Atmospheric aerosol formation from biogenic vapors is strongly affected by air pollutants, like NOx, SO2, and NH3.

Secondary organic aerosols (SOA) forms a major fraction of organic aerosols in the atmosphere. Knowledge of SOA properties that affect their dynamics in the atmosphere is needed for improving climate models. By combining experimental and modeling techniques, we investigated the factors controlling SOA evaporation under different humidity conditions. Our experiments support the conclusion of particle phase diffusivity limiting the evaporation under dry conditions. Viscosity of particles at dry conditions was estimated to increase several orders of magnitude during evaporation, up to 109 Pa s. However, at atmospherically relevant relative humidity and time scales, our results show that diffusion limitations may have a minor effect on evaporation of the studied α‐pinene SOA particles. Based on previous studies and our model simulations, we suggest that, in warm environments dominated by biogenic emissions, the major uncertainty in models describing the SOA particle evaporation is related to the volatility of SOA constituents.

The terrestrial vegetation emits large amounts of volatile organic compounds (VOC) into the atmosphere, which on oxidation produce secondary organic aerosol (SOA). By acting as cloud condensation nuclei (CCN), SOA influences cloud formation and climate. In a warming climate, changes in environmental factors can cause stresses to plants, inducing changes of the emitted VOC. These can modify particle size and composition. Here we report how induced emissions eventually affect CCN activity of SOA, a key parameter in cloud formation. For boreal forest tree species, insect infestation by aphids causes additional VOC emissions which modifies SOA composition thus hygroscopicity and CCN activity. Moderate heat increases the total amount of constitutive VOC, which has a minor effect on hygroscopicity, but affects CCN activity by increasing the particles' size. The coupling of plant stresses, VOC composition and CCN activity points to an important impact of induced plant emissions on cloud formation and climate.

Secondary organic aerosol (SOA) impact climate by scattering and absorbing radiation and contributing to cloud formation. SOA models are based on studies of simplified chemical systems that do not account for the chemical complexity in the atmosphere. This study investigated SOA formation from a mixture of real Scots pine (Pinus sylvestris) emissions including a variety of monoterpenes and sesquiterpenes. SOA generation was characterized from different combinations of volatile compounds as the plant emissions were altered with an herbivore stress treatment. During active herbivore feeding, monoterpene and sesquiterpene emissions increased, but SOA mass yields decreased after accounting for absorption effects. SOA mass yields were controlled by sesquiterpene emissions in healthy plants. In contrast, SOA mass yields from stressed plant emissions were controlled by the specific blend of monoterpene emissions. Conservative estimates using a box model approach showed a 1.5- to 2.3-fold aerosol enhancement when the terpene complexity was taken into account. This enhancement was relative to the commonly used model monoterpene, “α-pinene”. These results suggest that simplifying terpene complexity in SOA models could lead to underpredictions in aerosol mass loading.

Abstract. During the measurement campaign FROST 2 (FReezing Of duST 2), the Leipzig Aerosol Cloud Interaction Simulator (LACIS) was used to investigate the influence of various surface modifications on the ice nucleating ability of Arizona Test Dust (ATD) particles in the immersion freezing mode. The dust particles were exposed to sulfuric acid vapor, to water vapor with and without the addition of ammonia gas, and heat using a thermodenuder operating at 250 • C. Size selected, quasi monodisperse particles with a mobility diameter of 300 nm were fed into LACIS and droplets grew on these particles such that each droplet contained a single particle. Temperature dependent frozen fractions of these droplets were determined in a temperature range between −40 • C ≤T ≤−28 • C. The pure ATD particles nucleated ice over a broad temperature range with their freezing behavior being separated into two freezing branches characterized through different slopes in the frozen fraction vs. temperature curves. Coating the ATD particles with sulfuric acid resulted in the particles' IN potential significantly decreasing in the first freezing branch (T >−35 • C) and a slight increase in the second branch (T ≤−35 • C). The addition of water vapor after the sulfuric acid coating caused the disappearance Correspondence to: D. Niedermeier (niederm@tropos.de) of the first freezing branch and a strong reduction of the IN ability in the second freezing branch. The presence of ammonia gas during water vapor exposure had a negligible effect on the particles' IN ability compared to the effect of water vapor. Heating in the thermodenuder led to a decreased IN ability of the sulfuric acid coated particles for both branches but the additional heat did not or only slightly change the IN ability of the pure ATD and the water vapor exposed sulfuric acid coated particles. In other words, the combination of both sulfuric acid and water vapor being present is a main cause for the ice active surface features of the ATD particles being destroyed. A possible explanation could be the chemical transformation of ice active metal silicates to metal sulfates. The strongly enhanced reaction between sulfuric acid and dust in the presence of water vapor and the resulting significant reductions in IN potential are of importance for atmospheric ice cloud formation. Our findings suggest that the IN concentration can decrease by up to one order of magnitude for the conditions investigated.

The Mediterranean region is expected to experience substantial climatic change in the next 50 years. But, possible effects of climate change on biogenic volatile organic compound (VOC) emissions as well as on the formation of secondary organic aerosols (SOA) produced from these VOC are yet unexplored. To address such issues, the effects of temperature on the VOC emissions of Mediterranean Holm Oak and small Mediterranean stand of Wild Pistacio, Aleppo Pine, and Palestine Oak have been studied in the Jülich plant aerosol atmosphere chamber. For Holm Oak the optical and microphysical properties of the resulting SOA were investigated. <br><br> Monoterpenes dominated the VOC emissions from Holm Oak (97.5%) and Mediterranean stand (97%). Higher temperatures enhanced the overall VOC emission but with different ratios of the emitted species. The amount of SOA increased linearly with the emission strength with a fractional mass yield of 6.0&plusmn;0.6%, independent of the detailed emission pattern. The investigated particles were highly scattering with no absorption abilities. Their average hygroscopic growth factor of 1.13&plusmn;0.03 at 90% RH with a critical diameter of droplet activation was 100&plusmn;4 nm at a supersaturation of 0.4%. All microphysical properties did not depend on the detailed emission pattern, in accordance with an invariant O/C ratio (0.57(+0.03/−0.1)) of the SOA observed by high resolution aerosol mass spectrometry. <br><br> The increase of Holm oak emissions with temperature (≈20% per degree) was stronger than e.g. for Boreal tree species (≈10% per degree). The SOA yield for Mediterranean trees determined here is similar as for Boreal trees. Increasing mean temperature in Mediterranean areas could thus have a stronger impact on BVOC emissions and SOA formation than in areas with Boreal forests

Atmospheric new-particle formation (NPF) affects climate by contributing to a large fraction of the cloud condensation nuclei (CCN). Highly oxygenated organic molecules (HOMs) drive the early particle growth and therefore substantially influence the survival of newly formed particles to CCN. Nitrogen oxide (NOx) is known to suppress the NPF driven by HOMs, but the underlying mechanism remains largely unclear. Here, we examine the response of particle growth to the changes of HOM formation caused by NOx. We show that NOx suppresses particle growth in general, but the suppression is rather nonuniform and size dependent, which can be quantitatively explained by the shifted HOM volatility after adding NOx. By illustrating how NOx affects the early growth of new particles, a critical step of CCN formation, our results help provide a refined assessment of the potential climatic effects caused by the diverse changes of NOx level in forest regions around the globe.

Abstract. Interaction of biogenic volatile organic compounds (VOCs) with Anthropogenic VOC (AVOC) affects the physicochemical properties of secondary organic aerosol (SOA). We investigated cloud droplet activation (CCN activity), droplet growth kinetics, and hygroscopicity of mixed anthropogenic and biogenic SOA (ABSOA) compared to pure biogenic SOA (BSOA) and pure anthropogenic SOA (ASOA). Selected monoterpenes and aromatics were used as representative precursors of BSOA and ASOA, respectively.We found that BSOA, ASOA, and ABSOA had similar CCN activity despite the higher oxygen to carbon ratio (O/C) of ASOA compared to BSOA and ABSOA. For individual reaction systems, CCN activity increased with the degree of oxidation. Yet, when considering all different types of SOA together, the hygroscopicity parameter, κCCN, did not correlate with O/C. Droplet growth kinetics of BSOA, ASOA, and ABSOA were comparable to that of (NH4)2SO4, which indicates that there was no delay in the water uptake for these SOA in supersaturated conditions.In contrast to CCN activity, the hygroscopicity parameter from a hygroscopic tandem differential mobility analyzer (HTDMA) measurement, κHTDMA, of ASOA was distinctively higher (0.09–0.10) than that of BSOA (0.03–0.06), which was attributed to the higher degree of oxidation of ASOA. The ASOA components in mixed ABSOA enhanced aerosol hygroscopicity. Changing the ASOA fraction by adding biogenic VOC (BVOC) to ASOA or vice versa (AVOC to BSOA) changed the hygroscopicity of aerosol, in line with the change in the degree of oxidation of aerosol. However, the hygroscopicity of ABSOA cannot be described by a simple linear combination of pure BSOA and ASOA systems. This indicates that additional processes, possibly oligomerization, affected the hygroscopicity.Closure analysis of CCN and HTDMA data showed κHTDMA was lower than κCCN by 30–70 %. Better closure was achieved for ASOA compared to BSOA. This discrepancy can be attributed to several reasons. ASOA seemed to have higher solubility in subsaturated conditions and/or higher surface tension at the activation point than that of BSOA.