.5. With the explicit chemical mechanism, we find that IEPOX SOA is predicted to increase on average under all future SSP scenarios but with some variability in the results depending on regions and the scenario chosen. Isoprene emissions are the main driver of IEPOX SOA changes in the future climate, but the IEPOX SOA yield from isoprene emissions also changes by up to 50 % depending on the SSP scenario, in particular due to different sulfur emissions. We conduct sensitivity simulations with and without CO2 inhibition of isoprene emissions that is highly uncertain, which results in factor of 2 differences in the predicted IEPOX SOA global burden, especially for the high-CO2 scenarios (SSP3–7.0 and SSP5–8.5). Aerosol pH also plays a critical role in the IEPOX SOA formation rate, requiring accurate calculation of aerosol pH in chemistry models. On the other hand, isoprene SOA calculated with the VBS scheme predicts a nearly constant SOA yield from isoprene emissions across all SSP scenarios; as a result, it mostly follows isoprene emissions regardless of region and scenario. This is because the VBS scheme does not consider heterogeneous chemistry; in other words, there is no dependency on aerosol properties. The discrepancy between the explicit mechanism and VBS parameterization in this study is likely to occur for other SOA components as well, which may also have dependencies that cannot be captured by VBS parameterizations. This study highlights the need for more explicit chemistry or for parameterizations that capture the dependence on key physicochemical drivers when predicting SOA concentrations for climate studies. 

Abstract. Acidity, defined as pH, is a central component of aqueouschemistry. In the atmosphere, the acidity of condensed phases (aerosolparticles, cloud water, and fog droplets) governs the phase partitioning ofsemivolatile gases such as HNO3, NH3, HCl, and organic acids andbases as well as chemical reaction rates. It has implications for theatmospheric lifetime of pollutants, deposition, and human health. Despiteits fundamental role in atmospheric processes, only recently has this fieldseen a growth in the number of studies on particle acidity. Even with thisgrowth, many fine-particle pH estimates must be based on thermodynamic modelcalculations since no operational techniques exist for direct measurements.Current information indicates acidic fine particles are ubiquitous, butobservationally constrained pH estimates are limited in spatial and temporalcoverage. Clouds and fogs are also generally acidic, but to a lesser degreethan particles, and have a range of pH that is quite sensitive toanthropogenic emissions of sulfur and nitrogen oxides, as well as ambientammonia. Historical measurements indicate that cloud and fog droplet pH haschanged in recent decades in response to controls on anthropogenicemissions, while the limited trend data for aerosol particles indicateacidity may be relatively constant due to the semivolatile nature of thekey acids and bases and buffering in particles. This paper reviews andsynthesizes the current state of knowledge on the acidity of atmosphericcondensed phases, specifically particles and cloud droplets. It includesrecommendations for estimating acidity and pH, standard nomenclature, asynthesis of current pH estimates based on observations, and new modelcalculations on the local and global scale. 

Understanding the formation processes of particles and cloud condensation nuclei (CCN) in pristine environments is a major challenge in assessing the anthropogenic impacts on climate change. Using a state‐of‐the‐art model that systematically simulates the new‐particle formation (NPF) from condensable vapors and multi‐scale transport of chemical species, we find that NPF contributes ∼90% of the particle number and ∼80% of the CCN at 0.5% supersaturation (CCN0.5%) in the pristine Amazon boundary layer during the wet season. The corresponding contributions are only ∼30% and ∼20% during the dry season because of prevalent biomass burning. In both seasons, ∼50% of the NPF‐induced particles and ∼85% of the NPF‐induced CCN0.5% in the boundary layer originate from the long‐range transport of new particles formed hundreds to thousands of kilometers away. Moreover, about 50%–65% of the NPF‐induced particles and 35%–50% of the NPF‐induced CCN0.5% originate from the downward transport of new particles formed aloft.

 

Soot particles form during combustion of carbonaceous materials and impact climate and air quality. When freshly emitted, they are typically fractal-like aggregates. After atmospheric aging, they can act as cloud condensation nuclei, and water condensation or evaporation restructure them to more compact aggregates, affecting their optical, aerodynamic, and surface properties. Here we survey the morphology of ambient soot particles from various locations and different environmental and aging conditions. We used electron microscopy and show extensive soot compaction after cloud processing. We further performed laboratory experiments to simulate atmospheric cloud processing under controlled conditions. We find that soot particles sampled after evaporating the cloud droplets, are significantly more compact than freshly emitted and interstitial soot, confirming that cloud processing, not just exposure to high humidity, compacts soot. Our findings have implications for how the radiative, surface, and aerodynamic properties, and the fate of soot particles are represented in numerical models.

 

An advanced aerosol treatment, with a focus on semivolatile nitrate formation, is introduced into the Community Atmosphere Model version 5 with interactive chemistry (CAM5‐chem) by coupling the Model for Simulating Aerosol Interactions and Chemistry (MOSAIC) with the 7‐mode Modal Aerosol Module (MAM7). An important feature of MOSAIC is dynamic partitioning of all condensable gases to the different fine and coarse mode aerosols, as governed by mode‐resolved thermodynamics and heterogeneous chemical reactions. Applied in the free‐running mode from 1995 to 2005 with prescribed historical climatological conditions, the model simulates global distributions of sulfate, nitrate, and ammonium in good agreement with observations and previous studies. Inclusion of nitrate resulted in ∼10% higher global average accumulation mode number concentrations, indicating enhanced growth of Aitken mode aerosols from nitrate formation. While the simulated accumulation mode nitrate burdens are high over the anthropogenic source regions, the sea‐salt and dust modes respectively constitute about 74% and 17% of the annual global average nitrate burden. Regional clear‐sky shortwave radiative cooling of up to −5 W m⁻²due to nitrate is seen, with a much smaller global average cooling of −0.05 W m⁻². Significant enhancements in regional cloud condensation nuclei (at 0.1% supersaturation) and cloud droplet number concentrations are also attributed to nitrate, causing an additional global average shortwave cooling of −0.8 W m⁻². Taking into consideration of changes in both longwave and shortwave radiation under all‐sky conditions, the net change in the top of the atmosphere radiative fluxes induced by including nitrate aerosol is −0.7 W m⁻².

 

Abstract. Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO₃) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than 3 decades, during which time a large body of research has emerged from laboratory, field, and modeling studies. NO₃-BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone, and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number of important uncertainties remain. These include an incomplete understanding of the rates, mechanisms, and organic aerosol yields for NO₃-BVOC reactions, lack of constraints on the role of heterogeneous oxidative processes associated with the NO₃ radical, the difficulty of characterizing the spatial distributions of BVOC and NO₃ within the poorly mixed nocturnal atmosphere, and the challenge of constructing appropriate boundary layer schemes and non-photochemical mechanisms for use in state-of-the-art chemical transport and chemistry–climate models.

This review is the result of a workshop of the same title held at the Georgia Institute of Technology in June 2015. The first half of the review summarizes the current literature on NO₃-BVOC chemistry, with a particular focus on recent advances in instrumentation and models, and in organic nitrate and secondary organic aerosol (SOA) formation chemistry. Building on this current understanding, the second half of the review outlines impacts of NO₃-BVOC chemistry on air quality and climate, and suggests critical research needs to better constrain this interaction to improve the predictive capabilities of atmospheric models.