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Particles containing secondary organic material (SOM) are ubiquitous in the atmosphere and play a role in climate and air quality. Recently, research has shown that liquid-liquid phase separation (LLPS) occurs at high relative humidities (RH) (greater than ~ 95 %) in α-pinene-derived SOM particles free of inorganic salts while LLPS does not occur in isoprene-derived SOM particles free of inorganic salts. We expand on these findings by investigating LLPS in SOM particles free of inorganic salts produced from ozonolysis of β-caryophyllene, ozonolysis of limonene, and photo-oxidation of toluene. LLPS was observed at greater than ~ 95 % RH in the biogenic SOM particles derived from β-caryophyllene and limonene while LLPS was not observed in the anthropogenic SOM particles derived from toluene at 290 ± 1 K. This work combined with the earlier work on LLPS in SOM particles free of inorganic salts suggests that the occurrence of LLPS in SOM particles free of inorganic salts is related to the average oxygen-to-carbon elemental ratio (O : C) of the organic material. When the average O : C is between 0.25 and 0.60, LLPS was observed, but when the average O : C was between 0.52 and 1.3, LLPS was not observed. These results help explain the difference between the hygroscopic parameter k of SOM particles measured above and below water saturation in the laboratory and field, and have implications for predicting the cloud condensation nucleation properties of SOM particles.

A number of new measurement methods for ice nucleating particles (INPs) have been introduced in recent years, and it is important to address how these methods compare. Laboratory comparisons of instruments sampling major INP types are common, but few comparisons have occurred for ambient aerosol measurements exploring the utility, consistency and complementarity of different methods to cover the large dynamic range of INP concentrations that exists in the atmosphere. In this study, we assess the comparability of four offline immersion freezing measurement methods (Colorado State University Ice Spectrometer, IS; North Carolina State University Cold Stage, CS; National Institute for Polar Research Cryogenic Refrigerator Applied to Freezing Test, CRAFT; University of British Columbia Micro-Orifice Uniform Deposit Impactor – Droplet Freezing Technique, MOUDI-DFT) and an online method (continuous flow diffusion chamber, CFDC) used in a manner deemed to promote/maximize immersion freezing, for the detection of INP in ambient aerosols at different locations and in different sampling scenarios. We also investigated the comparability of different aerosol collection methods used with offline immersion freezing instruments. Excellent agreement between all methods could be obtained for several cases of co-sampling with perfect temporal overlap. Even for sampling periods that were not fully equivalent, the deviations between atmospheric INP number concentrations measured with different methods were mostly less than one order of magnitude. In some cases, however, the deviations were larger and not explicable without sampling and measurement artifacts. Overall, the immersion freezing methods seem to effectively capture INP that activate as single particles in the modestly supercooled temperature regime (> −20 °C), although more comparisons are needed in this temperature regime that is difficult to capture with online methods. Relative to the CFDC method, three immersion freezing methods that disperse particles into a bulk liquid (IS, CS, CRAFT) exhibit a positive bias in measured INP number concentrations at below −20 °C, increasing with decreasing temperature. This bias was present, but much less pronounced for a method that condenses separate water droplets onto limited numbers of particles prior to cooling and freezing (MOUDI-DFT). Potential reasons for the observed differences are discussed, and further investigations are required to elucidate the role of all factors involved.

The sea–surface microlayer and bulk seawater can contain ice-nucleating particles (INPs) and these INPs can be emitted into the atmosphere. Our current understanding of the properties, concentrations, spatial and temporal distributions of INPs in the microlayer and bulk seawater is limited. In this study we investigate the concentrations and properties of INPs in microlayer and bulk seawater samples collected in the Canadian Arctic during the summer of 2014. INPs were ubiquitous in the microlayer and bulk seawater with freezing temperatures as high as −14 °C. A strong negative correlation (R = −0.7, p = 0.02) was observed between salinity and freezing temperatures (after correction for freezing depression by the salts). One possible explanation is that INPs were associated with melting sea ice. Heat and filtration treatments of the samples show that the INPs were likely biological materials with sizes between 0.02 μm and 0.2 μm in diameter, consistent with previous measurements off the coast of North America and near Greenland in the Arctic. The concentrations of INPs in the microlayer and bulk seawater were consistent with previous measurements at several other locations off the coast of North America. However, our average microlayer concentration was lower than previous observations made near Greenland in the Arctic. This difference could not be explained by chlorophyll a concentrations derived from satellite measurements. In addition, previous studies found significant INP enrichment in the microlayer, relative to bulk seawater, which we did not observe in this study. While further studies are needed to understand these differences, we confirm that there is a source of INP in the microlayer and bulk seawater in the Canadian Arctic that may be important for atmospheric INP concentrations.

When simulating the formation and life cycle of secondary organic aerosol (SOA) with chemical transport models, it is often assumed that organic molecules are well mixed within SOA particles on the timescale of 1 h. While this assumption has been debated vigorously in the literature, the issue remains unresolved in part due to a lack of information on the mixing times within SOA particles as a function of both temperature and relative humidity. Using laboratory data, meteorological fields, and a chemical transport model, we estimated how often mixing times are α-pinene SOA using room-temperature and low-temperature viscosity data for α-pinene SOA generated in the laboratory using mass concentrations of ∼ 1000 µg m−3. Based on this parameterization, the mixing times within α-pinene SOA are 0.5 µg m−3 at the surface). Next, as a starting point to quantify how often mixing times of organic molecules are α-pinene SOA generated using low, atmospherically relevant mass concentrations, we developed a temperature-independent parameterization for viscosity using the room-temperature viscosity data for α-pinene SOA generated in the laboratory using a mass concentration of ∼ 70 µg m−3. Based on this temperature-independent parameterization, mixing times within α-pinene SOA are α-pinene SOA generated using low, atmospherically relevant mass concentrations. Finally, a parameterization for viscosity of anthropogenic SOA as a function of temperature and RH was developed using sucrose–water data. Based on this parameterization, and assuming sucrose is a good proxy for anthropogenic SOA, 70 and 83 % of the mixing times within anthropogenic SOA in the PBL are

Ice nucleating particles (INP) are known to affect the amount of ice in mixed-phase clouds, thereby influencing many of their properties. The atmospheric INP concentration changes by orders of magnitude from terrestrial to marine environments, which typically contain much lower concentrations. Many modelling studies use parameterizations for heterogeneous ice nucleation and cloud ice processes that do not account for this difference because they were developed based on measurements predominantly from terrestrial environments. Errors in the assumed INP concentration will influence the simulated amount of ice in mixed-phase clouds, leading to errors in top-of-atmosphere radiative flux and ultimately the climate sensitivity of climate models. Here we develop a global model of INP concentrations relevant for mixed-phase clouds based on laboratory and field measurements of ice nucleation by K-feldspar (an ice-active component of desert dust) and marine organic aerosols (from sea spray). The simulated global distribution of INP concentrations based on these two-species agrees much better with currently available ambient measurements than when INP concentrations are assumed to depend only on temperature or particle size. Underestimation of INP concentrations in some terrestrial locations may be due to neglect of INP from other terrestrial sources. Our model indicates that, on a monthly or yearly average basis, desert dusts dominate the contribution to the INP population over much of the world, but marine organics become increasingly important in the world's remote oceans and can dominate in the Southern Ocean at some time of the year. Furthermore, we show that day-to-day variability is important and since desert dust aerosol tends to be sporadic, marine organics dominate the INP population on many days per month in much of the mid and high latitude northern hemisphere. This study advances our understanding of which aerosol species need to be included in order to adequately describe the global and regional distribution of INP in models, which will guide ice nucleation researchers on where to focus future laboratory and field work.

© 2017 American Chemical Society. Laboratory studies of atmospheric chemistry characterize the nature of atmospherically relevant processes down to the molecular level, providing fundamental information used to assess how human activities drive environmental phenomena such as climate change, urban air pollution, ecosystem health, indoor air quality, and stratospheric ozone depletion. Laboratory studies have a central role in addressing the incomplete fundamental knowledge of atmospheric chemistry. This article highlights the evolving science needs for this community and emphasizes how our knowledge is far from complete, hindering our ability to predict the future state of our atmosphere and to respond to emerging global environmental change issues. Laboratory studies provide rich opportunities to expand our understanding of the atmosphere via collaborative research with the modeling and field measurement communities, and with neighboring disciplines.

We observed a transient noncentrosymmetric phase of ice at water/mineral interfaces during freezing, which enhanced the intensity of the IR-visible sum frequency generation intensity by up to 20-fold. The lifetime of the transient phase was several minutes. Since the most stable form of ice, hexagonal and cubic ice, are centrosymmetric, our study suggests the transient existence of stacking-disordered ice during the freezing process at water/mineral interfaces. Stacking-disordered ice, which has only been observed in bulk ice at temperatures lower than −20 °C, is a random mixture of layers of hexagonal ice and cubic ice. However, the transient phase at the ice/mineral interface was observed at temperatures as high as −1 °C. It suggests that the mineral surface may play a role in promoting and stabilizing the formation of stacking-disordered ice at the interface.

Heterogeneous nucleation of ice induced by organic materials is of fundamental importance for climate, biology, and industry. Among organic ice-nucleating surfaces, monolayers of long chain alcohols are particularly effective, while monolayers of fatty acids are significantly less so. As these monolayers expose to water hydroxyl groups with an order that resembles the one in the basal plane of ice, it was proposed that lattice matching between ice and the surface controls their ice-nucleating efficiency. Organic monolayers are soft materials and display significant fluctuations. It has been conjectured that these fluctuations assist in the nucleation of ice. Here we use molecular dynamic simulations and laboratory experiments to investigate the relationship between the structure and fluctuations of hydroxylated organic surfaces and the temperature at which they nucleate ice. We find that these surfaces order interfacial water to form domains with ice-like order that are the birthplace of ice. Both mismatch and fluctuations decrease the size of the preordered domains and monotonously decrease the ice freezing temperature. The simulations indicate that fluctuations depress the freezing efficiency of monolayers of alcohols or acids to half the value predicted from lattice mismatch alone. The model captures the experimental trend in freezing efficiencies as a function of chain length and predicts that alcohols have higher freezing efficiency than acids of the same chain length. These trends are mostly controlled by the modulation of the structural mismatch to ice. We use classical nucleation theory to show that the freezing efficiencies of the monolayers are directly related to their free energy of binding to ice. This study provides a general framework to relate the equilibrium thermodynamics of ice binding to a surface and the nonequilibrium ice freezing temperature and suggests that these could be predicted from the structure of interfacial water.

As one aspect of the NETwork on Climate and Aerosols: addressing key uncertainties in Remote Canadian Environments (NETCARE), measurements of the cloud condensation nucleation properties of 50 and 100 nm aerosol particles were conducted at Ucluelet on the west coast of Vancouver Island in August 2013. The overall hygroscopicity parameter of the aerosol (κambient) exhibited a wide variation, ranging from 0.14 ± 0.05 to 1.08 ± 0.40 (where the uncertainty represents the systematic error). The highest κ values arose when the organic-to-sulfate ratio of the aerosol was lowest and when winds arrived from the west after transport through the marine boundary layer. The average κambient during this time was 0.57 ± 0.16, where the uncertainty represents the standard deviation. At most other times, the air was predominantly influenced by both marine and continental emissions, which had lower average PM1 κambient values (max value, 0.41 ± 0.08). The two-day average aerosol ionic composition also showed variation, but was consistently acidic and dominated by ammonium (18–56% by mole) and sulfate (19–41% by mole), with only minor levels of sodium or chloride. Average κorg (hygroscopicity parameter for the aerosol's organic component) values were estimated using PM1 aerosol composition data and by assuming that the ratio of aerosol organic to sulfate mass is related directly to the composition of the size-selected particles.

Heterogeneous ice nucleation at solid surfaces is important in many physical systems including the Earth's atmosphere. AgI is one of the best ice nucleating agents known; however, why AgI is such an effective ice nucleus is unclear. Using molecular dynamics simulations, we show that a good lattice match between ice and a AgI surface is insufficient to predict the ice nucleation ability of the surface. Seven faces modeled to represent surfaces of both β-AgI and γ-AgI, each having a good lattice match with hexagonal and/or cubic ice, are considered, but ice nucleation is observed for only three. Our model simulations clearly show that the detailed atomistic structure of the surface is of crucial importance for ice nucleation. For example, when AgI is cleaved along certain crystal planes two faces result, one with silver ions and the other with iodide ions exposed as the outermost layer. Both faces have identical lattice matches with ice, but in our simulations ice nucleation occurred only at silver exposed surfaces. Moreover, although hexagonal ice is often the only polymorph of ice considered in discussions of heterogeneous ice nucleation, cubic ice was frequently observed in our simulations. We demonstrate that one possible mechanism of ice nucleation by AgI consists of particular AgI surfaces imposing a structure in the adjacent water layer that closely resembles a layer that exists in bulk ice (hexagonal or cubic). Ice nucleates at these surfaces and grows almost layer-by-layer into the bulk.

We studied the ice nucleation properties of 12 different species of fungal spores chosen from three classes: Agaricomycetes, Ustilaginomycetes, and Eurotiomycetes. Agaricomycetes include many types of mushroom species and are widely distributed over the globe. Ustilaginomycetes are agricultural pathogens and have caused widespread damage to crops. Eurotiomycetes are found on all types of decaying material and include important human allergens. We focused on these classes because they are thought to be abundant in the atmosphere and because there is very little information on the ice nucleation ability of these classes of spores in the literature. All of the fungal spores investigated contained some fraction of spores that serve as ice nuclei at temperatures warmer than homogeneous freezing. The cumulative number of ice nuclei per spore was 0.001 at temperatures between −19 °C and −29 °C, 0.01 between −25.5 °C and −31 °C, and 0.1 between −26 °C and −31.5 °C. On average, the order of ice nucleating ability for these spores is Ustilaginomycetes > Agaricomycetes ≃ Eurotiomycetes. The freezing data also suggests that, at temperatures ranging from −20 °C to −25 °C, all of the fungal spores studied here are less efficient ice nuclei compared to Asian mineral dust on a per surface area basis. We used our new freezing results together with data in the literature to compare the freezing temperatures of spores from the phyla Basidiomycota and Ascomycota, which together make up 98% of known fungal species found on Earth. The data show that within both phyla (Ascomycota and Basidiomycota), there is a wide range of freezing properties, and also that the variation within a phylum is greater than the variation between the average freezing properties of the phyla. Using a global chemistry–climate transport model, we investigated whether ice nucleation on the studied spores, followed by precipitation, can influence the transport and global distributions of these spores in the atmosphere. Simulations suggest that inclusion of ice nucleation scavenging of these fungal spores in mixed-phase clouds can decrease the annual mean concentrations of fungal spores in near-surface air over the oceans and polar regions, and decrease annual mean concentrations in the upper troposphere.

Laboratory studies of liquid–liquid phase separation in particles containing organic species and inorganic salts of atmospheric relevance are reviewed. The oxygen-to-carbon elemental ratio (O:C) of the organic component appears to be the most useful parameter for estimating, to a first approximation, the occurrence of liquid–liquid phase separation and the separation relative humidity (SRH) in these particles. A trend of decreasing SRH for increasing O:C was found for simple organic–inorganic mixtures (

As the relative humidity varies from high to low values in the atmosphere, particles containing organic species and inorganic salts may undergo liquid–liquid phase separation. The majority of the laboratory work on this subject has used ammonium sulfate as the inorganic salt. In the following we studied liquid–liquid phase separation in particles containing organics mixed with the following salts: ammonium sulfate, ammonium bisulfate, ammonium nitrate and sodium chloride. In each experiment one organic was mixed with one inorganic salt and the liquid–liquid phase separation relative humidity (SRH) was determined. Since we studied 23 different organics mixed with four different salts, a total of 92 different particle types were investigated. Out of the 92 types, 49 underwent liquid–liquid phase separation. For all the inorganic salts, liquid–liquid phase separation was never observed when the oxygen-to-carbon elemental ratio (O : C) &geq; 0.8 and was always observed for O : C < 0.5. For 0.5 &leq; O : C < 0.8, the results depended on the salt type. Out of the 23 organic species investigated, the SRH of 20 organics followed the trend: (NH4)2SO4 &geq; NH4HSO4 &geq; NaCl &geq; NH4NO3. This trend is consistent with previous salting out studies and the Hofmeister series. Based on the range of O : C values found in the atmosphere and the current results, liquid–liquid phase separation is likely a frequent occurrence in both marine and non-marine environments.

The phase states of atmospheric particles influence their roles in physicochemical processes related to air quality and climate. The phases of particles containing secondary organic materials (SOMs) are still uncertain, especially for SOMs produced from aromatic precursor gases. In this work, efflorescence and deliquescence phase transitions, as well as phase separation, in particles composed of toluene-derived SOM, ammonium sulfate, and water were studied by hygroscopic tandem differential mobility analysis (HTDMA) and optical microscopy. The SOM was produced in the Harvard Environmental Chamber by photo-oxidation of toluene at chamber relative humidities of5 and 40%. The efflorescence and deliquescence relative humidities (ERH and DRH, respectively, studied by HTDMA) of ammonium sulfate decreased as the SOM organic fraction ε in the particle increased, dropping from DRH = 80% and ERH = 31% for ε = 0.0 to DRH = 58% and ERH = 0% for ε = 0.8. For ε0.2, the DRH and ERH to first approximation did not change with the organic volume fraction. This observation is consistent with independent behaviors for ε0.2 of water-infused toluene-derived SOM and aqueous ammonium sulfate, suggesting phase immiscibility between the two. Optical microscopy of particles prepared for ε = 0.12 confirmed phase separation for RH85%. For ε from 0.2 to 0.8, the DRH and ERH values steadily decreased, as studied by HTDMA. This result is consistent with one-phase mixing of ammonium sulfate, SOM, and water. Optical microscopy for particles of ε = 0.8 confirmed this result. Within error, increased exposure times of the aerosol in the HTDMA from 0.5 to 30 s affected neither the ERH(ε) nor DRH(ε) curves, implying an absence of kinetic effects on the observations over the studied time scales. For ε0.5, the DRH values of ammonium sulfate in mixtures with SOM produced at5% RH were offset by -3 to -5% RH compared to the results for SOM produced at 40% RH, suggesting differences in SOM chemistry. The observed miscibility gap (i.e., phase separation) between toluene-derived SOM and aqueous ammonium sulfate across a limited range of organic volume fractions differentiates this SOM from previous reports for isoprene-derived SOM of full miscibility and for α-pinene-derived SOM of nearly full immiscibility with aqueous ammonium sulfate.

[1] Rust and bunt spores that act as ice nuclei (IN) could change the formation characteristics and properties of ice-containing clouds. In addition, ice nucleation on rust and bunt spores, followed by precipitation, may be an important removal mechanism of these spores from the atmosphere. Using an optical microscope, we studied the ice nucleation properties of spores from four rust species (Puccinia graminis, Puccinia triticina, Puccinia allii, and Endocronartium harknesssii) and two bunt species (Tilletia laevis and Tilletia tritici) immersed in water droplets. We show that the cumulative number of IN per spore is 5 × 10−3, 0.01, and 0.10 at temperatures of roughly −24°C, −25°C, and −28°C, respectively. Using a particle dispersion model, we also investigated if these rust and bunt spores will reach high altitudes in the atmosphere where they can cause heterogeneous freezing. Simulations suggest that after 3 days and during periods of high spore production, between 6 and 9% of 15 µm particles released over agricultural regions in Kansas (U.S.), North Dakota (U.S.), Saskatchewan (Canada), and Manitoba (Canada) can reach at least 6 km in altitude. An altitude of 6 km corresponds to a temperature of roughly −25°C for the sites chosen. The combined results suggest that (a) ice nucleation by these fungal spores could play a role in the removal of these particles from the atmosphere and (b) ice nucleation by these rust and bunt spores are unlikely to compete with mineral dust on a global and annual scale at an altitude of approximately 6 km.

Particles composed of secondary organic material (SOM) are abundant in the lower troposphere. The viscosity of these particles is a fundamental property that is presently poorly quantified yet required for accurate modeling of their formation, growth, evaporation, and environmental impacts. Using two unique techniques, namely a “bead-mobility” technique and a “poke-flow” technique, in conjunction with simulations of fluid flow, the viscosity of the water-soluble component of SOM produced by α -pinene ozonolysis is quantified for 20- to 50-μm particles at 293–295 K. The viscosity is comparable to that of honey at 90% relative humidity (RH), similar to that of peanut butter at 70% RH, and at least as viscous as bitumen at ≤30% RH, implying that the studied SOM ranges from liquid to semisolid or solid across the range of atmospheric RH. These data combined with simple calculations or previous modeling studies are used to show the following: ( i ) the growth of SOM by the exchange of organic molecules between gas and particle may be confined to the surface region of the particles for RH ≤ 30%; ( ii ) at ≤30% RH, the particle-mass concentrations of semivolatile and low-volatility organic compounds may be overpredicted by an order of magnitude if instantaneous equilibrium partitioning is assumed in the bulk of SOM particles; and ( iii ) the diffusivity of semireactive atmospheric oxidants such as ozone may decrease by two to five orders of magnitude for a drop in RH from 90% to 30%. These findings have possible consequences for predictions of air quality, visibility, and climate.

Herein, a method for the determination of viscosities of small sample volumes is introduced, with important implications for the viscosity determination of particle samples from environmental chambers (used to simulate atmospheric conditions). The amount of sample needed is < 1 μl, and the technique is capable of determining viscosities (η) ranging between 10−3 and 103 Pascal seconds (Pa s) in samples that cover a range of chemical properties and with real-time relative humidity and temperature control; hence, the technique should be well-suited for determining the viscosities, under atmospherically relevant conditions, of particles collected from environmental chambers. In this technique, supermicron particles are first deposited on an inert hydrophobic substrate. Then, insoluble beads (~1 μm in diameter) are embedded in the particles. Next, a flow of gas is introduced over the particles, which generates a shear stress on the particle surfaces. The sample responds to this shear stress by generating internal circulations, which are quantified with an optical microscope by monitoring the movement of the beads. The rate of internal circulation is shown to be a function of particle viscosity but independent of the particle material for a wide range of organic and organic-water samples. A calibration curve is constructed from the experimental data that relates the rate of internal circulation to particle viscosity, and this calibration curve is successfully used to predict viscosities in multicomponent organic mixtures.

In the following we determine the viscosity of four polyols (2-methyl-1,4-butanediol, 1,2,3-butanetriol, 2-methyl-1,2,3,4-butanetetrol, and 1,2,3,4-butanetetrol) and three saccharides (glucose, raffinose and maltohexaose) mixed with water. The polyol studies were carried out to quantify the relationship between viscosity and the number of hydroxyl (OH) functional groups in organic molecules, whilst the saccharide studies were carried out to quantify the relationship between viscosity and molar mass for highly oxidised organic molecules. Each of the polyols was of viscosity less than or equal to ≤ 6.5e2 Pa s, and a linear relationship was observed between log10 (viscosity) and the number of OH functional groups (R2 ≥ 0.99) for several carbon backbones. The linear relationship suggests that viscosity increases by 1–2 orders of magnitude with the addition of an OH functional group to a carbon backbone. For saccharide-water particles, studies at 28 % RH show an increase in viscosity of 3.6–6.0 orders of magnitude as the molar mass of the saccharide is increased from 180 to 342 g mol−1, and studies at 77–80 % RH, show an increase in viscosity 4.6–6.2 orders of magnitude as molar mass increases from 180 to 991 g mol−1. These results suggest oligomerisation of highly oxidised compounds in atmospheric SOM could lead to large increases in viscosity, and may be at least partially responsible for the high viscosities that are observed in some SOM. Finally, two quantitative structure-property relationship models were used to predict the viscosity of the four polyols studied. The model of Sastri and Rao (1992) was determined to over-predict the viscosity of each of the polyols, with the over-prediction being up to 19 orders of magnitude. The viscosities predicted by the model of Marrero-Morejón and Pardillo-Fontdevila (2000) were much closer to the experimental values, with no values differing by more than 1.3 orders of magnitude.

Biomass burning emissions emit a significant amount of trace gases and aerosols and can affect atmospheric chemistry and radiative forcing for hundreds or thousands of kilometres downwind. They can also contribute to exceedances of air quality standards and have negative impacts on human health. We present a case study of an intense wildfire plume from Siberia that affected the air quality across the Pacific Northwest on 6–10 July 2012. Using satellite measurements (MODIS True Colour RGB imagery and MODIS AOD), we track the wildfire smoke plume from its origin in Siberia to the Pacific Northwest where subsidence ahead of a subtropical Pacific High made the plume settle over the region. The normalized enhancement ratios of O3 and PM1 relative to CO of 0.26 and 0.08 are consistent with a plume aged 6–10 days. The aerosol mass in the plume was mainly submicron in diameter (PM1 ∕ PM2.5 = 0.96) and the part of the plume sampled at the Whistler High Elevation Monitoring Site (2182 m a.s.l.) was 88 % organic material. Stable atmospheric conditions along the coast limited the initial entrainment of the plume and caused local anthropogenic emissions to build up. A synthesis of air quality from the regional surface monitoring networks describes changes in ambient O3 and PM2.5 during the event and contrasts them to baseline air quality estimates from the AURAMS chemical transport model without wildfire emissions. Overall, the smoke plume contributed significantly to the exceedances in O3 and PM2.5 air quality standards and objectives that occurred at several communities in the region during the event. Peak enhancements in 8 h O3 of 34–44 ppbv and 24 h PM2.5 of 10–32 µg m−3 were attributed to the effects of the smoke plume across the Interior of British Columbia and at the Whistler Peak High Elevation Site. Lesser enhancements of 10–12 ppbv for 8 h O3 and of 4–9 µg m−3 for 24 h PM2.5 occurred across coastal British Columbia and Washington State. The findings suggest that the large air quality impacts seen during this event were a combination of the efficient transport of the plume across the Pacific, favourable entrainment conditions across the BC interior, and the large scale of the Siberian wildfire emissions. A warming climate increases the risk of increased wildfire activity and events of this scale reoccurring under appropriate meteorological conditions.

Ice nucleating particles (INPs) are vital for ice initiation in, and precipitation from, mixed-phase clouds. A source of INPs from oceans within sea spray aerosol (SSA) emissions has been suggested in previous studies but remained unconfirmed. Here, we show that INPs are emitted using real wave breaking in a laboratory flume to produce SSA. The number concentrations of INPs from laboratory-generated SSA, when normalized to typical total aerosol number concentrations in the marine boundary layer, agree well with measurements from diverse regions over the oceans. Data in the present study are also in accord with previously published INP measurements made over remote ocean regions. INP number concentrations active within liquid water droplets increase exponentially in number with a decrease in temperature below 0 °C, averaging an order of magnitude increase per 5 °C interval. The plausibility of a strong increase in SSA INP emissions in association with phytoplankton blooms is also shown in laboratory simulations. Nevertheless, INP number concentrations, or active site densities approximated using “dry” geometric SSA surface areas, are a few orders of magnitude lower than corresponding concentrations or site densities in the surface boundary layer over continental regions. These findings have important implications for cloud radiative forcing and precipitation within low-level and midlevel marine clouds unaffected by continental INP sources, such as may occur over the Southern Ocean.

Silver iodide is one of the most effective ice nuclei known. We use molecular dynamics simulations to investigate ice nucleation by AgI disks and plates with radii ranging from 1.15 to 2.99 nm. It is shown that disks and plates in this size range are effective ice nuclei, nucleating bulk ice at temperatures as warm as 14 K below the equilibrium freezing temperature, on simulation time scales (up to a few hundred nanoseconds). Ice nucleated on the Ag exposed surface of AgI disks and plates. Shortly after supercooling an ice cluster forms on the AgI surface. The AgI-stabilized ice cluster fluctuates in size as time progresses, but, once formed, it is constantly present. Eventually, depending on the disk or plate size and the degree of supercooling, a cluster fluctuation achieves critical size, and ice nucleates and rapidly grows to fill the simulation cell. Larger AgI disks and plates support larger ice clusters and hence can nucleate ice at warmer temperatures. This work may be useful for understanding the mechanism of ice nucleation on nanoparticles and active sites of larger atmospheric particles.

Detailed information on the size of ice-nucleating particles (INPs) may be useful in source identification, modeling their transport in the atmosphere to improve climate predictions, and determining how effectively or ineffectively instrumentation used for quantifying INPs in the atmosphere captures the full INP population. In this study we report immersion-mode INP number concentrations as a function of size at six ground sites in North America and one in Europe using the micro-orifice uniform-deposit impactor droplet freezing technique (MOUDI-DFT), which combines particle size-segregation by inertial impaction and a microscope-based immersion freezing apparatus. The lowest INP number concentrations were observed at Arctic and alpine locations and the highest at suburban and agricultural locations, consistent with previous studies of INP concentrations in similar environments. We found that 91 ± 9, 79 ± 17, and 63 ± 21 % of INPs had an aerodynamic diameter > 1 µm at ice activation temperatures of −15, −20, and −25 °C, respectively, when averaging over all sampling locations. In addition, 62 ± 20, 55 ± 18, and 42 ± 17 % of INPs were in the coarse mode (> 2.5 µm) at ice activation temperatures of −15, −20, and −25 °C, respectively, when averaging over all sampling locations. These results are consistent with six out of the nine studies in the literature that have focused on the size distribution of INPs in the atmosphere. Taken together, these findings strongly suggest that supermicron and coarse-mode aerosol particles are a significant component of the INP population in many different ground-level environments. Further size-resolved studies of INPs as a function of altitude are required since the size distribution of INPs may be different at high altitudes due to size-dependent removal processes of atmospheric particles.

The hygroscopic phase transitions of ammonium sulfate mixed with isoprene-derived secondary organic material were investigated in aerosol experiments. The organic material was produced by isoprene photo-oxidation at 40% and 60% relative humidity. The low volatility fraction of the photo-oxidation products condensed onto ammonium sulfate particles. The particle-phase organic material had oxygen-to-carbon ratios of 0.67 to 0.74 (±0.2) for mass concentrations of 20 to 30 μg m−3. The deliquescence, efflorescence, and phase miscibility of the mixed particles were investigated using a dual arm tandem differential mobility analyzer. The isoprene photo-oxidation products induced deviations in behavior relative to pure ammonium sulfate. Compared to an efflorescence relative humidity (ERH) of 30 to 35% for pure ammonium sulfate, efflorescence was eliminated for aqueous particles having organic volume fractions &varepsilon; of 0.6 and greater. Compared to a deliquescence relative humidity (DRH) of 80% for pure ammonium sulfate, the DRH steadily decreased with increasing &varepsilon;, approaching a DRH of 40% for &varepsilon; of 0.9. Parameterizations of the DRH(&varepsilon;) and ERH(&varepsilon;) curves were as follows: DRH(&varepsilon;)= ∑i ci,d &varepsilon;i valid for 0 ≤ &varepsilon; ≤0.86 and ERH(&varepsilon;)= ∑ i ci,e &varepsilon;i valid for 0 ≤ &varepsilon; ≤ 0.55 for the coefficients c0,d= 80.67, c0,e = 28.35, c1,d = −11.45, c1,e = −13.66, c2,d = 0, c2,e = 0, c3,d = 57.99, c3,e = -83.80, c4,d = −106.80, and c4,e = 0. The molecular description that is thermodynamically implied by these strongly sloped DRH(&varepsilon;) and ERH(&varepsilon;) curves is that the organic isoprene photo-oxidation products, the inorganic ammonium sulfate, and water form a miscible liquid phase even at low relative humidity. This phase miscibility is in contrast to the liquid-liquid separation that occurs for some other types of secondary organic material. These differences in liquid-liquid separation are consistent with a prediction recently presented in the literature that the bifurcation between liquid-liquid phase separation versus mixing depends on the oxygen-to-carbon ratio of the organic material. The conclusions are that the influence of secondary organic material on the hygroscopic properties of ammonium sulfate varies with organic composition and that the degree of oxygenation of the organic material, which is a measurable characteristic of complex organic materials, is an important variable influencing the hygroscopic properties of mixed organic-inorganic particles.

Owing to the large-scale transport of pollution-derived aerosols from the mid-latitudes to the Arctic, most of the aerosols are coated with acidic sulfate during winter in the Arctic. Recent laboratory experiments have shown that acid coating on dust particles substantially reduces the ability of these particles to nucleate ice crystals. Simulations performed using the Limited Area version of the Global Multiscale Environmental Model (GEM-LAM) are used to assess the potential effect of acid-coated ice nuclei on the Arctic cloud and radiation processes during January and February 2007. Ice nucleation is treated using a new parameterization based on laboratory experiments of ice nucleation on sulphuric acid-coated and uncoated kaolinite particles. Results show that acid coating on dust particles has an important effect on cloud microstructure, atmospheric dehydration, radiation and temperature over the Central Arctic, which is the coldest part of the Arctic. Mid and upper ice clouds are optically thinner while low-level mixed-phase clouds are more frequent and persistent. These changes in the cloud microstructures affect the radiation at the top of the atmosphere with longwave negative cloud forcing values ranging between 0 and − 6 W m−2 over the region covered by the Arctic air mass. Copyright © 2012 Royal Meteorological Society

Deposition nucleation on two mineral species, kaolinite and illite, was studied using a flow cell coupled to an optical microscope. The results show that the Sice conditions when ice first nucleated, defined as the onset Sice (Sice,onset), is a strong function of the surface area available for nucleation, varying from 100% to 125% at temperatures between 242 and 239 K. The surface area dependent data could not be described accurately using classical nucleation theory and the assumption of a single contact angle (defined here as the single-α model). These results suggest that caution should be applied when using contact angles determined from Sice,onset data and the single-α model. In contrast to the single-α model, the active site model, the deterministic model, and a model with a distribution of contact angles fit the data within experimental uncertainties. Parameters from the fits to the data are presented.

Six microphysics schemes implemented in the climate version of the Environment Canada's Global Multiscale Environmental (GEM) model are used to simulate the cloud and radiation processes observed during Surface Heat Budget of the Arctic Ocean (SHEBA) field experiment. The simplest microphysics scheme (SUN) has one prognostic variable: the total cloud water content. The second microphysics scheme (MLO) has 12 prognostic variables. The four other microphysics schemes are modified versions of MLO. A new parameterization for heterogeneous ice nucleation based on laboratory experiments is included in these versions of MLO. One is for uncoated ice nuclei (ML-NAC) and another is for sulfuric acid coated ice nuclei (ML-AC). ML-AC and ML-NAC have been developed to distinguish non-polluted and polluted air masses, the latter being common over the Arctic during winter and spring. A sensitivity study, in which the dust concentration is reduced by a factor 5, is also performed to assess the sensitivity of the results to the dust concentration in ML-AC-test and ML-NAC-test. Results show that SUN, ML-AC and ML-AC-test reproduce quite well the downward longwave radiation and cloud radiative forcing during the cold season. The good results obtained with SUN are due to compensating errors. It overestimates cloud fraction and underestimates cloud liquid water path during winter. ML-AC and ML-AC-test reproduces quite well all these variables and their relationships. MLO, ML-NAC and ML-NAC-test underestimate the cloud liquid water path and cloud fraction during the cold season, which leads to an underestimation of the downward longwave radiation at surface. During summer, all versions of the model underestimate the downward shortwave radiation at surface. ML-AC and ML-NAC overestimate the total cloud water during the warm season, however, they reproduce relatively well the relationships between cloud radiative forcing and cloud microstructure, which is not the case for the most simple scheme SUN.

On 30 August 2009, intense forest fires in interior British Columbia (BC) coupled with winds from the east and northeast resulted in transport of a broad forest fire plume across southwestern BC. The physico-chemical and optical characteristics of the plume as observed from Saturna Island (AERONET), CORALNet-UBC and the Whistler Mountain air chemistry facility were consistent with forest fire plumes that have been observed elsewhere in continental North America. However, the importance of three-dimensional transport in relation to the interpretation of mountaintop chemistry observations is highlighted on the basis of deployment of both a CL31 ceilometer and a single particle mass spectrometer (SPMS) in a mountainous setting. The SPMS is used to identify the biomass plume based on levoglucosan and potassium markers. Data from the SPMS are also used to show that the biomass plume was correlated with nitrate, but not correlated with sulphate or sodium. This study not only provides baseline measurements of biomass burning plume physico-chemical characteristics in western Canada, but also highlights the importance of lidar remote sensing methods in the interpretation of mountaintop chemistry measurements.

Grand canonical Monte Carlo simulations are employed to investigate the structure of water adsorbed on kaolinite surfaces with trenchlike defects. The results obtained for two water models (SPC/E and TIP5P-E) at 235 K are essentially the same. Calculation of water density profiles in all three dimensions shows that a dense ordered state is present in our trench systems. The narrowest trenches have the highest water density and display clearly layered structures along the width and depth of a trench. The water within a trench shows distinct proton order and is strongly ferroelectric. These ordered structures might be important in the initial stages of nucleation and growth of ice on kaolinite surfaces.

Recent laboratory studies of water adsorption on kaolinite at 296 K, and at relative humidity (RH) values relevant for the atmosphere, have reported coverages ranging up to tens of monolayers. In contrast, recent simulations have suggested that atomistically smooth kaolinite surfaces uptake only monolayers (some slightly overgrown) at similar RH values. In an effort to possibly explain the laboratory data, we have performed water adsorption calculations on kaolinite surfaces containing trenchlike structures using the grand canonical Monte Carlo simulation method at 298 K. The results obtained show that the granularity of the surfaces can play a major role in the adsorption of multiple layers of water. For all trenches considered, multilayers of water were observed over a large range of RH. The narrowest trench investigated remained filled with water even in the very low RH regime (or=0.0003%). Increasing the trench width resulted in partial or complete trench filling depending on the RH value, with large water mounds growing on the step edges. This strong affinity for water is explained by very attractive water-lattice interactions inside the trenches, especially near the walls. Our calculations suggest that water adsorption in trenches, and possibly in other similar defects, can offer an explanation of the experimental results.

Grand canonical Monte Carlo calculations are employed to investigate water adsorption on kaolinite at 298 and 235 K. Both basal planes (the Al and Si surfaces) as well as two edge-like surfaces are considered. The general force field CLAYFF is used together with the SPC/E and TIP5P-E models for water. Problems that occur in single slab simulations due to arbitrary truncation of the point charge lattice are identified, and a working remedy is discussed. The edges and the Al surface adsorb water at subsaturation in the atmospherically relevant pressure range. The Si surface remains dry up to saturation. Both edges have a very strong affinity for water and adsorb continuously up to monolayer coverage. The Al surface has a weaker affinity for water but forms a subsaturation monolayer. On the Al surface, the monolayer is formed in an essentially sharp transition, and strong hysteresis is observed upon desorption. This indicates collective behavior among the water molecules which is not present for the edges. Binding energies of singly adsorbed water molecules at 10 K were determined to understand the differences in water uptake by the four kaolinite surfaces. Binding energies (SPC/E) of -21.6, -46.4, -73.5, and -94.1 kJ/mol, were determined for the Si surface, Al surface, unprotonated edge, and protonated edge, respectively. The water monolayer on the Al surface, particularly at 235 K, exhibits hexagonal patterns. However, the associated lattice parameters are not compatible with ice Ih. Water density and hydrogen bonding in the monolayers at both 298 and 235 K were also determined to better understand the structure of the adsorbed water.

A novel aerosol ion trap mass spectrometer combining pulsed IR laser desorption with electron impact (EI) ionization for single particle studies is described. The strengths of this instrument include a two-step desorption and ionization process to minimize matrix effects; electron impact ionization, a universal and well-characterized ionization technique; vaporization and ionization inside the ion trap to improve sensitivity; and an ion trap mass spectrometer for MSn experiments. The instrument has been used for mass spectral identification of laboratory generated pure aerosols in the 600 nm–1.1 μm geometric diameter range of a variety of aromatic and aliphatic compounds, as well as for tandem mass spectrometry studies (up to MS3) of single caffeine particles. We investigate the effect of various operational parameters on the mass spectrum and fragmentation patterns. The single particle detection limit of the instrument was found to be a 325 nm geometric diameter particle (8.7 × 107 molecules or 22 fg) for 2,4-dihydroxybenzoic acid. Lower single particle detection limits are predicted to be attainable by modifying the EI pulse. The use of laser desorption-electron impact (LD-EI) in an ion trap is a promising technique for determining the size and chemical composition of single aerosol particles in real time.

A laser based vacuum ultraviolet (VUV) light source using resonance enhanced four wave difference mixing in xenon gas was developed for near threshold ionization of organics in atmospheric aerosol particles. The source delivers high intensity pulses of VUV light (in the range of 1010 to 1013 photons/pulse depending on wavelength, 5 ns FWHM) with a continuously tunable wavelength from 122 nm (10.2 eV) to 168 nm (7.4 eV). The setup allows for tight (

A new flow reactor has been developed that allows the study of heterogeneous kinetics on an aqueous surface coated by an organic monolayer. Computational fluid dynamics simulations have been used to determine the flow characteristics for various experimental conditions. In addition a mathematical framework has been developed to derive the true first-order wall loss rate coefficient, k(1st)(w), from the experimentally observed wall loss rate, k(obs). Validation of the new flow reactor is performed by measuring the uptake of O(3) by canola oil as a function of pressure and flow velocity and the reactive uptake coefficients of N(2)O(5) by aqueous 60 wt % and 80 wt % H(2)SO(4). Using this new flow reactor, we also determined the reactive uptake coefficient of N(2)O(5) on aqueous 80 wt % H(2)SO(4) solution coated with an 1-octadecanol (C(18)H(37)OH) monolayer. The uptake coefficient was determined as (8.1 +/- 3.2) x 10-4, which is about 2 orders of magnitude lower compared to the reactive uptake coefficient on a pure aqueous 80 wt % H(2)SO(4) solution. Our measured reactive uptake coefficient can be considered as a lower limit for the reactive uptake coefficient of aqueous aerosols coated with organic monolayers in the atmosphere, because in the atmosphere organic monolayers will likely also consist of surfactants with shorter lengths and branched structures which will have a smaller overall effect.

The diffusion of OH, HO2, and O3 in He, and of OH in air, has been investigated using a coated-wall flow tube reactor coupled to a chemical ionization mass spectrometry. The diffusion coefficients were determined from measurements of the loss of the reactive species to the flow tube wall as a function of pressure. On the basis of the experimental results, D(OH-He) = 662 +/- 33 Torr cm2 s-1, D(OH-air) = 165 +/- 20 Torr cm2 s-1, D(HO2-He) = 430 +/- 30 Torr cm2 s-1, and D(O3-He) = 410 +/- 25 Torr cm2 s-1 at 296 K. We show that the measured values for OH and HO2 are in better agreement with measured values of their polar analogues (H2O and H2O2) compared with measured values of their nonpolar analogues (O and O2). The measured value for OH in air is 25% smaller than that for O (the nonpolar analogue). The difference between the measured value for HO2 and O2 (the nonpolar analogue) in air is expected to be even larger. Also we show that calculations of the diffusion coefficients based on Lennard-Jones potentials are in excellent agreement with the measurements. This gives further confidence that these calculations can be used to estimate accurate diffusion coefficients for conditions where laboratory data currently do not exist.

The reactivity of secondary organic material (SOM) of variable viscosity, ranging from nonliquid to liquid physical states, was studied. The SOM, produced in aerosol form from terpenoid and aromatic precursor species, was reacted with ammonia at variable relative humidity (RH). The ammonium-to-organic mass ratio (MNH4+/MOrg) increased monotonically from5% RH to a limiting value at a threshold RH, implicating a transition from particle reactivity limited by diffusion at low RH to one limited by other factors at higher RH. For the studied size distributions and reaction times, the transition corresponded to a diffusivity above 10-17.5 ± 0.5 m2 s-1. The threshold RH values for the transition were5% RH for isoprene-derived SOM, 35-45% RH for SOM derived from α-pinene, toluene, m-xylene, and 1,3,5-trimethylbenzene, and90% for β-caryophyllene-derived SOM. The transition RH for reactivity differed in all cases from the transition RH of a nonliquid to a liquid state. For instance, for α-pinene-derived SOM the transition for chemical reactivity of 35-45% RH can be compared to the nonliquid to liquid transition of 65-90% RH. These differences imply that chemical transport models of atmospheric chemistry should not use the SOM liquid to nonliquid phase transition as one-to-one surrogates of SOM reactivity.

Structural changes of aggregates composed of inorganic salts exposed to relative humidity (RH) between 0 and 80% after formation at selected RH between 0 and 60% were investigated using a tandem differential mobility analyzer (TDMA) and fluorescence microscopy. The TDMA was used to measure a shift in peak mobility diameter for 100-700 nm aggregates of hygroscopic aerosol particles composed of NaCl, Na2SO4, (NH4)2SO4, and nonhygroscopic Al2O3 as the RH was increased. Aggregates of hygroscopic particles were found to shrink when exposed to RH greater than that during the aggregation process. The degree of aggregate restructuring is greater for larger aggregates and greater increases in RH. Growth factors (GF) calculated from mobility diameter measurements as low as 0.77 were seen for NaCl before deliquescence. The GF subsequently increased to 1.23 at 80% RH, indicating growth after deliquescence. Exposure to RH lower than that experienced during aggregation did not result in structural changes. Fluorescent microscopy confirmed that aggregates formed on wire surfaces undergo an irreversible change in structure when exposed to elevated RH. Analysis of 2D movement of aggregates shows a displacement of 5-13% compared to projected length of initial aggregate from a wire surface. Surface tension due to water adsorption within the aggregate structure is a potential cause of the structural changes.

Laboratory studies with supermicrometer particles have shown that mineral particles coated with sulfuric acid are relatively poor ice nuclei. We investigated this phenomenon, which is of atmospheric relevance, by probing the structure of water at the mineral-aqueous acid interface as a function of the sulfuric acid concentration using sum frequency generation vibrational spectroscopy. We found that ordered water structures at water/mica interfaces drastically diminished at molarities of sulfuric acid equal to 0.5 M and totally disappeared when the molarities reached 5 M. The decrease in ordered water structures at the interface was caused by a combined effect of the decreased mica surface potential at low pH, the adsorption of sulfates on mica, and the lack of free water molecules in high concentrations of acidic solution. The good ice nucleation ability above liquid water saturation is correlated with the presence of structured water, suggesting that structured water at the interface may be needed for efficient heterogeneous ice nucleation.

Secondary organic material (SOM) constitutes a large mass fraction of atmospheric aerosol particles. Understanding its impact on climate and air quality relies on accurate models of interactions with water vapour. Recent research shows that SOM can be highly viscous and can even behave mechanically like a solid, leading to suggestions that particles exist out of equilibrium with water vapour in the atmosphere. In order to quantify any kinetic limitation we need to know water diffusion coefficients for SOM, but this quantity has, until now, only been estimated and has not yet been measured. We have directly measured water diffusion coefficients in the water soluble fraction of α-pinene SOM between 240 and 280 K. Here we show that, although this material can behave mechanically like a solid, at 280 K water diffusion is not kinetically limited on timescales of 1 s for atmospheric-sized particles. However, diffusion slows as temperature decreases. We use our measured data to constrain a Vignes-type parameterisation, which we extend to lower temperatures to show that SOM can take hours to equilibrate with water vapour under very cold conditions. Our modelling for 100 nm particles predicts that under mid- to upper-tropospheric conditions radial inhomogeneities in water content produce a low viscosity surface region and more solid interior, with implications for heterogeneous chemistry and ice nucleation.

Atmospheric aerosols can undergo phase transitions including liquid-liquid phase separation (LLPS) while responding to changes in the ambient relative humidity (RH). Here, we report results of chemical imaging experiments using environmental scanning electron microscopy (ESEM) and scanning transmission X-ray microscopy (STXM) to investigate the LLPS of micrometer-sized particles undergoing a full hydration-dehydration cycle. Internally mixed particles composed of ammonium sulfate (AS) and either: limonene secondary organic carbon (LSOC), α, 4-dihydroxy-3-methoxybenzeneaceticacid (HMMA), or polyethylene glycol (PEG-400) were studied. Events of LLPS were observed for all samples with both techniques. Chemical imaging with STXM showed that both LSOC/AS and HMMA/AS particles were never homogeneously mixed for all measured RH's above the deliquescence point and that the majority of the organic component was located in the outer phase. The outer phase composition was estimated as 65:35 organic: inorganic in LSOC/AS and as 50:50 organic: inorganic for HMMA/AS. PEG-400/AS particles showed fully homogeneous mixtures at high RH and phase separated below 89-92% RH with an estimated 70:30% organic to inorganic mix in the outer phase. These two chemical imaging techniques are well suited for in situ analysis of the hygroscopic behavior, phase separation, and surface composition of collected ambient aerosol particles.

The amount of ice present in clouds can affect cloud lifetime, precipitation and radiative properties. The formation of ice in clouds is facilitated by the presence of airborne ice-nucleating particles. Sea spray is one of the major global sources of atmospheric particles, but it is unclear to what extent these particles are capable of nucleating ice. Sea-spray aerosol contains large amounts of organic material that is ejected into the atmosphere during bubble bursting at the organically enriched sea-air interface or sea surface microlayer. Here we show that organic material in the sea surface microlayer nucleates ice under conditions relevant for mixed-phase cloud and high-altitude ice cloud formation. The ice-nucleating material is probably biogenic and less than approximately 0.2 micrometres in size. We find that exudates separated from cells of the marine diatom Thalassiosira pseudonana nucleate ice, and propose that organic material associated with phytoplankton cell exudates is a likely candidate for the observed ice-nucleating ability of the microlayer samples. Global model simulations of marine organic aerosol, in combination with our measurements, suggest that marine organic material may be an important source of ice-nucleating particles in remote marine environments such as the Southern Ocean, North Pacific Ocean and North Atlantic Ocean.

There is growing evidence that a metastable phase of ice, cubic ice, plays an important role in the Earth's troposphere and stratosphere. Cubic ice may also be important in diverse fields such as cryobiology and planetary sciences. Using X-ray diffraction, we studied the formation of cubic ice in pure water droplets suspended in an oil matrix as a function of droplet size. The results show that droplets of volume median diameter 5.6 microm froze dominantly to cubic ice with stacking faults. These results support previous suggestions that cubic ice is the crystalline phase that nucleates when pure water droplets freeze homogeneously at approximately 235 K. It is also shown that as the size of the water droplets increased from 5.6 to 17.0 microm, the formation of the stable phase of ice, hexagonal ice, was favoured. This size dependence can be rationalised with heat transfer calculations. We also investigated the stability of cubic ice that forms in water droplets suspended in an oil matrix. We observe cubic ice up to 243 K, much higher in temperature than observed in many previous studies. This result adds to the existing literature that shows bulk ice I(c) can persist up to approximately 240 K. The transformation of cubic ice to hexagonal ice also showed a complex time and temperature dependence, proceeding rapidly at first and then slowing down and coming to a halt. These combined results help explain why cubic ice forms in some experiments described in the literature and not others.

The heterogeneous reaction of O3 with lauric acid/oleic acid (LA/OA) mixtures and myristic acid/oleic acid (MA/OA) mixtures were studied as a function of composition, physical state, and microstructure at 298 K. Lauric acid and myristic acid are both alkanoic acids, whereas oleic acid is an alkenoic acid. Additionally, we investigated the uptake of O3 by multicomponent mixtures that closely represent the composition of meat-cooking aerosols. These measurements were performed with a rotating-wall flow-tube reactor coupled to a chemical ionization mass spectrometer. The reactive uptake coefficients (gamma) of O3 on liquid LA/OA and MA/OA solutions range from 4 x 10(-4) to 7.2 x 10(-4). The gamma values measured for solid-liquid LA/OA and MA/OA mixtures (which consist of solid LA or solid MA in equilibrium with a liquid) range from 2 x 10(-5) to 1.7 x 10(-4). These experiments show that only 7% solid by mass in the solid-liquid mixture can decrease gamma by an order of magnitude compared to the liquid mixtures. The gamma values for solid-liquid mixtures that closely represent the composition of meat-cooking aerosols range from 1.6 x 10(-5) to 6.9 x 10(-5). We found that gamma of solid-liquid mixtures depends on the microstructure of the mixtures, which in turn depends on the method of preparing the films. Furthermore, experiments employing solid-liquid mixtures show an increase in gamma with increasing film age. This can be explained either by the formation of a nonequilibrium phase followed by its relaxation to the stable phase or by Ostwald's ripening, which refers to a change in the solid microstructure due to a tendency to minimize the total surface free energy of the solid. We used the obtained gamma values to estimate OA lifetimes for polluted atmospheric conditions. For liquid solutions, the lifetimes were on the order of a few minutes. The lifetimes derived for solid-liquid mixtures are up to 75 min, significantly longer than for liquid solutions. Our study emphasizes the effect of the physical state and microstructure of multicomponent mixtures on the heterogeneous chemistry.

An important mechanism for ice cloud formation in the Earth's atmosphere is homogeneous nucleation of ice in aqueous droplets, and this process is generally assumed to produce hexagonal ice1,2. However, there are some reports that the metastable crystalline phase of ice, cubic ice, may form in the Earth's atmosphere3,4,5. Here we present laboratory experiments demonstrating that cubic ice forms when micrometre-sized droplets of pure water and aqueous solutions freeze homogeneously at cooling rates approaching those found in the atmosphere. We find that the formation of cubic ice is dominant when droplets freeze at temperatures below 190 K, which is in the temperature range relevant for polar stratospheric clouds and clouds in the tropical tropopause region. These results, together with heat transfer calculations, suggest that cubic ice will form in the Earth's atmosphere. If there were a significant fraction of cubic ice in some cold clouds this could increase their water vapour pressure, and modify their microphysics and ice particle size distributions5. Under specific conditions this may lead to enhanced dehydration of the tropopause region5.

The deliquescence and crystallization of ammonium sulfate particles internally mixed with water-soluble organic material have been studied, restricted to an organic mass fraction of less than 0.6. The organic species used were malonic acid, glycerol, levoglucosan (1,6-anhydro-β-d-glucopyranose), and Suwannee River fulvic acid. Our deliquescence results for systems with malonic acid and fulvic acid are in agreement with existing literature values. Glycerol deliquescence results are slightly lower than previous measurements. The levoglucosan results are the first of this kind. Total deliquescence relative humidities for the different systems are the same within the uncertainty of the measurements when the organic mole fraction is less than approximately 0.35. At an organic mole fraction of 0.6, the maximum deviation of total deliquescence relative humidities between the systems is approximately 10% relative humidity. We show that thermodynamic calculations based on a simplified version of a model recently p...