Most studies of the role of biological entities as atmospheric ice-nucleating particles have focused on relatively rare supermicron particles such as bacterial cells, fungal spores and pollen grains. However, it is not clear that there are sufficient numbers of these particles in the atmosphere to strongly influence clouds. Here we show that the ice-nucleating activity of a fungus from the ubiquitous genus Fusarium is related to the presence of nanometre-scale particles which are far more numerous, and therefore potentially far more important for cloud glaciation than whole intact spores or hyphae. In addition, we quantify the ice-nucleating activity of nano-ice nucleating particles (nano-INPs) washed off pollen and also show that nano-INPs are present in a soil sample. Based on these results, we suggest that there is a reservoir of biological nano-INPs present in the environment which may, for example, become aerosolised in association with fertile soil dust particles.

Abstract. Agricultural dust emissions have been estimated to contribute around 20 % to the global dust burden. In contrast to dusts from arid source regions, the ice-nucleating abilities of which have been relatively well studied, soil dusts from fertile sources often contain a substantial fraction of organic matter. Using an experimental methodology which is sensitive to a wide range of ice nucleation efficiencies, we have characterised the immersion mode ice-nucleating activities of dusts (d < 11 µm) extracted from fertile soils collected at four locations around England. By controlling droplet sizes, which ranged in volume from 10 −12 to 10 −6 L (concentration = 0.02 to 0.1 wt % dust), we have been able to determine the ice nucleation behaviour of soil dust particles at temperatures ranging from 267 K (−6 • C) down to the homogeneous limit of freezing at about 237 K (−36 • C). At temperatures above 258 K (−15 • C) we find that the ice-nucleating activity of soil dusts is diminished by heat treatment or digestion with hydrogen peroxide, suggesting that a major fraction of the ice nuclei stems from biogenic components in the soil. However, below 258 K, we find that the ice active site densities tend towards those expected from the mineral components in the soils, suggesting that the inorganic fraction of soil dusts, in particular the K-feldspar fraction, becomes increasingly important in the initiation of the ice phase at lower temperatures. We conclude that dusts from agricultural activities could contribute significantly to atmospheric IN concentrations, if such dusts exhibit similar activities to those observed in the current laboratory study.

We report the first direct measurements of water diffusion coefficients in secondary organic aerosol.

Abstract. Mineral dust is an important component of the climate system, affecting the radiation balance, cloud properties, biogeochemical cycles, regional circulation and precipitation, as well as having negative effects on aviation, solar energy generation and human health. Dust size and composition has an impact on all these processes. However, changes in dust size distribution and composition during transport, particularly for coarse particles, are poorly understood and poorly represented in climate models. Here we present new in situ airborne observations of dust in the Saharan Air Layer (SAL) and the marine boundary layer (MBL) at the beginning of its transatlantic transport pathway, from the AERosol Properties – Dust (AER-D) fieldwork in August 2015, within the peak season of North African dust export. This study focuses on coarse-mode dust properties, including size distribution, mass loading, shape, composition, refractive indices and optical properties. Size distributions from 0.1 to 100 µm diameter (d) are presented, fully incorporating the coarse and giant modes of dust. Within the MBL, mean effective diameter (deff) and volume median diameter (VMD) were 4.6 and 6.0 µm respectively, giant particles with a mode at 20–30 µm were observed, and composition was dominated by quartz and alumino-silicates at d > 1 µm. Within the SAL, particles larger than 20 µm diameter were always present up to 5 km altitude, in concentrations over 10−5 cm−3, constituting up to 40 % of total dust mass. Mean deff and VMD were 4.0 and 5.5 µm respectively. Larger particles were detected in the SAL than can be explained by sedimentation theory alone. Coarse-mode composition was dominated by quartz and alumino-silicates; the accumulation mode showed a strong contribution from sulfate-rich and sea salt particles. In the SAL, measured single scattering albedos (SSAs) at 550 nm representing d < 2.5 µm were 0.93 to 0.98 (mean 0.97). Optical properties calculated for the full size distribution (0.1 < d < 100 µm) resulted in lower SSAs of 0.91–0.98 (mean 0.95) and mass extinction coefficients of 0.27–0.35 m2 g−1 (mean 0.32 m2 g−1). Variability in SSA was mainly controlled by variability in dust composition (principally iron) rather than by variations in the size distribution, in contrast with previous observations over the Sahara where size is the dominant influence. It is important that models are able to capture the variability and evolution of both dust composition and size distribution with transport in order to accurately represent the impacts of dust on climate. These results provide a new SAL dust dataset, fully representing coarse and giant particles, to aid model validation and development.

Abstract. Recent research suggests that under certain temperature and relative humidity conditions atmospheric aerosol may be present in the form of a glassy solid. In order to understand the impacts that this may have on aerosolcloud interactions and atmospheric chemistry, knowledge of water diffusion within such aerosol particles is required. Here, a method is described in which Raman spectroscopy is used to observe D 2 O diffusion in high-viscosity aqueous solutions, enabling a quantitative assessment of water diffusion coefficients, D water , as a function of relative humidity. Results for sucrose solutions compare well with literature data at 23.5 ± 0.3 • C, and demonstrate that water diffusion is slow (D water ∼ 5 × 10 −17 m 2 s −1 ), but not arrested, just below the glass transition at a water activity of 0.2. Room temperature water diffusion coefficients are also presented for aqueous levoglucosan and an aqueous mixture of raffinose, dicarboxylic acids and ammonium sulphate: at low humidity, diffusion is retarded but still occurs on millisecond to second timescales in atmospherically relevant-sized particles. The effect of gel formation on diffusion in magnesium sulfate solutions is shown to be markedly different from the gradual decrease in diffusion coefficients of highly viscous liquids. We show that using the Stokes-Einstein equation to determine diffusion timescales from viscosity leads to values which are more than 5 orders of magnitude too big, which emphasises the need to make measurements of diffusion coefficients. In addition, comparison of bounce fraction data for levoglucosan with measured diffusion data reveals that even when particles bounce the diffusion timescales for water are a fraction of a second for a 100 nm particle. This suggests a high bounce fraction does not necessarily indicate retarded water diffusion.

Desert dust is one of the most important atmospheric ice‐nucleating aerosol species around the globe. However, there have been very few measurements of ice‐nucleating particle (INP) concentrations in dusty air close to desert sources. In this study we report the concentration of INPs in dust laden air over the tropical Atlantic within a few days' transport of one of the world's most important atmospheric sources of desert dust, the Sahara. These measurements were performed as part of the Ice in Clouds Experiment‐Dust campaign based in Cape Verde, during August 2015. INP concentrations active in the immersion mode, determined using a droplet‐on‐filter technique, ranged from around 102 m−3 at −12°C to around 105 m−3 at −23°C. There is about 2 orders of magnitude variability in INP concentration for a particular temperature, which is determined largely by the variability in atmospheric dust loading. These measurements were made at altitudes from 30 to 3,500 m in air containing a range of dust loadings. The ice active site density (ns) for desert dust dominated aerosol derived from our measurements agrees with several laboratory‐based parameterizations for ice nucleation by desert dust within 1 to 2 orders of magnitude. The small variability in ns values determined from our measurements (within about 1 order of magnitude) is striking given that the back trajectory analysis suggests that the sources of dust were geographically diverse. This is consistent with previous work, which indicates that desert dust's ice‐nucleating activity is only weakly dependent on source.

Abstract. Atmospheric secondary organic aerosol (SOA) is likely to exist in a semi-solid or glassy state, particularly at low temperatures and humidities. Previously, it has been shown that glassy aqueous citric acid aerosol is able to nucleate ice heterogeneously under conditions relevant to cirrus in the tropical tropopause layer (TTL). In this study we test if glassy aerosol distributions with a range of chemical compositions heterogeneously nucleate ice under cirrus conditions. Three single component aqueous solution aerosols (raffinose, 4-hydroxy-3-methoxy-DL-mandelic acid (HMMA) and levoglucosan) and one multi component aqueous solution aerosol (raffinose mixed with five dicarboxylic acids and ammonium sulphate) were studied in both the liquid and glassy states at a large cloud simulation chamber. The investigated organic compounds have similar functionality to oxidised organic material found in atmospheric aerosol and have estimated temperature/humidity induced glass transition thresholds that fall within the range predicted for atmospheric SOA. A small fraction of aerosol particles of all compositions were found to nucleate ice heterogeneously in the deposition mode at temperatures relevant to the TTL (< 200 K). Raffinose and HMMA, which form glasses at higher temperatures, nucleated ice heterogeneously at temperatures as high as 214.6 and 218.5 K respectively. We present the calculated ice active surface site density, n s , of the aerosols tested here and also of glassy citric acid aerosol as a function of relative humidity with respect to ice (RH i ). We also propose a parameterisation which can be used to estimate heterogeneous ice nucleation by glassy aerosol for use in cirrus cloud models up to ∼ 220 K. Finally, we show that heterogeneous nucleation by glassy aerosol may compete with ice nucleation on mineral dust particles in midlatitudes cirrus.

We report the first direct measurements of sucrose diffusion in aqueous solution at sucrose mass fractions above 0.75.