Determination of Total Peroxide Content in Secondary Organic Aerosol Particles

Secondary organic aerosol particles (SOA) formed from the oxidation of monoterpenes can impact the Earth’s radiation balance, act as cloud condensation nuclei and negatively affect human health. In the initial Visiting Faculty Program application, we proposed the use of an ultraviolet-visible spectrometer equipped with a liquid waveguide capillary flow cell to determine the extent to which SOA absorb visible light. The inclusion of Concordia University in the Secondary Organic Aerosol From Forest Emissions Experiment (SOAFFEE) laboratory campaign at PNNL necessitated a change in the proposed experiments. An iodometric-spectrophotometric (IS) technique was developed to quantify the total peroxide content in SOA. The experimental technique was validated by measuring the peroxide content in commercially available products. After the validation of the experimental technique, the total peroxide content of SOA formed from a variety of experimental conditions was quantified. It was found that the amount of peroxides in the SOA generated at PNNL was similar to that found in previous research studies. The research carried out at PNNL will be included in an undergraduate senior thesis at Concordia University - Portland (CU). It is also expected that the research will be included in peer-reviewed journal articles. It is our hope that the success of our work will result in future collaborations between PNNL and CU

Raspberry Pi Sensor Array

The Raspberry Pi is a fully operational, credit card sized computer that costs $40. When a monitor and keyboard are connected, it can perform any task that a desktop computer can accomplish. The Raspberry Pi uses Linux based operating systems which can be easy to use and learn. Integrating the Pi into projects is made easy by connecting specific hardware components and programming them with the Python computer language. Python is widely used by many companies including Google and Reddit. The Pi is faster and more user-friendly than similar boards such as Arduino. Additionally, there are online support forums from Pi customers and support teams. In the summer of 2017, we were able to outfit the Pi to operate an air quality sensor array

Determination of the Optical Properties of Secondary Organic Aerosol Particles

The enhanced greenhouse effect is currently considered to be our most important global environmental problem. While the magnitude of radiation absorbed by greenhouse gases is known to a high certainty, the absorption of radiation by atmospheric aerosol particles is not. In the initial Visiting Faculty Program application, we proposed the use of an ultraviolet-visible (UV/Vis) spectrometer equipped with a liquid waveguide capillary flow cell to determine the extent to which secondary organic aerosol particles (SOA) absorb visible light. Early in the research period, the UV/Vis technique was optimized for three solvent systems (methanol, water and 0.1 M hydrochloric acid). Using the optimized UV/Vis technique optical properties such as mass specific absorption cross-section and imaginary refractive index were determined for SOA dissolved in different solvent systems. The end result of the UV/Vis studies is the inclusion of SOA optical properties into climate models developed at the Pacific Northwest National Laboratory (PNNL). This knowledge will help to improve climate models, which currently do not include the effect of SOA. We also utilized Fourier Transform Infrared Spectroscopy to help elucidate the chemical composition of SOA. Finally, an experimental method was developed to determine the peroxide content of SOA. It is expected that these studies will connect the chemical composition of SOA to their optical properties. The research carried out at PNNL will be included in two undergraduate senior theses at Concordia University - Portland (CU). It is also expected that this research will be included in a peer-reviewed journal article. It is our hope that success of our work will result in future collaborations between PNNL and CU students

Ice Nucleation in Internally Mixed Ammonium Sulfate/Dicarboxylic Acid Particles

Recent studies have shown that tropospheric sulfate aerosols commonly contain 50% or more by mass organic species. The influence of these organics on the chemical and physical properties of sulfate aerosols is not fully established. Using an aerosol flow tube technique, we have determined ice nucleation temperatures for particles composed of ammonium sulfate and mixtures of ammonium sulfate with a series of dicarboxylic acids. A calibration curve was developed to allow us to convert the freezing temperatures to a saturation ratio required for ice nucleation. At levels detectable by our experimental technique we find that the freezing temperatures and critical ice saturation ratios of each system were identical, for a given water activity of the solution, even though the solutions contained varying fractions of inorganic and organic components. Further experiments showed that the freezing behavior of pure dicarboxylic acid particles was identical to that of the other systems studied if the water activity was identical. Although the apparent freezing temperatures reported here are substantially warmer than those predicted by the water activity based nucleation theory of T. Koop et al., we find that solution water activity defined the freezing conditions for the systems studied here

Deliquescence Behavior of Organic/Ammonium Sulfate Aerosol

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 water-soluble 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

Hygroscopic Growth of Ammonium Sulfate/Dicarboxylic Acids

Recent studies have shown that tropospheric sulfate aerosols commonly contain 50% by mass organic species. The influence of these organics on the chemical and physical properties of sulfate aerosols is not fully established. We have measured the water activity of pure dicarboxylic acids and eutonic mixtures of ammonium sulfate/dicarboxylic acids at 25°C and have calculated van\u27t Hoff factors for each individual system. We have also used the vapor pressure data to determine the hygroscopic growth curves for pure dicarboxylic acids and eutonic mixtures and provide power law fits to the data. For the systems studied we find that the presence of soluble dicarboxylic acids at the eutonic proportion depresses hygroscopic growth when compared to pure ammonium sulfate. In addition, we find that the presence of low-solubility dicarboxylic acids at the eutonic proportion has no effect on the hygroscopic growth when compared to pure ammonium sulfate. To model the hygroscopic growth curves of the eutonic solutions, we employed the Zdanovskii, Stokes, and Robinson method. It was found that this approximation was accurate to within 17% for all the systems studied

A ruggedness evaluation of procedures for damage threshold testing optical materials

A ruggedness evaluation of approaches to damage threshold testing was performed to determine the influence of three procedural variables on damage threshold data. The differences between the number of test sites evaluated at an applied fluence level (1 site versus 10 sites), the number of laser pulses at each test site (1 pulse versus 200 pulses), and the beam diameter (0.35 mm versus 0.70 mm) were all found to significantly influence the damage threshold data over a 99-percent confidence interval

Hygroscopic Behavior of NaCl-Bearing Natural Aerosol Particles Using Environmental Transmission Electron Microscopy

We used conventional and environmental transmission electron microscopes to determine morphology, composition, and water uptake of individual natural inorganic aerosol particles collected from industrial pollution plumes and from clean and polluted marine environments. Five particle types are described in detail. They range from relatively insoluble mineral grains to internally mixed particles containing NaCl with other soluble or relatively insoluble material. We studied the hygroscopic behavior of these particles from 0 to 100% relative humidity (RH). Relatively insoluble materials do not take up water over the experimental RH range. Single crystals of NaCl from both natural and laboratory sources have a well-defined deliquescence point of approximately 76% RH at 291 K. NaCl-bearing aggregate particles appear to deliquesce between 74 and 76% RH (same RH within error) when NaCl is internally mixed with relatively insoluble phases, but the particles deliquesce at lower RH when aggregated with other soluble phases such as NaNO3. For all NaCl-bearing particles studied, hygroscopic growth is pronounced above 76% RH, and water uptake by the particles is dominated by the soluble phase. Furthermore, the soluble phase initiating deliquescence controls the locus of further hygroscopic growth of the aggregate particle. Our results demonstrate that composition and mixing state affect water uptake of natural aerosol particles. Furthermore, internally mixed particles are confirmed to deliquesce at lower RH values than predicted from the individual components

Phase Changes in Internally Mixed Maleic Acid/Ammonium Sulfate Aerosols

A temperature controlled flow tube system equipped with Fourier transform infrared (FTIR) detection of particle phase and relative humidity was used to measure the deliquescence and efflorescence of ammonium sulfate, maleic acid, and internally mixed maleic acid/ammonium sulfate particles. Our results indicate that maleic acid aerosols begin to take up water starting at a low relative humidity, ∼20%, and continue the constant uptake of water until the final deliquescence relative humidity (DRH), 89%, is reached. Internally mixed particles containing maleic acid and ammonium sulfate were found to deliquesce at a lower relative humidity (RH) than either of the pure species. Efflorescence studies indicated that while pure maleic acid particles crystallize at ∼18% RH, pure ammonium sulfate and all mixed aerosols effloresce at or just below 30% RH. Taken together, our results suggest that the presence of water-soluble organics internally mixed with ammonium sulfate aerosol could increase the range of conditions under which the aerosol is a solution

\u3ci\u3eStaphylococcus aureus\u3c/i\u3e Hyaluronidase Is a CodY-Regulated Virulence Factor

Staphylococcus aureus is a Gram-positive pathogen that causes a diverse range of bacterial infections. Invasive S. aureus strains secrete an extensive arsenal of hemolysins, immunomodulators, and exoenzymes to cause disease. Our studies have focused on the secreted enzyme hyaluronidase (HysA), which cleaves the hyaluronic acid polymer at the β-1,4 glycosidic bond. In the study described in this report, we have investigated the regulation and contribution of this enzyme to S. aureus pathogenesis. Using the Nebraska Transposon Mutant Library (NTML), we identified eight insertions that modulate extracellular levels of HysA activity. Insertions in the sigB operon, as well as in genes encoding the global regulators SarA and CodY, significantly increased HysA protein levels and activity. By altering the availability of branched-chain amino acids, we further demonstrated CodY-dependent repression of HysA activity. Additionally, through mutation of the CodY binding box upstream of hysA, the repression of HysA production was lost, suggesting that CodY is a direct repressor of hysA expression. To determine whether HysA is a virulence factor, a ΔhysA mutant of a community-associated methicillin-resistant S. aureus (CA-MRSA) USA300 strain was constructed and found to be attenuated in a neutropenic, murine model of pulmonary infection. Mice infected with this mutant strain exhibited a 4-log-unit reduction in bacterial burden in their lungs, as well as reduced lung pathology and increased levels of pulmonary hyaluronic acid, compared to mice infected with the wild-type, parent strain. Taken together, these results indicate that S. aureus hyaluronidase is a CodY-regulated virulence factor