Allan K. Bertram

Viscosity of α-pinene secondary organic material and implications for particle growth and reactivity

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.

A marine biogenic source of atmospheric ice-nucleating 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.

The formation of cubic ice under conditions relevant to Earth's atmosphere.

An important mechanism for ice cloud formation in the Earths atmosphere is homogeneous nucleation of ice in aqueous droplets, and this process is generally assumed to produce hexagonal ice. However, there are some reports that the metastable crystalline phase of ice, cubic ice, may form in the Earths atmosphere. 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 Earths 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 distributions. Under specific conditions this may lead to enhanced dehydration of the tropopause region.

Images reveal that atmospheric particles can undergo liquid–liquid phase separations

A large fraction of submicron atmospheric aerosol particles contains both organic material and inorganic salts. As the relative humidity cycles in the atmosphere and the water content of the particles correspondingly changes, these mixed particles can undergo a range of phase transitions, possibly including liquid–liquid phase separation. If liquid–liquid phase separation occurs, the gas-particle partitioning of atmospheric semivolatile organic compounds, the scattering and absorption of solar radiation, and the reactive uptake of gas species on atmospheric particles may be affected, with important implications for climate predictions. The actual occurrence of liquid–liquid phase separation within individual atmospheric particles has been considered uncertain, in large part because of the absence of observations for real-world samples. Here, using optical and fluorescence microscopy, we present images that show the coexistence of two noncrystalline phases for real-world samples collected on multiple days in Atlanta, GA as well as for laboratory-generated samples under simulated atmospheric conditions. These results reveal that atmospheric particles can undergo liquid–liquid phase separations. To explore the implications of these findings, we carried out simulations of the Atlanta urban environment and found that liquid–liquid phase separation can result in increased concentrations of gas-phase NO3 and N2O5 due to decreased particle uptake of N2O5.

Sea spray aerosol as a unique source of ice nucleating particles

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.

Reactive uptake of NO3, N2O5, NO2, HNO3, and O3 on three types of polycyclic aromatic hydrocarbon surfaces.

We investigated the reactive uptake of NO3, N2O5, NO2, HNO3, and O3 on three types of solid polycyclic aromatic hydrocarbons (PAHs) using a coated wall flow tube reactor coupled to a chemical ionization mass spectrometer. The PAH surfaces studied were the 4-ring systems pyrene, benz[a]anthracene, and fluoranthene. Reaction of NO3 radicals with all three PAHs was observed to be very fast with the reactive uptake coefficient, gamma, ranging from 0.059 (+0.11/-0.049) for benz[a]anthracene at 273 K to 0.79 (+0.21/-0.67) for pyrene at room temperature. In contrast to the NO3 reactions, reactions of the different PAHs with the other gas-phase species (N2O5, NO2, HNO3, and O3) were at or below the detection limit (gamma <or= 6.6 x 10(-5)) in all cases, illustrating that these reactions are at best slow. For NO3 we also investigated the time dependence of the reactive uptake to determine if the surface-bound PAH molecules were active participants in the reaction (i.e., reactants). Reaction of NO3 on all three PAH surfaces slowed down at 263 K after long NO3 exposure times, suggesting that the PAH molecules were reactants. Additionally, NO2 and HNO3 were identified as major gas-phase products. Our results show that under certain atmospheric conditions, NO3 radicals can be a more important sink for PAHs than NO2, HNO3, N2O5, or O3 and impact tropospheric lifetimes of surface-bound PAHs.

Formation and stability of cubic ice in water droplets

There is growing evidence that a metastable phase of ice, cubic ice, plays an important role in the Earths 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.

N2O5 Reactive Uptake on Aqueous Sulfuric Acid Solutions Coated with Branched and Straight-Chain Insoluble Organic Surfactants

A flow reactor coupled to a chemical ionization mass spectrometer was used to study the reactive uptake coefficients at 273 K of N2O5 on aqueous 60 wt % sulfuric acid solutions coated with insoluble organic monolayers. Both straight-chain surfactants (1-hexadecanol, 1-octadecanol, and stearic acid) and a branched surfactant (phytanic acid) were studied. The reactive uptake coefficient decreased dramatically for straight-chain surfactants. The decrease ranged from a factor of 17 to a factor of 61 depending on the type of straight-chain surfactant. In contrast to the straight-chain data, the presence of phytanic acid did not have a significant effect on the N2O5 reactive uptake coefficient (the decrease was less than the uncertainty in the data) compared to the uncoated solution. In addition to measuring the reactive uptake coefficients, we also investigated the relationship between properties of the monolayers and the reactive uptake coefficients. The reactive uptake coefficients measured on aqueous sulfuric acid subphases showed a relationship to the surface area occupied by the surfactant molecules. However, data obtained with other subphases did not overlap with this trend.

Liquid–liquid phase separation in atmospherically relevant particles consisting of organic species and inorganic salts

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 (<11 species). Phase separation in particles composed of laboratory-produced secondary organic material and sulphate species and in ambient particles is generally consistent with this trend. A further constraint is that liquid–liquid phase separation was always observed for O:C < 0.5 and was never observed for O:C ≥ 0.8. For organic materials of intermediate O:C ranging from 0.5 to 0.8, phase separation in simple organic–inorganic mixtures was influenced by the organic functional groups represented. The organic-to-inorganic mass ratio (OIR) affected the occurrence of liquid–liquid phase separation in a small number of cases. A dependence on salt type was observed with 87% of the studied organics exhibiting the following trend in SRH values: (NH4)2SO4 ≥ NH4HSO4 ≥ NaCl ≥ NH4NO3, consistent with previous salting-out studies and the Hofmeister series. Liquid–liquid phase separation does not appear to be strongly influenced by the number of species making up the organic material. The morphology of phase separated particles appears to depend on composition, including O:C of the organic material, the inorganic salt and the OIR.

Reactive uptake of N2O5 on aqueous H2SO4 solutions coated with 1-component and 2-component monolayers.

Reactive uptake of N(2)O(5) on aqueous sulfuric acid solutions was studied in the presence of 1-component (octadecanol) and 2-component (octadecanol + phytanic acid) monolayers. In the 1-component monolayer experiments, the reactive uptake coefficient depended strongly on the molecular surface area of the surfactant. Also, the 1-component monolayer showed significant resistance to mass transfer even when the fractional surface coverage of the surfactant was less than 1. For example, a monolayer of 1-octadecanol with a fractional surface coverage of 0.75 decreased the reactive uptake coefficient by a factor of 10. This is consistent with previous studies. In the 2-component monolayer experiments, the reactive uptake coefficient depended strongly on the composition of the monolayer. When the monolayer contained only straight-chain molecules (1-octadecanol), the reactive uptake coefficient decreased by a factor of 42 due to the presence of the monolayer. However, when the monolayer contained 0.20 mole fraction of a branched surfactant (phytanic acid) the reactive uptake coefficient only decreased by a factor of 2. Hence, a small amount of branched surfactant drastically changes the overall resistance to reactive uptake. Also, our results show that the overall resistance to reactive uptake of 2-component monolayers can be predicted reasonably accurately by a model that assumes the resistances to mass transfer can be combined in parallel.