Sarah D. Brooks

Deliquescence behavior of organic/ammonium sulfate aerosol

Received 15 January 2002; revised 16 May 2002; accepted 23 May 2002; published 8 October 2002. [1] Recent studies have shown that tropospheric aerosols composed of internal mixtures of organics with sulfates are quite common with the organic composing up to 50% of the particle mass. The influences of the organics on the chemical and physical properties of the aerosol are not known. In this paper, we report the solubility of a series of dicarboxylic acids in saturated ammonium sulfate solution as a function of temperature. We also report the deliquescence relative humidity (DRH) of the pure dicarboxylic acids and of mixtures of dicarboxylic acids with ammonium sulfate. For the systems studied, we find that the presence of watersoluble dicarboxylic acids caused deliquescence to occur at a lower relative humidity (RH) than pure ammonium sulfate. In contrast, the less soluble dicarboxylic acids had no measurable effect on the deliquescence relative humidity of ammonium sulfate. INDEX TERMS: 0305 Atmospheric Composition and Structure: Aerosols and particles (0345, 4801); 0320 Atmospheric Composition and Structure: Cloud physics and chemistry; 0340 Atmospheric Composition and Structure: Middle atmosphere—composition and chemistry. Citation: Brooks, S. D., M. E. Wise, M. Cushing, and M. A. Tolbert, Deliquescence behavior of organic/ammonium sulfate aerosol, Geophys. Res. Lett., 29(19), 1917, doi:10.1029/2002GL014733, 2002.

Infrared spectroscopic study of the deliquescence and efflorescence of ammonium sulfate aerosol as a function of temperature

The deliquescence and efflorescence phase transitions of ammonium sulfate aerosols have been studied as a function of relative humidity (RH) over the temperature range from 234 K to 295 K. Polydisperse submicrometer ammonium sulfate particles produced by atomization were monitored in a temperature-controlled flow tube system using Fourier transform infrared spectroscopy. The relative humidity in the aerosol flow was controlled using a sulfuric acid bath conditioner and the addition of a known flow of dry nitrogen. The relative humidity was measured using a dew point hygrometer and infrared absorption features. The deliquescence transition was observed to be nearly independent of temperature, changing from 80% RH at 294.8 K to 82% RH at 258.0 K near the ice saturation line, in good agreement with previous results. The relative humidity at the efflorescence transition also increased slightly (32% to 39%) with decreasing temperature (294.8 K to 234.3 K). These results suggest that once a crystalline ammonium sulfate particle deliquesces, the droplet can exist as a metastable solution droplet over a broad region of temperature and water pressures under the conditions in the upper troposphere. The persistence of metastable ammonium sulfate solution droplets may have important implications for cirrus cloud formation and heterogeneous reaction rates in the upper troposphere.

Examinations of ice formation processes in Florida cumuli using ice nuclei measurements of anvil ice crystal particle residues

[1] A continuous flow diffusion chamber (CFDC) was used to measure ice formation by cloud particle residuals during the Cirrus Regional Study of Tropical Anvils and Cirrus Layers-Florida Area Cirrus Experiment. These measurements were directed toward determining the relative contributions of homogeneous nucleation, heterogeneous nucleation, and secondary ice formation processes to the concentrations of ice crystals in anvil cirrus formed from convection. The CFDC sampled residual particles remaining after evaporation of cloud particles initially collected by a counterflow virtual impactor. This allowed, for the first time, determination of the ice nucleation ability of particles that included the presumed nuclei for cloud-ice formation. The approach proved successful for estimating concentrations of heterogeneous ice nuclei (IN) transported into anvil clouds, but experimental issues limited measurements of homogeneous freezing and, consequently, in determining the role of secondary ice formation. Results suggest agreement within a factor of 2–3 between CFDC heterogeneous IN concentrations and anvil ice crystal concentrations in the size range above 30 mm. IN concentrations also correlated with ice concentrations inferred from measurements by the FSSP (Forward Scattering Spectrometer Probe). However, measured IN concentrations were nearly two orders of magnitude lower than FSSP concentrations. This difference may have resulted from homogeneous freezing, secondary ice formation, or other unidentified ice formation processes that were not fully captured by the CFDC. The data suggest that heterogeneous nucleation played a smaller role than homogeneous nucleation in determining anvil ice crystal concentrations, except during periods of strong desert dust ingestion by cumuli. Nevertheless, heterogeneous nucleation may provide the source for larger ice crystals present in anvil regions.

Ice nucleation in sulfuric acid and ammonium sulfate particles

Cirrus clouds are composed of ice particles and are expected to form in the upper troposphere when highly dilute sulfate aerosols cool and become supersaturated with respect to ice. In the laboratory we have used Fourier transform infrared spectroscopy to monitor ice nucleation from sulfate particles for relevant compositions of sulfuric acid/water and ammonium sulfate/water aerosols. Measured freezing temperatures are presented as a function of aerosol composition, and results are compared to existing aerosol data. We find that sulfuric acid solution aerosol exhibits greater supercooling than ammonium sulfate solution aerosol of similar weight percent. Ice saturation ratios based on these measurements are also reported. We find that ammonium sulfate solution aerosol exhibits a relatively constant ice saturation of S∼1.48 for ice nucleation from 232 to 222 K, while sulfuric acid solution aerosol shows an increase in ice saturation from S∼1.53 to S∼1.6 as temperature decreases from 220 K to 200 K. These high-saturation ratios imply selective nucleation of ice from sulfate aerosols.

Pollen as atmospheric cloud condensation nuclei

Anemophilous (wind-dispersed) pollen grains are emitted in large quantities by vegetation in the midlatitudes for reproduction. Pollen grains are coarse particles (5–150 µm) that can rupture when wet to form submicron subpollen particles (SPP) that may have a climatic role. Laboratory CCN experiments of six fresh pollen samples show that SPP activate as CCN at a range of sizes, requiring supersaturations from 0.81 (± 0.07)% for 50 nm particles, 0.26 (± 0.03)% for 100 nm particles, and 0.12 (± 0.00)% for 200 nm particles. Compositional analyses indicate that SPP contain carbohydrates and proteins. The SPP contribution to global CCN is uncertain but could be important depending on pollen concentrations outside the surface layer and the number of SPP generated from a single pollen grain. The production of hygroscopic SPP from pollen represents a novel, biologically driven cloud formation pathway that may influence cloud optical properties and lifetimes, thereby influencing climate.

Effects of Chemical Aging on the Ice Nucleation Activity of Soot and Polycyclic Aromatic Hydrocarbon Aerosols

The role of soot particles as ice nuclei (IN) in heterogeneous freezing processes in the atmosphere remains uncertain. Determination of the freezing efficiency of soot is complicated by the changing properties of soot particles undergoing atmospheric aging processes. In this study, the heterogeneous freezing temperatures of droplets in contact with fresh and oxidized soot particles were determined using an optical microscope apparatus equipped with a sealed cooling stage and a CCD video camera. Experiments were also conducted using fresh and oxidized polycyclic aromatic hydrocarbons (PAHs), including anthracene, pyrene, and phenanthrene, as potential ice nuclei. Chemical changes at the surface of the aerosols caused by exposure to ozone were characterized using Fourier transform infrared spectroscopy with horizontal attenuated total reflectance (FTIR-HATR). In addition, Brunauer-Emmett-Teller (BET) measurements were used to determine the specific surface areas of the soot particles. Mean freezing temperatures on fresh particles ranged from -19 to -24 °C, depending on the IN composition and size. In all cases, exposure to ozone facilitated ice nucleation at warmer temperatures, by 2-3 °C, on average. In addition, nucleation rate coefficients for a single temperature and IN type increased by as much as 4 orders of magnitude because of oxidation. Furthermore, a fraction of the oxidized soot particles froze at temperatures above -10 °C. A modified version of classical nucleation theory that accounts for a range of contact angles on nucleation sites within an IN population was used to derive the probability of freezing as a function of temperature for each type of IN. In summary, our results suggest that atmospheric oxidation processes may both extend the range over which particles can act as ice nuclei to warmer temperatures and increase heterogeneous nucleation rates on soot and pollutant aerosols.

Using Raman Microspectroscopy to Determine Chemical Composition and Mixing State of Airborne Marine Aerosols over the Pacific Ocean

Chemical composition and mixing state of aerosols collected over an 11,000 km latitudinal cruise in the Pacific Ocean are reported here as determined by a new application of Raman spectroscopy. The Raman microspectroscopy technique employs a Raman spectrometer coupled to an optical microscope to identify the chemical composition and internal mixing state of single particles. By analyzing multiple particles in a collected ensemble, the degree of external mixing of particles was also determined. To lend context to the Pacific aerosol population sampled, atmospheric aerosol concentration, and the critical supersaturation required for the aerosols to activate as cloud condensation nuclei, and chlorophyll a concentration in the underlying water (a metric for phytoplankton biomass in the ocean) were also obtained. Our results indicate that long chain organic molecules were prevalent in the marine aerosol samples throughout the cruise, including during coastal and open ocean locations, in both hemispheres, and in the seasons of autumn and spring. Long chain organic compounds tended to be present in internal mixtures with other organic and inorganic components. Although variations in the fraction of aerosols activated as CCN were observed, no simple correlation between organics and CCN activation was found. According to our measurements, marine aerosol in the Pacific Ocean may be generally characterized as multicomponent aerosol containing and often dominated by a high organic fraction. Our results suggest that the prevalence of organics and the high degree of internal mixing of aerosol must be accounted for in accurate modeling of the role of marine aerosols in cloud formation and climate. Copyright 2014 American Association for Aerosol Research

Raman spectroscopy of glyoxal oligomers in aqueous solutions.

Raman microscopy and Attenuated Total Reflection infrared spectroscopy were utilized to facilitate investigations of equilibria between various hydrated and oligomeric forms of glyoxal in aqueous glyoxal solution droplets. The assignment of spectra is obtained with the assistance of B3LYP density functional quantum chemical calculations of vibrational wavenumbers, Raman activities, and infrared intensities. Several forms of glyoxal derivatives with similar functional groups, e.g., hydroxyl and dioxolane rings, are found to be present. The absence of a Raman spectral peak corresponding to the vibrational carbonyl stretch provides evidence that both carbonyl groups of a glyoxal molecule become hydrated in solutions of a broad concentration range. The presence of bands corresponding to deformation vibrations of the dioxolane ring indicates that dihydrated glyoxal oligomers are formed in glyoxal solutions with concentrations of 1 M and higher. Under typical ambient temperature and humidity conditions, concentrated glyoxal solution droplets undergo evaporation with incomplete water loss. Our results suggest that formation of crystalline glyoxal trimer dihydrate from concentrated solutions droplets is hindered by the high viscosity of the amorphous trimer and requires dry conditions that could rarely be achieved in the atmosphere. However, crystallization may be possible for droplets of low initial glyoxal concentrations, such as those produced by evaporating cloud droplets.

Solubility and freezing effects of Fe2+ and Mg2+ in H2SO4 solutions representative of upper tropospheric and lower stratospheric sulfate particles

Chemical elements characteristic of earth minerals and meteorites are present withinbackground tropospheric and stratospheric sulfate aerosol particles. However, it isunknown if these elements are present predominantly as solids, including possiblesulfates, carbonates, and oxides, or rather as soluble aqueous metal ions or complexes.Further, it is unclear how these impurities could affect particle freezing. To addressthese questions, we have determined the total equilibrium metal solubility ([Fe

Atmospheric Ammonia Mixing Ratios at an Open-Air Cattle Feeding Facility

Abstract Mixing ratios of total and gaseous ammonia were measured at an open-air cattle feeding facility in the Texas Panhandle in the summers of 2007 and 2008. Samples were collected at the nominally upwind and downwind edges of the facility. In 2008, a series of far-field samples was also collected 3.5 km north of the facility. Ammonium concentrations were determined by two complementary laboratory methods, a novel application of visible spectrophotometry and standard ion chromatography (IC). Results of the two techniques agreed very well, and spectrophotometry is faster, easier, and cheaper than chromatography. Ammonia mixing ratios measured at the immediate downwind site were drastically higher (∼2900 parts per billion by volume [ppbv]) than those measured at the upwind site (≤200 ppbv). In contrast, at 3.5 km away from the facility, ammonia mixing ratios were reduced to levels similar to the upwind site (≤200 ppbv). In addition, PM10 (particulate matter <10 μm in optical diameter) concentrations obtained at each sampling location using Grimm portable aerosol spectrometers are reported. Time-averaged (1-hr) volume concentrations of PM10 approached 5 × 1012 nm3 cm−3. Emitted ammonia remained largely in the gas phase at the down-wind and far-field locations. No clear correlation between concentrations of ammonia and particles was observed. Overall, this study provides a better understanding of ammonia emissions from open-air animal feeding operations, especially under the hot and dry conditions present during these measurements.