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 O 3 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.autoxidation | ELVOC | monoterpenes | isoprene | new particle formation F ormation and subsequent growth of new aerosol particles is a major source of cloud condensation nuclei (CCN) in the global troposphere (1, 2), and a big contributor to the large reported uncertainty in the radiative forcing by aerosol−cloud interactions (3-7). Multiple field studies have shown that CCN production is tightly connected with the oxidation of biogenic volatile organic compounds (BVOC) emitted by terrestrial ecosystems (8-11). To explain these observations, large-scale model simulations demonstrate a need for a BVOC oxidation mechanism in the atmosphere that produces very low volatility organic vapors with molar formation yields of at least a few percent per reacted precursor compound (12)(13)(14).The existence and formation mechanisms of essentially nonvolatile organic vapors in the atmosphere have puzzled scientists for some time (14-16). Such extremely low volatile organic compounds (ELVOC) (17) were recently detected, both in laboratory studies and in the ambient atmosphere (18), yet typical atmospheric oxidation chemistry schemes do not explain ELVOC produced on a time scale of minutes or hours. Furthermore, current state-of-the-art models using available chemistry schemes have systematically failed to reproduce the observed concentrations and volatility of organic aerosol components (17, 19). A plausible exp...

Abstract. In this paper we describe and summarize the main achievements of the European Aerosol Cloud Climate and Air Quality Interactions project (EUCAARI). EUCAARI started on 1 January 2007 and ended on 31 December 2010 leaving a rich legacy including: (a) a comprehensive database with a year of observations of the physical, chemical and optical properties of aerosol particles over Europe, (b) comprehensive aerosol measurements in four developing countries, (c) a database of airborne measurements of aerosols and clouds over Europe during May 2008, (d) comprehensive modeling tools to study aerosol processes fron nano to global scale and their effects on climate and air quality. In addition a new Pan-European aerosol emissions inventory was developed and evaluated, a new cluster spectrometer was built and tested in the field and several new aerosol parameterizations and computations modules for chemical transport and global climate models were developed and evaluated. These achievements and related studies have substantially improved our understanding and reduced the uncertainties of aerosol radiative forcing and air quality-climate interactions. The EUCAARI results can be utilized in European and global environmental policy to assess the aerosol impacts and the corresponding abatement strategies.

Abstract. The global aerosol-climate model ECHAM5-HAM was modified to improve the representation of new particle formation in the boundary layer. Activation-type nucleation mechanism was introduced to produce observed nucleation rates in the lower troposphere. A simple and computationally efficient model for biogenic secondary organic aerosol (BSOA) formation was implemented. Here we study the sensitivity of the aerosol and cloud droplet number concentrations (CDNC) to these additions. Activationtype nucleation significantly increases aerosol number concentrations in the boundary layer. Increased particle number concentrations have a significant effect also on cloud droplet number concentrations and therefore on cloud properties. We performed calculations with activation nucleation coefficient values of 2×10 −7 s −1 , 2×10 −6 s −1 and 2×10 −5 s −1 to evaluate the sensitivity to this parameter. For BSOA we have used yields of 0.025, 0.07 and 0.15 to estimate the amount of monoterpene oxidation products available for condensation. The hybrid BSOA formation scheme induces large regional changes to size distribution of organic carbon, and therefore affects particle optical properties and cloud droplet number concentrations locally. Although activation-type nuCorrespondence to: R. Makkonen (risto.makkonen@helsinki.fi) cleation improves modeled aerosol number concentrations in the boundary layer, the use of a global activation coefficient generally leads to overestimation of aerosol number. Overestimation can also arise from underestimation of primary emissions.

Abstract. The number concentration of cloud droplets determines several climatically relevant cloud properties. A major cause for the high uncertainty in the indirect aerosol forcing is the availability of cloud condensation nuclei (CCN), which in turn is highly sensitive to atmospheric new particle formation. Here we present the effect of new particle formation on anthropogenic aerosol forcing in present-day (year 2000) and future (year 2100) conditions. The present-day total aerosol forcing is increased from −1.0 W m −2 to −1.6 W m −2 when nucleation is introduced into the model. Nucleation doubles the change in aerosol forcing between years 2000 and 2100, from +0.6 W m −2 to +1.4 W m −2 . Two climate feedbacks are studied, resulting in additional negative forcings of −0.1 W m −2 (+10 % DMS emissions in year 2100) and −0.5 W m −2 (+50 % BVOC emissions in year 2100). With the total aerosol forcing diminishing in response to air pollution control measures taking effect, warming from increased greenhouse gas concentrations can potentially increase at a very rapid rate.

Abstract. The sectional aerosol module SALSA is introduced. The model has been designed to be implemented in large scale climate models, which require both accuracy and computational efficiency. We have used multiple methods to reduce the computational burden of different aerosol processes to optimize the model performance without losing physical features relevant to problematics of climate importance. The optimizations include limiting the chemical compounds and physical processes available in different size sections of aerosol particles; division of the size distribution into size sections using size sections of variable width depending on the sensitivity of microphysical processing to the particles sizes; the total amount of size sections to describe the size distribution is kept to the minimum; furthermore, only the relevant microphysical processes affecting each size section are calculated. The ability of the module to describe different microphysical processes was evaluated against explicit microphysical models and several microphysical models used in air quality models. The results from the current module show good consistency when compared to more explicit models. Also, the module was used to simulate a new particle formation event typical in highly polluted conditions with comparable results to more explicit model setup.

Abstract. Oxidation processes in Earth's atmosphere are tightly connected to many environmental and human health issues and are essential drivers for biogeochemistry. Until the recent discovery of the atmospheric relevance of the reaction of stabilized Criegee intermediates (sCIs) with SO 2 , atmospheric oxidation processes were thought to be dominated by a few main oxidants: ozone, hydroxyl radicals (OH), nitrate radicals and, e.g. over oceans, halogen atoms such as chlorine. Here, we report results from laboratory experiments at 293 K and atmospheric pressure focusing on sCI formation from the ozonolysis of isoprene and the most abundant monoterpenes (α-pinene and limonene), and subsequent reactions of the resulting sCIs with SO 2 producing sulfuric acid (H 2 SO 4 ). The measured total sCI yields were (0.15 ± 0.07), (0.27 ± 0.12) and (0.58 ± 0.26) for α-pinene, limonene and isoprene, respectively. The ratio between the rate coefficient for the sCI loss (including thermal decomposition and the reaction with water vapour) and the rate coefficient for the reaction of sCI with SO 2 , k(loss) / k(sCI + SO 2 ), was determined at relative humidities of 10 and 50 %. Observed values represent the average reactivity of all sCIs produced from the individual alkene used in the ozonolysis. For the monoterpene-derived sCIs, the relative rate coefficients k(loss) / k(sCI + SO 2 ) were in the range (2.0-2.4) × 10 12 molecules cm −3 and nearly independent of the relative humidity. This fact points to a minor importance of the sCI + H 2 O reaction in the case of the sCI arising from α-pinene and limonene. For the isoprene sCIs, however, the ratio k(loss) / k(sCI + SO 2 ) was strongly dependent on the relative humidity. To explore whether sCIs could have a more general role in atmospheric oxidation, we investigated as an example the reactivity of acetone oxide (sCI from the ozonolysis of 2,3-dimethyl-2-butene) toward small organic acids, i.e. formic and acetic acid. Acetone oxide was found to react faster with the organic acids than with SO 2 ; k(sCI + acid) / k(sCI + SO 2 ) = (2.8 ± 0.3) for formic acid, and k(sCI + acid) / k(sCI + SO 2 ) = (3.4 ± 0.2) for acetic acid. This finding indicates that sCIs can play a role in the formation and loss of other atmospheric constituents besides SO 2 .

Abstract. The Earth system model EC-Earth3 for contributions to CMIP6 is documented here, with its flexible coupling framework, major model configurations, a methodology for ensuring the simulations are comparable across different high-performance computing (HPC) systems, and with the physical performance of base configurations over the historical period. The variety of possible configurations and sub-models reflects the broad interests in the EC-Earth community. EC-Earth3 key performance metrics demonstrate physical behavior and biases well within the frame known from recent CMIP models. With improved physical and dynamic features, new Earth system model (ESM) components, community tools, and largely improved physical performance compared to the CMIP5 version, EC-Earth3 represents a clear step forward for the only European community ESM. We demonstrate here that EC-Earth3 is suited for a range of tasks in CMIP6 and beyond.

Abstract. We document model updates and present and discuss modeling and validation results from a further developed production-tagged aerosol module, OsloAero5.3, for use in Earth system models. The aerosol module has in this study been implemented and applied in CAM5.3-Oslo. This model is based on CAM5.3–CESM1.2 and its own predecessor model version CAM4-Oslo. OsloAero5.3 has improved treatment of emissions, aerosol chemistry, particle life cycle, and aerosol–cloud interactions compared to its predecessor OsloAero4.0 in CAM4-Oslo. The main new features consist of improved aerosol sources; the module now explicitly accounts for aerosol particle nucleation and secondary organic aerosol production, with new emissions schemes also for sea salt, dimethyl sulfide (DMS), and marine primary organics. Mineral dust emissions are updated as well, adopting the formulation of CESM1.2. The improved model representation of aerosol–cloud interactions now resolves heterogeneous ice nucleation based on black carbon (BC) and mineral dust calculated by the model and treats the activation of cloud condensation nuclei (CCN) as in CAM5.3. Compared to OsloAero4.0 in CAM4-Oslo, the black carbon (BC) mass concentrations are less excessive aloft, with a better fit to observations. Near-surface mass concentrations of BC and sea salt aerosols are also less biased, while sulfate and mineral dust are slightly more biased. Although appearing quite similar for CAM5.3-Oslo and CAM4-Oslo, the validation results for organic matter (OM) are inconclusive, since both of the respective versions of OsloAero are equipped with a limited number of OM tracers for the sake of computational efficiency. Any information about the assumed mass ratios of OM to organic carbon (OC) for different types of OM sources is lost in the transport module. Assuming that observed OC concentrations scaled by 1.4 are representative for the modeled OM concentrations, CAM5.3-Oslo with OsloAero5.3 is slightly inferior for the very sparsely available observation data. Comparing clear-sky column-integrated optical properties with data from ground-based remote sensing, we find a negative bias in optical depth globally; however, it is not as strong as in CAM4-Oslo, but has positive biases in some areas typically dominated by mineral dust emissions. Aerosol absorption has a larger negative bias than the optical depth globally. This is reflected in a lower positive bias in areas where mineral dust is the main contributor to absorption. Globally, the low bias in absorption is smaller than in CAM4-Oslo. The Ångström parameter exhibits small biases both globally and regionally, suggesting that the aerosol particle sizes are reasonably well represented. Cloud-top droplet number concentrations over oceans are generally underestimated compared to satellite retrievals, but seem to be overestimated downwind of major emissions of dust and biomass burning sources. Finally, we find small changes in direct radiative forcing at the top of the atmosphere, while the cloud radiative forcing due to anthropogenic aerosols is now more negative than in CAM4-Oslo, being on the strong side compared to the multi-model estimate in IPCC AR5. Although not all validation results in this study show improvement for the present CAM5.3-Oslo version, the extended and updated aerosol module OsloAero5.3 is more advanced and applicable than its predecessor OsloAero4.0, as it includes new parameterizations that more readily facilitate sensitivity and process studies and use in climate and Earth system model studies in general.