ALBERT

Description: Cirrus clouds are composed of ice particles and their formation pathways have been studied extensively in the laboratory. The ability of ammonium sulfate particles to act as nuclei for cirrus clouds has been of particular importance because of their ubiquitous presence in the upper troposphere. The results of past laboratory experiments of homogeneous ice nucleation from ammonium sulfate particles show a wide range of freezing conditions. In the present study, a flow tube apparatus equipped with Fourier transform infrared spectroscopy was used to resolve these discrepancies. It was found that when ammonium sulfate particles were preconditioned at 100% relative humidity (RH) prior to experimentation, the particles froze at conditions predicted by the homogeneous ice nucleation model developed by Koop et al. (2000). If the particles were not preconditioned at 100% RH, they froze at warmer temperatures and lower ice saturation ratios than predicted by Koop et al. (2000). In order to determine if a population of effloresced particles affected freezing conditions for particles that were not preconditioned at 100% RH, a series of depositional ice nucleation experiments were carried out on dry ammonium sulfate particles. For freezing temperatures between 215 and 231 K, ice nucleated on the particles at ice saturation ratios (Sice) between 1 and 1.05. These conditions are much lower than predicted by Koop et al. (2000) and explain the differences in freezing conditions among preconditioning methods. In similar experiments, Abbatt et al. (2006) hypothesized that a small fraction of effloresced ammonium sulfate particles induced ice nucleation at Sice values lower than expected. The current study confirms the Abbatt et al. (2006) hypothesis and, to our knowledge, is the first study to directly observe ice nucleating onto freely flowing dry ammonium sulfate particles at Sice values approaching unity.

Description: Heterogeneous ice nucleation on solid ammonium sulfate and solid amorphous glutaric acid particles was studied using optical microscopy and Raman spectroscopy. Optical microscopy was used to detect selective nucleation events as water vapor was slowly introduced into an environmental sample cell. Particles that nucleated ice were dried via sublimation and examined in detail using Raman spectroscopy. Depositional ice nucleation occurred preferentially on just a few ammonium sulfate and glutaric acid particles in each sample. For freezing temperatures between 214 K and 235 K average ice saturation ratios of S=1.10±0.07 for solid ammonium sulfate and S=1.39±0.16 for solid amorphous glutaric acid particles were determined. Experiments with externally mixed particles further show that ammonium sulfate is a more potent ice nucleus that glutaric acid. Our results suggest that heterogeneous nucleation on ammonium sulfate may be an important pathway for atmospheric ice nucleation and cirrus cloud formation when solid aerosol particles are available for ice formation. This pathway for ice formation may be particularly significant near the tropopause region where sulfates are abundant and other species known to be good ice nuclei are depleted.

Description: While water insoluble organics are prevalent in the atmosphere, it is not clear how the presence of such species alters the chemical and physical properties of atmospheric aerosols. Here we use a combination of FTIR spectroscopy, Transmission Electron Microscopy (TEM) and Aerosol Mass Spectrometry (AMS) to characterize ammonium sulfate particles coated with palmitic acid. Coated aerosols were generated by atomizing pure ammonium sulfate, mixing the particles with a heated flow of nitrogen with palmitic acid vapor, and then flowing the mixture through an in-line oven to create internally mixed particles. The mixing state of the particles was probed using the AMS data and images from the TEM. Both of these probes suggest that the particles were internally mixed. Water uptake by the mixed particles was then probed at 273 K. It was found that for ammonium sulfate containing ~20 wt% palmitic acid the deliquescence relative humidity (DRH) was the same as for pure ammonium sulfate (80±3% RH). For particles with ~50 wt% palmitic acid however, the mixed particles began to take up water at relative humidities as low at 69% and continued to slowly take up water to 85% RH without fully deliquescing. In addition to studies of water uptake, water loss was also investigated. Here coatings of up to 50 wt% had no impact on the efflorescence relative humidity. These studies suggest that even if insoluble substances coat salt particles in the atmosphere, there may be relatively little effect on the resulting water uptake and loss.

Description: Cirrus clouds are composed of ice particles and their formation pathways have been studied extensively in the laboratory. The ability of ammonium sulfate particles to act as nuclei for cirrus clouds has been of particular importance because of their ubiquitous presence in the upper troposphere. The results of past laboratory experiments of homogeneous ice nucleation from ammonium sulfate particles show a wide range of freezing conditions. In the present study, a flow tube apparatus equipped with Fourier transform infrared spectroscopy was used to reexamine these discrepancies. It was found that when ammonium sulfate particles were preconditioned at 100% relative humidity (RH) prior to experimentation, the particles began to freeze at conditions predicted by the homogeneous ice nucleation model developed by Koop et al. (2000). If the particles were not preconditioned at 100% RH, some froze at warmer temperatures and lower ice saturation ratios than predicted by Koop et al. (2000). It is hypothesized that a population of effloresced particles affected freezing conditions for particles that were not preconditioned at 100% RH.

Description: While water insoluble organics are prevalent in the atmosphere, it is not clear how the presence of such species alters the chemical and physical properties of atmospheric aerosols. Here we use a combination of FTIR spectroscopy, Transmission Electron Microscopy (TEM) and Aerosol Mass Spectrometry (AMS) to characterize ammonium sulfate particles coated with palmitic acid. Coated aerosols were generated by atomizing pure ammonium sulfate, mixing the particles with a heated flow of nitrogen with palmitic acid vapor, and then flowing the mixture through an in-line oven to create internally mixed particles. The mixing state of the particles was probed using the AMS data and images from the TEM. Both of these probes suggest that the particles were internally mixed. Water uptake by the mixed particles was then probed at 273 K. It was found that for ammonium sulfate containing ~20 wt% palmitic acid the deliquescence relative humidity (DRH) was the same as for pure ammonium sulfate (80±3% RH). For particles with ~50 wt% palmitic acid however, the mixed particles began to take up water at relative humidities as low at 69% and continued to slowly take up water to 85% RH without fully deliquescing. In addition to studies of water uptake, water loss was also investigated. Here coatings of up to 50 wt% had no impact on the efflorescence relative humidity. These studies suggest that even if insoluble substances coat salt particles in the atmosphere, there may be relatively little effect on the resulting water uptake and loss.