Date of Degree
Access restricted until 08/31/2019
PhD (Doctor of Philosophy)
Chemical and Biochemical Engineering
Charles O. Stanier
First Committee Member
Gregory R. Carmichael
Second Committee Member
Third Committee Member
Keri C. Hornbuckle
Fourth Committee Member
Scott N. Spak
Cyclic volatile methyl siloxanes (cVMS) are anthropogenic chemicals present in a range of consumer personal care products such as antiperspirants and lotions. They are highly volatile, and readily released to the atmosphere by personal care product use. Generally unreactive, they are found in high concentrations in indoor environments, and transported long distances in the atmosphere. A major removal pathway for these silicon-containing gases is reaction with the OH radical, which has been recently shown to yield secondary Si-containing aerosol compounds in addition to the gas phase products. Despite the significance of the atmospheric fate of these compounds, much of the previous work has focused on the aquatic fate, and almost exclusively on the parent compounds. The oxidation products and potential aerosol species have received much less attention, with almost no ambient measurements or experimental physical property data. This work investigates cVMS with a focus on providing much needed information on potential loadings of the oxidation products, their distribution, and particle phase properties using an atmospheric model and laboratory experiments. Specifically, cVMS was added to the Community Multiscale Air Quality (CMAQ) model; expected concentrations, spatial distribution, and seasonal trends were quantified; cVMS secondary aerosols generated and physical properties characterized; and secondary aerosol parameters for atmospheric modeling developed.
The CMAQ model code was modified to update the chemical mechanism with cVMS, develop emissions, boundary, and deposition parameters to simulate four separate seasons at a spatial resolution of 36 km over North America. Typical model concentrations showed parent compounds were highly dependent on population density as cities had monthly averaged peak decamethylcyclopentasiloxane (D5) concentrations up to 432 ng m−3. Peak oxidized D5 concentrations were significantly less, up to 9 ng m−3, and were located downwind of major urban areas. Model results were compared to available measurements and previous simulation results. Parent compound concentrations in urban locations were sensitive to transport factors, while parent compounds in rural areas and oxidized product concentrations were influenced by large-scale seasonal variability in OH.
Secondary aerosols were formed by reacting cVMS gas in an oxidation flow reactor. The particles were characterized for concentration, size, aerosol yield, morphology, energy-dispersive spectroscopy (EDS) individual particle chemical composition, hygroscopicity (cloud condensation nuclei formation potential), and volatility. Aerosol concentrations were 68 – 220 µg m-3 with aerosol mass fractions (i.e. yields) of 0.22-0.50. Aerosol yield was sensitive to chamber OH, indicating an interplay between oxidation conditions and the concentration of lower volatility species. The D5 oxidation products were non-volatile, with only the smallest particles (10 nm) exhibiting more than 4% of diameter decrease upon heating to 190°C temperature. The D5 oxidation aerosols were relatively non-hygroscopic, with average hygroscopicity kappa of ~0.01.
Experimental data was analyzed to develop secondary aerosol parameters for the CMAQ model. Chamber yield data was fit to a two-product Odum volatility model with yield values of 0.14 and 0.82, corresponding to saturation concentrations of 0.95 and 484 µg m-3, respectively. The recommended enthalpy of vaporization is 18 kJ mol-1 based on other modeled secondary organic aerosol. Recommended molecular weights for the D5 low volatility Odum, high volatility Odum, and non-volatile oligomerization species are 588, 373, and 733 g mol-1 corresponding to OH substituted ring-opened, monomer, and dimer species, respectively.
This work provides simulations of expected concentrations, spatial patterns, and seasonal influence of the parent and oxidized cVMS species to extend beyond the few parent cVMS measurements and nonexistent oxidation product measurements. The modeling work serves as an important tool to guide future field measurements especially important for the confirmation of particle phase oxidation products. Extensive aerosol characterization measurements provide much needed physical property data important for future modeling, risk, and exposure studies.
CMAQ, Cyclic Siloxane, Oxidation Flow Reactor, Personal Care Product, Secondary Organic Aerosol
xvii, 209 pages
Includes bibliographical references (page 54).
Copyright © 2018 Nathan Joseph Janechek
Janechek, Nathan Joseph. "Atmospheric modeling and experimental characterization of gas and aerosol phase cyclic volatile methyl siloxanes." PhD (Doctor of Philosophy) thesis, University of Iowa, 2018.
Available for download on Saturday, August 31, 2019