M. L. Smith

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.

Biogenic Potassium Salt Particles as Seeds for Secondary Organic Aerosol in the Amazon

Salty Origins of Fresh Water Cloud droplets above the Amazonian rain forest form mostly around organic aerosols, but the source of the aerosols has been a mystery. Pöhlker et al. (p. 1075) report that particles rich in potassium salts emitted by Amazonian vegetation can act as the seeds for the growth of organic aerosol particles that function as condensation nuclei for water droplets. These specks of biogenic salts provide a surface for the condensation of low- or semi-volatile organic compounds formed by the atmospheric oxidation of isoprene and terpenes, molecules produced in great abundance by many kinds of Amazonian plants. Potassium salt particles account for the previously mysterious initiation sites of aerosol growth above the Amazonian rainforest. The fine particles serving as cloud condensation nuclei in pristine Amazonian rainforest air consist mostly of secondary organic aerosol. Their origin is enigmatic, however, because new particle formation in the atmosphere is not observed. Here, we show that the growth of organic aerosol particles can be initiated by potassium-salt–rich particles emitted by biota in the rainforest. These particles act as seeds for the condensation of low- or semi-volatile organic compounds from the atmospheric gas phase or multiphase oxidation of isoprene and terpenes. Our findings suggest that the primary emission of biogenic salt particles directly influences the number concentration of cloud condensation nuclei and affects the microphysics of cloud formation and precipitation over the rainforest.

Chemical synaptic activity modulates nearby electrical synapses

Most electrically coupled neurons also receive numerous chemical synaptic inputs. Whereas chemical synapses are known to be highly dynamic, gap junction-mediated electrical transmission often is considered to be less modifiable and variable. By using simultaneous pre- and postsynaptic recordings, we demonstrate at single mixed electrical and chemical synapses that fast chemical transmission interacts with gap junctions within the same ending to regulate their conductance. Such localized interaction is activity-dependent and could account for the large variation in strength of electrical coupling at auditory afferent synapses terminating on the Mauthner cell lateral dendrite. Thus, interactions between chemical and electrical synapses can regulate the degree of electrical coupling, making it possible for a given neuron to independently modify coupling at different electrical synapses with its neighbors.

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.

Secondary Organic Material Produced by the Dark Ozonolysis of α-Pinene Minimally Affects the Deliquescence and Efflorescence of Ammonium Sulfate

The hygroscopic phase transitions and growth factors of mixed particles having as components ammonium sulfate and secondary organic material (SOM) were measured. The SOM was generated by the dark ozonolysis of α-pinene, and organic particle mass concentrations of 1.63 and 12.2 μg m−3 were studied. The hygroscopic properties were investigated using a 1×3 tandem differential mobility analyzer (1×3-TDMA). The 1×3-TDMA takes advantage of the hysteresis between solid-to-aqueous and aqueous-to-solid phase transitions to determine the efflorescence and deliquescence relative humidities (ERH and DRH, respectively) of materials. Overall, the influence of the SOM produced by the dark ozonolysis of α-pinene on the ERH and DRH of ammonium sulfate was small, shifting for example the DRH from 80% for pure ammonium sulfate to 77% for organic volume fractions of 0.96. The ERH likewise shifted by only a small amount across this composition range, specifically from 31 to 29%. The SOM produced at the lower organic particle mass concentrations shifted ERH and DRH even less, indicating an influence of SOM chemical composition on phase transitions. The hygroscopic growth factors of the mixed particles were adequately modeled across the range of studied RH (50 to 83%) using volume-averaged growth factors of the pure materials. The results for ERH, DRH, and the growth factors were all consistent with a model of phase separation between the inorganic and organic phases in individual particles, at least for the studied RH values (<83%) and for SOM prepared by α-pinene ozonolysis.

The Dynamic Shape Factor of Sodium Chloride Nanoparticles as Regulated by Drying Rate

The influence of drying rate on the dynamic shape factor χ of NaCl particles was investigated. The drying rate at the efflorescence relative humidity (ERH) of 45% was controlled in a laminar flow tube and varied from 5.5 ± 0.9 to 101 ± 3 RH s–1 at ERH, where RH represents one percent unit of relative humidity. Dry particles having mobility diameters of 23–84 nm were studied, corresponding to aqueous particles of 37–129 nm at the RH (57%) prior to drying. At each mobility diameter and drying rate, the critical supersaturation of cloud-condensation activation was also measured. The mobility diameter and the critical supersaturation were combined in an analysis to determine the value of χ. The measured values varied from 1.02 to 1.26. For fixed particle diameter the χ value decreased with increasing drying rate. For fixed drying rate, a maximum occurred in χ between 35- and 40-nm dry mobility diameter, with a lower χ for both smaller and larger particles. The results of this study, in conjunction with the introduced apparatus for obtaining quantified drying rates, can allow the continued development of a more detailed understanding of the morphology of submicron salt particles, with the potential for the follow-on development of quantitative modeling of evaporation and crystal growth at these dimensions.

Phase Transitions and Phase Miscibility of Mixed Particles of Ammonium Sulfate, Toluene-Derived Secondary Organic Material, and Water

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 of <5 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 ε < 0.2, the DRH and ERH to first approximation did not change with the organic volume fraction. This observation is consistent with independent behaviors for ε < 0.2 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 RH < 85%. 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 ε > 0.5, the DRH values of ammonium sulfate in mixtures with SOM produced at <5% 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.

An Analytic Equation for the Volume Fraction of Condensationally Grown Mixed Particles and Applications to Secondary Organic Material Produced in Continuously Mixed Flow Reactors

Secondary condensation of organic material onto primary seed particles is one pathway of particle growth in the atmosphere, and many properties of the resulting mixed particles depend on organic volume fraction. Environmental chambers can be used to simulate the production of these types of particles, and the optical, hygroscopic, and other properties of the mixed particles can be studied. In the interpretation of the measured properties, the probability density function p(ϵ;d) of volume fraction ϵ of the condensing material for particle diameter d in the outflow of the chamber is typically needed. In this article, analytic equations are derived p(ϵ;d) for condensational growth in a continuously mixed flow reactor. The equation predictions are compared to measurements for the condensation of secondary organic material on quasi-monodisperse sulfate seed particles. Equations are presented herein for discrete, Gaussian, and triangular distribution functions for the seed particle number–diameter distributions, including generalization to any linearly segmented distributions. The analytic equations are useful both for the interpretation of laboratory data from environmental chambers, such as the construction of probability density functions for use in interpretation of hygroscopic growth data, cloud–condensation–nuclei data, or other laboratory data sets dependent on organic volume fraction, as well as for understanding atmospheric processes at times that condensational growth processes prevail. Copyright 2014 American Association for Aerosol Research