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The cosmogenic radionuclides 7Be and 10Be are useful aerosol tracers for atmospheric transport studies. Combining 7Be and 10Be measurements with an atmospheric transport model can not only improve our understanding of the radionuclide transport and deposition processes but also provide an evaluation of the transport process in the model. To simulate these aerosol tracers, it is critical to evaluate the influence of radionuclides production uncertainties on simulations. Here we use the GEOS-Chem chemical transport model driven by the MERRA-2 reanalysis to simulate 7Be and 10Be with different production scenarios: the default production rate in GEOS-Chem based on an empirical approach (denoted as LP67), and two production rates from the CRAC:Be (Cosmic Ray Atmospheric Cascade: Beryllium) model considering only geomagnetic cut-off rigidities for a geocentric axial dipole (denoted as P16) or realistic spatial geomagnetic cut-off rigidity variations due to non-dipole moments of the geomagnetic field (denoted as P16spa). The model results are comprehensively evaluated with a large number of measurements including surface air concentrations and deposition fluxes. The model with the P16spa production can reproduce the absolute values and temporal variability of 7Be and 10Be surface concentrations and deposition fluxes on annual and sub-annual scales, as well as the vertical profiles of air concentrations. Simulations with the LP67 production tend to overestimate the absolute values of 7Be and 10Be concentrations. The P16 simulations suggest less than 10 % differences compared to P16spa but tend to produce a significant positive bias (>20 %) in the 7Be deposition fluxes over East Asia. We find that the deposition fluxes are more sensitive to the production in the troposphere and downward transport from the stratosphere. Independent of the production models, surface air concentrations and deposition fluxes from all simulations show similar seasonal variations, suggesting a dominant meteorological influence. The model can also reasonably simulate the stratosphere-troposphere exchange process of 7Be and 10Be by producing stratospheric contribution and 10Be / 7Be ratio values that agree with measurements. Finally, we illustrate the importance of including the time-varying solar modulation in the production calculation, which can significantly improve the agreement between model results and measurements, especially at mid- and high- latitudes. Reduced uncertainties in the production rates, as demonstrated in this study, improve the utility of 7Be and 10Be as aerosol tracers for evaluating and testing transport and scavenging processes in global models.

Dissociation of organic acids is currently not included in most atmospheric aerosol models. Organic dissociation in aqueous aerosols could alter the H+ concentrations and affect the cloud activating properties. We implemented a simple representation of organic dissociation in a box model version of the aerosol–chemistry–climate model ECHAM-HAMMOZ and investigated the impact on cloud droplet number concentrations and short-wave radiative effect through changes in kinetically driven sulfate concentrations in an aerosol population. Organic dissociation has been observed in X-ray photo-electron spectroscopy measurements to be significantly suppressed in the aqueous surface. We therefore additionally introduced an empirical account of this mechanism to explore the potential further impact on aerosol effects. Malonic acid and decanoic acid were used as proxies for atmospheric organic acid aerosols. Both acids were found to yield sufficient hydrogen ion concentrations from dissociation in an aqueous droplet population to strongly influence the sulfur chemistry, leading to enhanced cloud droplet number concentrations and a cooling short-wave radiative effect. Further considering surface modulated suppressed dissociation, the impact on cloud microphysics was smaller than according to the well-known bulk solution organic dissociation, but still significant. Our results show that organic aerosol acidity can significantly influence predictions of aerosol formation and aerosol-cloud-climate effects. Furthermore, it may be important to also consider the specific influence of surface effects, also in relation to bulk solution phenomena such as organic acid dissociation.

Surface active compounds (surfactants) are frequently found in atmospheric aerosols and droplets. As they adsorb to the surfaces of microscopic systems, surfactants can decrease aqueous surface tension and simultaneously deplete the bulk concentration. These processes may influence the activation of aerosols into cloud droplets and investigation of their role in cloud microphysics has been ongoing for decades. In this work, we have used six different models documented in the literature to represent surface activity in Köhler calculations of cloud droplet activation for particles consisting of one of three moderately surface active organics (malonic, succinic or glutaric acid) mixed with ammonium sulfate in varying mass ratios. For each of these organic acids, we find that the models predict comparable activation properties at small organic mass fractions in the dry particles, despite large differences in the predicted degree of bulk-to-surface partitioning. However, differences between the model predictions for the same dry particles regarding both the critical droplet diameters and supersaturations increase with the organic fraction in the particles. Comparison with available experimental data shows that models assuming complete bulk-to-surface partitioning of the moderately surface active component (total depletion of the bulk) do not adequately represent the droplet activation of particles with high organic mass fractions. When reduced droplet surface tension is also considered, these predictions somewhat improve. Models that consider partial bulk-to-surface partitioning of surface active components yield results comparable to experimental supersaturation data, even at high organic mass fractions in the particles, but predictions of the degree of organic bulk–surface partitioning strongly differ. This work highlights the need to use a thermodynamically consistent model framework to treat the surface activity of atmospheric aerosols and for firm experimental validation of model predictions across a wide range of droplet states relevant to the atmosphere.

This work presents a thermodynamically consistent framework that enables self-contained, predictive Köhler calculations of droplet growth and activation with considerations of surface adsorption, surface tension reduction, and non-ideal water activity for chemically complex and unresolved surface-active aerosol mixtures. The common presence of surface-active species in atmospheric aerosols is now well-established. However, the impacts of different effects driven by surface activity, in particular bulk–surface partitioning and resulting bulk depletion and/or surface tension reduction, on aerosol hygroscopic growth and cloud droplet activation remain to be generally established. Because specific characterization of key properties, including water activity and surface tension, remains exceedingly challenging for finite-sized activating droplets, a self-contained and thermodynamically consistent model framework is needed to resolve the individual effects of surface activity during droplet growth and activation. Previous frameworks have achieved this for simple aerosol mixtures, comprising at most a few well-defined chemical species. However, atmospheric aerosol mixtures and more realistic laboratory systems are typically chemically more complex and not well-defined (unresolved). Therefore, frameworks which require specific knowledge of the concentrations of all chemical species in the mixture and their composition-dependent interactions cannot be applied. For mixtures which are unresolved or where specific interactions between components are unknown, analytical models based on retrofitting can be applied, or the mixture can be represented by a proxy compound or mixture with well-known properties. However, the surface activity effects evaluated by such models cannot be independently verified. The presented model couples Köhler theory with the Gibbs adsorption and Szyszkowski-type surface tension equations. Contrary to previous thermodynamic frameworks, it is formulated on a mass basis to obtain a quantitative description of composition-dependent properties for chemically unresolved mixtures. Application of the model is illustrated by calculating cloud condensation nuclei (CCN) activity of aerosol particles comprising Nordic aquatic fulvic acid (NAFA), a chemically unresolved and strongly surface-active model atmospheric humic-like substance (HULIS), and NaCl, with dry diameters of 30–230 nm and compositions spanning the full range of relative NAFA and NaCl mixing ratios. For comparison with the model presented, several other predictive Köhler frameworks, with simplified treatments of surface-active NAFA, are also applied. Effects of NAFA surface activity are gauged via a suite of properties evaluated for growing and activating droplets. The presented framework predicts a similar influence of surface activity of the chemically complex NAFA on CCN activation as was previously shown for single, strong surfactants. Comparison to experimental CCN data shows that NAFA bulk–surface partitioning is well-represented by Gibbs adsorption thermodynamics. Contrary to several recent studies, no evidence of significantly reduced droplet surface tension at the point of activation was found. Calculations with the presented thermodynamic model show that throughout droplet growth and activation, the finite amounts of NAFA in microscopic and submicron droplets are strongly depleted from the bulk, due to bulk–surface partitioning, because surface areas for a given bulk volume are very large. As a result, both the effective hygroscopicity and ability of NAFA to reduce droplet surface tension are significantly lower in finite-sized activating droplets than in macroscopic aqueous solutions of the same overall composition. The presented framework enables the influence of surface activity on CCN activation for other chemically complex and unresolved aerosol mixtures, including actual atmospheric samples, to be systematically explored. Thermodynamic input parameters can be independently constrained from measurements, instead of being either approximated by a proxy or determined by retrofitting, potentially confounding several mechanisms influenced by surface activity.

We study the adsorption of water onto deposited inorganic sodium chloride and organic malonic acid and sucrose nanoparticles at ambient water pressures corresponding to relative humidities (RH) from 0 % to 16 %. To obtain information about water adsorption at conditions which are not accessible with typical aerosol instrumentation, we use surface-sensitive ambient pressure X-ray photoelectron spectroscopy (APXPS), which has a detection sensitivity starting at parts per thousand. Our results show that water is already adsorbed on sodium chloride particles at RH well below deliquescence and that the chemical environment on the particle surface is changing with increasing humidity. While the sucrose particles exhibit only very modest changes on the surface at these relative humidities, the chemical composition and environment of malonic acid particle surfaces is clearly affected. Our observations indicate that water uptake by inorganic and organic aerosol particles could already have an impact on atmospheric chemistry at low relative humidities. We also establish the APXPS technique as a viable tool for studying chemical changes on the surfaces of atmospherically relevant aerosol particles which are not detected with typical online mass- and volume-based methods.

We have used the COSMOtherm program to estimate activity coefficients and solubilities of mono- and α, ω-dicarboxylic acids, and water in binary acid-water systems. The deviation from ideality was found to be larger in the systems containing larger acids than in the systems containing smaller acids. We found a better agreement between estimated and experimental activity coefficients of monocarboxylic acids when the water clustering with a carboxylic acid and itself was taken into account using the dimerization, aggregation and reaction extension (COSMO-RS-DARE) of COSMOtherm. Based on effective equilibrium constants of different clustering reactions in the binary solutions, acid dimer formation is more dominant in systems containing larger dicarboxylic acids (C5–C8), while for monocarboxylic acids (C1–C6) and smaller dicarboxylic acids (C2–C4), hydrate formation is more favorable, especially in dilute solutions.

With a growing majority of the world’s population residing in cities, it is vital to advance a shift to low-emission urban mobility in order to mitigate climate change. Despite the fundamental role played by infrastructure, daily decisions and routines of individuals ultimately generate traffic. When people choose a conventionally fuelled private car, it causes externalities detrimental for both individuals and the urban system as a whole: congestion, noise, greenhouse gas emissions, air pollution. Empirical studies show that the awareness of and exposure to those do not provide enough motivation for people to shift to more sustainable travel modes. Convenience overpowers environmental values. To break the habits and manage emissions, authorities must deploy incentives or sanctions – structural, regulative, economic, persuasive – that can increase the comparative advantage of low-carbon traffic modes. The potential of different initiatives to reduce traffic emissions is invaluable information for decision makers. Our contribution investigates the variety of possible ways to advance the desired shift, and highlights the importance, challenges and key factors of high quality impact evaluations . A functional approach to test and evaluate traffic initiatives is multidisciplinary, with ways to quantify people’s behavior and preferences, traffic emerging from them, and the resulting atmospheric emissions. By shedding light on reliable approaches to reveal the real impacts of traffic initiatives, the efforts for climate change management may be reinforced.

A new monolayer model predicts the bulk-surface partitioning, surface composition, and thickness of droplets comprising chemically unresolved, atmospherically relevant organic aerosols., The droplet surface plays important roles in the interaction between organic aerosols with clouds and climate. Surface active organic compounds can partition to the droplet surface, depleting the solute from the droplet bulk or depressing the droplet surface tension. This may in turn affect the shape of the droplet growth curve, threshold of aerosol activation into cloud droplets, activated droplet size distributions, and cloud radiative effects. In this work, a new monolayer model along with a traditional Gibbs adsorption isotherm model was used in conjunction with equilibrium Köhler theory to predict cloud condensation nuclei (CCN) activation of both simple and complex surface active model aerosol systems. For the surface active aerosol considered, the monolayer droplet model produces similar results to the Gibbs model as well as comparable results to CCN measurements from the literature, even for systems where specific molecular identities and aqueous properties are unknown. The monolayer model is self-contained and fully prognostic, and provides a versatile, conceptually simple, yet physically based model for understanding the role of organic surfactants in cloud droplet formation.