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Description
Americans spend upwards of 90% of their time indoors, hence indoor air quality (IAQ) and the impact of IAQ on human health is a major public health concern. IAQ can be negatively impacted by outdoor pollution infiltrating indoors, the emission of indoor pollutants, indoor atmospheric chemistry and poor ventilation. Energy

Americans spend upwards of 90% of their time indoors, hence indoor air quality (IAQ) and the impact of IAQ on human health is a major public health concern. IAQ can be negatively impacted by outdoor pollution infiltrating indoors, the emission of indoor pollutants, indoor atmospheric chemistry and poor ventilation. Energy saving measures like retrofits to seal the building envelope to prevent the leakage of heated or cooled air will impact IAQ. However, existing studies have been inconclusive as to whether increased energy efficiency is leading to detrimental IAQ. In this work, field campaigns were conducted in apartment homes in Phoenix, Arizona to evaluate IAQ as it relates to particulate matter (PM), carbonyls, and tobacco specific nitrosamines (TSNA).

To investigate the impacts of an energy efficiency retrofit on IAQ, indoor and outdoor air quality sampling was carried out at Sunnyslope Manor, a city-subsidized senior living apartment complex. Measured indoor formaldehyde levels before the building retrofit exceeded reference exposure limits, but in the long term follow-up sampling, indoor formaldehyde decreased for the entire study population by a statistically significant margin. Indoor PM levels were dominated by fine particles and showed a statistically significant decrease in the long term follow-up sampling within certain resident subpopulations (i.e. residents who reported smoking and residents who had lived longer at the apartment complex). Additionally, indoor glyoxal and methylglyoxal exceeded outdoor concentrations, with methylglyoxal being more prevalent pre-retrofit than glyoxal, suggesting different chemical pathways are involved. Indoor concentrations reported are larger than previous studies. TSNAs, specifically N'-nitrosonornicotine (NNN), 4-(methyl-nitrosamino)-4-(3-pyridyl)-butanal (NNA) and 4-(methylnitrosoamino)-1-(3-pyridyl)-1-butanone (NNK) were evaluated post-retrofit at Sunnyslope Manor. Of the units tested, 86% of the smoking units and 46% of the non-smoking units had traces of at least one of the nitrosamines.
ContributorsFrey, Sarah E (Author) / Herckes, Pierre (Thesis advisor) / Fraser, Matthew P (Thesis advisor) / Destaillats, Hugo (Committee member) / Chizmeshya, Andrew (Committee member) / Arizona State University (Publisher)
Created2014
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Description
Bioparticles comprise a diverse amount of materials ubiquitously present in nature. From proteins to aerosolized biological debris, bioparticles have important roles spanning from regulating cellular functions to possibly influencing global climate. Understanding their structures, functions, and properties provides the necessary tools to expand our fundamental knowledge of biological

Bioparticles comprise a diverse amount of materials ubiquitously present in nature. From proteins to aerosolized biological debris, bioparticles have important roles spanning from regulating cellular functions to possibly influencing global climate. Understanding their structures, functions, and properties provides the necessary tools to expand our fundamental knowledge of biological systems and exploit them for useful applications. In order to contribute to this efforts, the work presented in this dissertation focuses on the study of electrokinetic properties of liposomes and novel applications of bioaerosol analysis. Using immobilized lipid vesicles under the influence of modest (less than 100 V/cm) electric fields, a novel strategy for bionanotubule fabrication with superior throughput and simplicity was developed. Fluorescence and bright field microscopy was used to describe the formation of these bilayer-bound cylindrical structures, which have been previously identified in nature (playing crucial roles in intercellular communication) and made synthetically by direct mechanical manipulation of membranes. In the biological context, the results of this work suggest that mechanical electrostatic interaction may play a role in the shape and function of individual biological membranes and networks of membrane-bound structures. A second project involving liposomes focused on membrane potential measurements in vesicles containing trans-membrane pH gradients. These types of gradients consist of differential charge states in the lipid bilayer leaflets, which have been shown to greatly influence the efficacy of drug targeting and the treatment of diseases such as cancer. Here, these systems are qualitatively and quantitatively assessed by using voltage-sensitive membrane dyes and fluorescence spectroscopy. Bioaerosol studies involved exploring the feasibility of a fingerprinting technology based on current understanding of cellular debris in aerosols and arguments regarding sampling, sensitivity, separations and detection schemes of these debris. Aerosolized particles of cellular material and proteins emitted by humans, animals and plants can be considered information-rich packets that carry biochemical information specific to the living organisms present in the collection settings. These materials could potentially be exploited for identification purposes. Preliminary studies evaluated protein concentration trends in both indoor and outdoor locations. Results indicated that concentrations correlate to certain conditions of the collection environment (e.g. extent of human presence), supporting the idea that bioaerosol fingerprinting is possible.
ContributorsCastillo Gutiérrez, Josemar Andreina (Author) / Hayes, Mark A. (Thesis advisor) / Herckes, Pierre (Committee member) / Ghrilanda, Giovanna (Committee member) / Arizona State University (Publisher)
Created2011
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Description
Understanding and predicting climate changes at the urban scale have been an important yet challenging problem in environmental engineering. The lack of reliable long-term observations at the urban scale makes it difficult to even assess past climate changes. Numerical modeling plays an important role in filling the gap of observation

Understanding and predicting climate changes at the urban scale have been an important yet challenging problem in environmental engineering. The lack of reliable long-term observations at the urban scale makes it difficult to even assess past climate changes. Numerical modeling plays an important role in filling the gap of observation and predicting future changes. Numerical studies on the climatic effect of desert urbanization have focused on basic meteorological fields such as temperature and wind. For desert cities, urban expansion can lead to substantial changes in the local production of wind-blown dust, which have implications for air quality and public health. This study expands the existing framework of numerical simulation for desert urbanization to include the computation of dust generation related to urban land-use changes. This is accomplished by connecting a suite of numerical models, including a meso-scale meteorological model, a land-surface model, an urban canopy model, and a turbulence model, to produce the key parameters that control the surface fluxes of wind-blown dust. Those models generate the near-surface turbulence intensity, soil moisture, and land-surface properties, which are used to determine the dust fluxes from a set of laboratory-based empirical formulas. This framework is applied to a series of simulations for the desert city of Erbil across a period of rapid urbanization. The changes in surface dust fluxes associated with urbanization are quantified. An analysis of the model output further reveals the dependence of surface dust fluxes on local meteorological conditions. Future applications of the models to environmental prediction are discussed.
ContributorsTahir, Sherzad Tahseen (Author) / Huang, Huei-Ping (Thesis advisor) / Phelan, Patrick (Committee member) / Herrmann, Marcus (Committee member) / Chen, Kangping (Committee member) / Clarke, Amanda (Committee member) / Arizona State University (Publisher)
Created2019
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Description
Dielectrophoresis (DEP) is a technique that influences the motion of polarizable particles in an electric field gradient. DEP can be combined with other effects that influence the motion of a particle in a microchannel, such as electrophoresis and electroosmosis. Together, these three can be used to probe properties

Dielectrophoresis (DEP) is a technique that influences the motion of polarizable particles in an electric field gradient. DEP can be combined with other effects that influence the motion of a particle in a microchannel, such as electrophoresis and electroosmosis. Together, these three can be used to probe properties of an analyte, including charge, conductivity, and zeta potential. DEP shows promise as a high-resolution differentiation and separation method, with the ability to distinguish between subtly-different populations. This, combined with the fast (on the order of minutes) analysis times offered by the technique, lend it many of the features necessary to be used in rapid diagnostics and point-of-care devices.

Here, a mathematical model of dielectrophoretic data is presented to connect analyte properties with data features, including the intercept and slope, enabling DEP to be used in applications which require this information. The promise of DEP to distinguish between analytes with small differences is illustrated with antibiotic resistant bacteria. The DEP system is shown to differentiate between methicillin-resistant and susceptible Staphylococcus aureus. This differentiation was achieved both label free and with bacteria that had been fluorescently-labeled. Klebsiella pneumoniae carbapenemase-positive and negative Klebsiella pneumoniae were also distinguished, demonstrating the differentiation for a different mechanism of antibiotic resistance. Differences in dielectrophoretic behavior as displayed by S. aureus and K. pneumoniae were also shown by Staphylococcus epidermidis. These differences were exploited for a separation in space of gentamicin-resistant and -susceptible S. epidermidis. Besides establishing the ability of DEP to distinguish between populations with small biophysical differences, these studies illustrate the possibility for the use of DEP in applications such as rapid diagnostics.
ContributorsHilton, Shannon (Author) / Hayes, Mark A. (Thesis advisor) / Borges, Chad (Committee member) / Herckes, Pierre (Committee member) / Arizona State University (Publisher)
Created2019
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Description
Biological fluids contain information-rich mixtures of biochemicals and particles such as cells, proteins, and viruses. Selective and sensitive analysis of these fluids can enable clinicians to accurately diagnose a wide range of pathologies. Fluid samples such as these present an intriguing challenge to researchers; they are packed with potentially vital

Biological fluids contain information-rich mixtures of biochemicals and particles such as cells, proteins, and viruses. Selective and sensitive analysis of these fluids can enable clinicians to accurately diagnose a wide range of pathologies. Fluid samples such as these present an intriguing challenge to researchers; they are packed with potentially vital information, but notoriously difficult to analyze. Rapid and inexpensive analysis of blood and other bodily fluids is a topic gaining substantial attention in both science and medicine. Current limitations to many analyses include long culture times, expensive reagents, and the need for specialized laboratory facilities and personnel. Improving these tests and overcoming their limitations would allow faster and more widespread testing for disease and pathogens, potentially providing a significant advantage for healthcare in many settings.

Both gradient separation techniques and dielectrophoresis can solve some of the difficulties presented by complex biological samples, thanks to selective capture, isolation, and concentration of analytes. By merging dielectrophoresis with a gradient separation-based approach, gradient insulator dielectrophoresis (g-iDEP) promises benefits in the form of rapid and specific separation of extremely similar bioparticles. High-resolution capture can be achieved by exploiting variations in the characteristic physical properties of cells and other bioparticles.

Novel implementation and application of the technique has demonstrated the isolation and concentration of blood cells from a complex biological sample, differentiation of bacterial strains within a single species, and separation of antibiotic-resistant and antibiotic-susceptible bacteria. Furthermore, this approach allows simultaneous concentration of analyte, facilitating detection and downstream analysis. A theoretical description of the resolving capabilities of g-iDEP was also developed. This theory explores the relationship between experimental parameters and resolution. Results indicate the possibility of differentiating particles with dielectrophoretic mobilities that differ by as little as one part in 100,000,000, or electrophoretic mobilities differing by as little as one part in 100,000. These results indicate the potential g-iDEP holds in terms of both separatory power and the possibility for diagnostic applications.
ContributorsJones, Paul Vernon (Author) / Hayes, Mark (Thesis advisor) / Ros, Alexandra (Committee member) / Herckes, Pierre (Committee member) / Arizona State University (Publisher)
Created2015
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Description
N-Nitrosodimethylamine (NDMA), a probable human carcinogen, has been found in clouds and fogs at concentration up to 500 ng/L and in drinking water as disinfection by-product. NDMA exposure to the general public is not well understood because of knowledge gaps in terms of occurrence, formation and fate both in air

N-Nitrosodimethylamine (NDMA), a probable human carcinogen, has been found in clouds and fogs at concentration up to 500 ng/L and in drinking water as disinfection by-product. NDMA exposure to the general public is not well understood because of knowledge gaps in terms of occurrence, formation and fate both in air and water. The goal of this dissertation was to contribute to closing these knowledge gaps on potential human NDMA exposure through contributions to atmospheric measurements and fate as well as aqueous formation processes.

Novel, sensitive methods of measuring NDMA in air were developed based on Solid Phase Extraction (SPE) and Solid Phase Microextraction (SPME) coupled to Gas Chromatography-Mass Spectrometry (GC-MS). The two measuring techniques were evaluated in laboratory experiments. SPE-GC-MS was applicable in ambient air sampling and NDMA in ambient air was found in the 0.1-13.0 ng/m3 range.

NDMA photolysis, the main degradation atmospheric pathway, was studied in the atmospheric aqueous phase. Water soluble organic carbon (WSOC) was found to have more impact than inorganic species on NDMA photolysis by competing with NDMA for photons and therefore could substantially increase the NDMA lifetime in the atmosphere. The optical properties of atmospheric WSOC were investigated in aerosol, fog and cloud samples and showed WSOC from atmospheric aerosols has a higher mass absorption efficiency (MAE) than organic matter in fog and cloud water, resulting from a different composition, especially in regards of volatile species, that are not very absorbing but abundant in fogs and clouds.

NDMA formation kinetics during chloramination were studied in aqueous samples including wastewater, surface water and ground water, at two monochloramine concentrations. A simple second order NDMA formation model was developed using measured NDMA and monochloramine concentrations at select reaction times. The model fitted the NDMA formation well (R2 >0.88) in all water matrices. The proposed model was then optimized and applied to fit the data of NDMA formation from natural organic matter (NOM) and model precursors in previously studies. By determining the rate constants, the model was able to describe the effect of water conditions such as DOC and pH on NDMA formation.
ContributorsZhang, Jinwei (Author) / Herckes, Pierre (Thesis advisor) / Westerhoff, Paul (Thesis advisor) / Fraser, Matthew (Committee member) / Shock, Everett (Committee member) / Arizona State University (Publisher)
Created2016
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Description

To investigate the impacts of an energy efficiency retrofit, indoor air quality and resident health were evaluated at a low‐income senior housing apartment complex in Phoenix, Arizona, before and after a green energy building renovation. Indoor and outdoor air quality sampling was carried out simultaneously with a questionnaire to characterize

To investigate the impacts of an energy efficiency retrofit, indoor air quality and resident health were evaluated at a low‐income senior housing apartment complex in Phoenix, Arizona, before and after a green energy building renovation. Indoor and outdoor air quality sampling was carried out simultaneously with a questionnaire to characterize personal habits and general health of residents. Measured indoor formaldehyde levels before the building retrofit routinely exceeded reference exposure limits, but in the long‐term follow‐up sampling, indoor formaldehyde decreased for the entire study population by a statistically significant margin. Indoor PM levels were dominated by fine particles and showed a statistically significant decrease in the long‐term follow‐up sampling within certain resident subpopulations (i.e. residents who report smoking and residents who had lived longer at the apartment complex).

ContributorsFrey, S.E. (Author) / Destaillats, H. (Author) / Cohn, S. (Author) / Ahrentzen, S. (Author) / Fraser, M.P. (Author)
Created2015
Description

Plasticizers are plastic additives used to enhance the physical properties of plastic and are ubiquitous in the environment. A class of plasticizer compounds called phthalate esters that are not fully eliminated in wastewater treatment facilities are relevant to the ecological health of downstream ecosystems and urban areas due to their

Plasticizers are plastic additives used to enhance the physical properties of plastic and are ubiquitous in the environment. A class of plasticizer compounds called phthalate esters that are not fully eliminated in wastewater treatment facilities are relevant to the ecological health of downstream ecosystems and urban areas due to their ecotoxicity, tendency for soil accumulation, and the emerging concern about their effects on public health. However, plasticizer concentrations in a constructed wetland environment have rarely been studied in the United States, prompting the need for a method of plasticizer quantification in the Tres Rios Constructed Wetlands which are sustained by the effluent of the 91st Avenue Wastewater Treatment Plant in Phoenix, Arizona. The concentrations of four common plasticizer compounds (dimethyl: DMP, diethyl: DEP, di-n-butyl: DnBP, and bis(2-ethylhexyl): DEHP phthalate) at five sites across the wetland surface water were quantified using solid-phase extraction followed by gas chromatography coupled with mass spectrometry (GC/MS). The sampling period included four sample sets taken from March 2022 to September 2022, which gave temporal data in addition to spatial concentration data. Quantification and quality control were performed using internal standard calibration, replicate samples, and laboratory blanks. Higher molecular weight phthalates accumulated in the wetland surface water at significantly higher average concentrations than those of lower molecular weight at a 95% confidence level, ranging from 8 ng/L to 7349 ng/L and 4 ng/L to 27876 ng/L for DnBP and DEHP, respectively. Concentrations for dimethyl phthalate and diethyl phthalate were typically less than 50 ng/L and were often below the method detection limit. Average concentrations of DnBP and DEHP were significantly higher during periods of high temperatures and arid conditions. The spatial distribution of phthalates was analyzed. Most importantly, a method for successful ultra-trace quantification of plasticizers at Tres Rios was established. These results confirm the presence of plasticizers at Tres Rios and a significant seasonal increase in their surface water concentrations. The developed analytical procedure provides a solid foundation for the Wetlands Environmental Ecology Lab at ASU to further investigate plasticizers and contaminants of emerging concern and determine their ultimate fate through volatilization, sorption, photodegradation, hydrolysis, microbial biodegradation, and phytoremediation studies.

ContributorsStorey, Garrett (Author) / Herckes, Pierre (Thesis director) / Childers, Dan (Committee member) / Borges, Chad (Committee member) / Barrett, The Honors College (Contributor) / School of Sustainability (Contributor) / School of Molecular Sciences (Contributor)
Created2023-05
Description

Quantifying halogen presence and speciation in particulate matter is crucial given the role atmospheric particulates play in transport and cycling. While some halogens (fluorine and chlorine) are often included in aerosol studies, iodine and bromine have rarely been examined, especially outside of a marine environment. Focus on this environment is,

Quantifying halogen presence and speciation in particulate matter is crucial given the role atmospheric particulates play in transport and cycling. While some halogens (fluorine and chlorine) are often included in aerosol studies, iodine and bromine have rarely been examined, especially outside of a marine environment. Focus on this environment is, in part, due to the existence of biogenic marine sources for both halogens. However, examining iodine and bromine in an urban environment has the potential to provide key insights into the transport and processing of these species in the atmosphere. As Tempe is set within a desert environment, bromine concentration is expected to be relatively high due to its presence in Earth’s crust, while iodine is expected to exist in higher concentrations near the coast. To detect presence and concentration, ICP-MS analysis was performed on samples taken in Tempe, AZ as well as sites in Bakersfield, CA and Davis, CA, which yielded preliminary results in line with these expectations. A secondary set of samples were taken in Tempe, AZ during dust storms, haboobs, and winter holidays. CIC was used to determine the organic fraction. In doing so, this study aims to identify species present in an urban environment as well as potential transportation pathways.

ContributorsLoera, Lourdes (Author) / Herckes, Pierre (Thesis director) / Richert, Ranko (Committee member) / Fraser, Matthew (Committee member) / Barrett, The Honors College (Contributor) / School of Molecular Sciences (Contributor) / School of Human Evolution & Social Change (Contributor)
Created2023-05
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Description
N-nitrosodimethylamine (NDMA) is a probable human carcinogen that has been detected in various environments including the atmosphere, clouds, surface waters, and drinking water. NDMA can form through natural reactions in the aqueous phase of the atmosphere and it can form as a disinfection byproduct in water treatment. Due to its

N-nitrosodimethylamine (NDMA) is a probable human carcinogen that has been detected in various environments including the atmosphere, clouds, surface waters, and drinking water. NDMA can form through natural reactions in the aqueous phase of the atmosphere and it can form as a disinfection byproduct in water treatment. Due to its carcinogenic nature, it is important to understand the mechanism of formation of NDMA in both engineered processes such as water treatment and in natural processes in fogs and clouds. NDMA might form through the reaction of chloramines with amines in both cases. This work analyzes polydiallyldimethyl ammonium chloride (PolyDADMAC), which is the most commonly used polymer at drinking water treatment plants and has the potential to form NDMA if free polymer is present during the chloramination (disinfection) process. The composition of industrial polyDADMAC solutions is not well understood and is difficult to analyze. This work uses 1H and 13C nuclear magnetic resonance (NMR) to analyze the polymer solution composition. Both 1H and 13C NMR allow investigation of the presence of trace impurities in the solution, gather structural information such as chain length, and inform on reaction mechanisms. The primary impurities of concern for NDMA formation were identified as dimethylamine (DMA) and short-chain oligomers of the polyDADMAC. 13C NMR was further used to confirm that NDMA likely forms from polyDADMAC via a Hofmann elimination. Chloramines might also form in fogs and clouds although to date the potential for chloramines to form NDMA in atmospheric fog and cloud droplets has not been investigated. This work uses computational modeling to determine that at reported atmospheric conditions, the chloramine pathway contributes to less than 0.01% NDMA formation. The numerical modeling identified a need for more atmospheric HOCl measurements. This work proposes a concept of using HOCl to react to form chloramine, which can react to form NDMA as a way to quantify atmospheric HOCl.
ContributorsDonovan, Samantha Jo (Author) / Herckes, Pierre (Thesis advisor) / Westerhoff, Paul (Committee member) / Hayes, Mark (Committee member) / Arizona State University (Publisher)
Created2022