Matching Items (25)
Description
Particulate trace metals can enter the atmosphere as mineral dust, sea spray, anthropogenic emissions, biomass burning, etc. Once in the atmosphere they can undergo a variety of transformations including aqueous phase (cloud) processing, photochemical reactions, interact with gases, and ultimately deposit. Metals in aerosols are of particular interest because of their natural and anthropogenic sources as well as their effects on local (human health) and global (climate change) scales. This work investigates the metal component of atmospheric particles and how it changes during physical and chemical processes at local, regional and global scales, through laboratory and field studies. In the first part of this work, the impact of local dust storms (haboobs) on ambient metal concentrations and speciation is investigated in Tempe, AZ. It was found that metal concentrations substantially increase (> 10 times) during these events before returning to pre-storm levels. In a second part of this work, the impact of fog processing on metal concentrations, solubility and speciation is examined through field observations in California’s Central Valley. The observations show that fog processing has a profound effect on local metal concentrations but the trends are not consistent between sites or even between events, indicating complex processes that need further investigation. For example, fogs have an effect on scavenging and solubility of iron in Davis, while in Fresno soluble iron content is indicative of the source of the aerosol. The last part of the thesis investigates the role of particle size on the solubilization of iron from mineral dust aerosols during global atmospheric transport through laboratory experiments. The experiments showed that mineralogy and pH have the greatest effect on iron solubility in atmospheric aerosols in general while particle size and photochemistry impact mainly the solubility of iron oxides.
ContributorsMarcotte, Aurelie Rose (Author) / Herckes, Pierre (Thesis advisor) / Anbar, Ariel (Thesis advisor) / Fraser, Matthew (Committee member) / Hayes, Mark (Committee member) / Arizona State University (Publisher)
Created2015
Description
Vapor intrusion (VI) pathway assessment often involves the collection and analysis of groundwater, soil gas, and indoor air data. There is temporal variability in these data, but little is understood about the characteristics of that variability and how it influences pathway assessment decision-making. This research included the first-ever collection of a long-term high-frequency indoor air data set at a house with VI impacts overlying a dilute chlorinated solvent groundwater plume. It also included periodic synoptic snapshots of groundwater and soil gas data and high-frequency monitoring of building conditions and environmental factors. Indoor air trichloroethylene (TCE) concentrations varied over three orders-of-magnitude under natural conditions, with the highest daily VI activity during fall, winter, and spring months. These data were used to simulate outcomes from common sampling strategies, with the result being that there was a high probability (up to 100%) of false-negative decisions and poor characterization of long-term exposure. Temporal and spatial variability in subsurface data were shown to increase as the sampling point moves from source depth to ground surface, with variability of an order-of-magnitude or more for sub-slab soil gas. It was observed that indoor vapor sources can cause subsurface vapor clouds and that it can take days to weeks for soil gas plumes created by indoor sources to dissipate following indoor source removal. A long-term controlled pressure method (CPM) test was conducted to assess its utility as an alternate approach for VI pathway assessment. Indoor air concentrations were similar to maximum concentrations under natural conditions (9.3 μg/m3 average vs. 13 μg/m3 for 24 h TCE data) with little temporal variability. A key outcome was that there were no occurrences of false-negative results. Results suggest that CPM tests can produce worst-case exposure conditions at any time of the year. The results of these studies highlight the limitations of current VI pathway assessment approaches and demonstrate the need for robust alternate diagnostic tools, such as CPM, that lead to greater confidence in data interpretation and decision-making.
ContributorsHolton, Chase Weston (Author) / Johnson, Paul C (Thesis advisor) / Fraser, Matthew (Committee member) / Forzani, Erica (Committee member) / Arizona State University (Publisher)
Created2015
Description
This thesis examines using thermal energy storage as a demand side management tool for air-conditioning loads with the goal of increasing photovoltaic penetration. It uses Arizona State University (ASU) as a case study. The analysis is completed with a modeling approach using typical meteorological year (TMY) data, along with ASU’s historical load data. Sustainability, greenhouse gas emissions, carbon neutrality, and photovoltaic (PV) penetration are all considered along with potential economic impacts.
By extrapolating the air-conditioning load profile from the existing data sets, it can be ensured that cooling demands can be met at all times under the new management method. Using this cooling demand data, it is possible to determine how much energy is required to meet these needs. Then, modeling the PV arrays, the thermal energy storage (TES), and the chillers, the maximum PV penetration in the future state can be determined.
Using this approach, it has been determined that ASU can increase their solar PV resources by a factor of 3.460, which would amount to a PV penetration of approximately 48%.
By extrapolating the air-conditioning load profile from the existing data sets, it can be ensured that cooling demands can be met at all times under the new management method. Using this cooling demand data, it is possible to determine how much energy is required to meet these needs. Then, modeling the PV arrays, the thermal energy storage (TES), and the chillers, the maximum PV penetration in the future state can be determined.
Using this approach, it has been determined that ASU can increase their solar PV resources by a factor of 3.460, which would amount to a PV penetration of approximately 48%.
ContributorsRouthier, Alexander F (Author) / Honsberg, Christiana (Thesis advisor) / Fraser, Matthew (Committee member) / Bowden, Stuart (Committee member) / Arizona State University (Publisher)
Created2016
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 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.
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
Environmental releases of neonicotinoid and fipronil insecticides via U.S. wastewater infrastructure
Description
This dissertation is focused on environmental releases from U.S. wastewater infrastructure of recently introduced, mass-produced insecticides, namely neonicotinoids as well as fipronil and its major degradates (sulfone, sulfide, amide, and desulfinyl derivatives), jointly known as fiproles. Both groups of compounds recently have caught the attention of regulatory agencies worldwide due to their toxic effects on pollinators and on aquatic invertebrates at very low, part-per-trillion levels (Chapter 1). Mass balance studies conducted for 13 U.S. wastewater treatment plants (WWTPs) showed ubiquitous occurrence (3-666 ng/L) and persistence of neonicotinoids (Chapter 2). For the years 2001 through 2016, a longitudinal nationwide study was conducted on the occurrence of fiproles, via analysis of sludge as well as raw and treated wastewater samples. Sludge analysis revealed ubiquitous fiprole occurrence since 2001 (0.2-385 µg/kg dry weight) and a significant increase (2.4±0.3-fold; p<0.005) to elevated levels found both in 2006/7 and 2015/6. This study established a marked persistence of fiproles during both wastewater and sludge treatment, while also identifying non-agricultural uses as a major source of fiprole loading to wastewater (Chapter 3). Eight WWTPs were monitored in Northern California to assess pesticide inputs into San Francisco Bay from wastewater discharge. Per-capita-contaminant-loading calculations identified flea and tick control agents for use on pets as a previously underappreciated source term dominating the mass loading of insecticides to WWTPs in sewage and to the Bay in treated wastewater (Chapter 4). A nationwide assessment of fipronil emissions revealed that pet products, while representing only 22±7% of total fipronil usage (2011-2015), accounted for 86±5% of the mass loading to U.S. surface waters (Chapter 5). In summary, the root cause for considerable annual discharges into U.S. surface waters of the neonicotinoid imidacloprid (3,700-5,500 kg/y) and of fipronil related compounds (1,600-2,400 kg/y) is domestic rather than agricultural insecticide use. Reclaimed effluent from U.S. WWTPs contained insecticide levels that exceed toxicity benchmarks for sensitive aquatic invertebrates in 83% of cases for imidacloprid and in 67% of cases for fipronil. Recommendations are provided on how to limit toxic inputs in the future.
ContributorsSadaria, Akash Mahendra (Author) / Halden, Rolf (Thesis advisor) / Fraser, Matthew (Committee member) / Perreault, Francois (Committee member) / Mascaro, Giuseppe (Committee member) / Arizona State University (Publisher)
Created2017
Description
Shifting to renewable energy from fossil fuels is not occurring rapidly. Determining where to locate renewable power plants could help expedite development. The project discussed here uses a GIS ranking tool to determine potential locations for solar and wind power plants in Arizona. Criteria include renewable input (irradiance/wind class), topographic slope, and distance from transmission lines. These are ranked and summed to determine areas with the most potential. The resulting outputs show that there is much more potential land for solar development than wind development. Further analysis in this paper will focus solely on solar due to wind's lower potential. Land sensitivity and ownership are used to assess the feasibility of development. There are many groupings of highly ranked land across the state, but the largest stretch of land runs from outside of Marana (south-central Arizona) northwest to about 60 miles west of Wickenburg (central-west). This regions is mainly on BLM, state, and privately owned land. Some of this land is considered sensitive, but non-sensitive areas with high potential are frequent throughout. Renewable potential in other states could be determined using this tool as well. Variables could be weighted or added depending on each area's need.
ContributorsZeck, Kevin Michael (Author) / Fraser, Matthew (Thesis director) / Pasqualetti, Martin (Committee member) / Cowger, Lane (Committee member) / Barrett, The Honors College (Contributor) / School of Geographical Sciences and Urban Planning (Contributor) / School of Sustainability (Contributor)
Created2013-05
Description
Life cycle assessment (LCA) is increasingly identified as the proper tool/framework for performing cradle to grave analysis of a product, technology, or supply chain. LCA proceeds by comparing the materials and energy needed for materials extraction, benefaction, and end-of-life management, in addition to the actual lifetime of the product. This type of analysis is commonly used to evaluate forms of renewable energy to ensure that we don't harm the environment in the name of saving it. For instance, LCA for photovoltaic (PV) technologies can be used to evaluate the environmental impacts. CdTe thin film solar cells rely on cadmium and tellurium metals which are produced as by-products in the refining of zinc and copper ore, respectively. In order to understand the environmental burdens of tellurium, it is useful to explore the extraction and refining process of copper. Copper can be refined using either a hydrometallurgical or pyrometallurgical process. I conducted a comparison of these two methods to determine the environmental impacts, the chemical reactions which take place, the energy requirements, and the extraction costs of each. I then looked into the extraction of tellurium from anode slime produced in the pyrometallurgical process and determined the energy requirements. I connected this to the production of CdTe and the power produced from a CdTe module, and analyzed the production cost of CdTe modules under increasing tellurium prices. It was concluded that tellurium production will be limited by increasing hydrometallurgical extraction of copper. Additionally, tellurium scarcity will not provide a physical constraint to CdTe commercial expansion; however it could affect the price reduction goals.
ContributorsMacIsaac, Kirsten Breanne (Author) / Seager, Thomas (Thesis director) / Fraser, Matthew (Committee member) / Wender, Ben (Committee member) / Barrett, The Honors College (Contributor) / Chemical Engineering Program (Contributor)
Created2013-05
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, 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
Description
The prevalence and unique properties of airborne nanoparticles have raised concerns regarding their potential adverse health effects. Despite their significance, the understanding of nanoparticle generation, transport, and exposure remains incomplete. This study first aimed to assess nanoparticle exposure in indoor workplace environments, in the semiconductor manufacturing industry. On-site observations during tool preventive maintenance revealed a significant release of particles smaller than 30 nm, which subsequent instrumental analysis confirmed as predominantly composed of transition metals. Although the measured mass concentration levels did not exceed current federal limits, it prompted concerns regarding how well filter-based air sampling methods would capture the particles for exposure assessment and how well common personal protective equipment would protect from exposure. To address these concerns, this study evaluated the capture efficiency of filters and masks. When challenged by aerosolized engineered nanomaterials, common filters used in industrial hygiene sampling exhibited capture efficiencies of over 60%. Filtering Facepiece Respirators, such as the N95 mask, exhibited a capture efficiency of over 98%. In contrast, simple surgical masks showed a capture efficiency of approximately 70%. The experiments showed that face velocity and ambient humidity influence capture performance and mostly identified the critical role of mask and particle surface charge in capturing nanoparticles. Masks with higher surface potential exhibited higher capture efficiency towards nanoparticles. Eliminating their surface charge resulted in a significantly diminished capture efficiency, up to 43%. Finally, this study characterized outdoor nanoparticle concentrations in the Phoenix metropolitan area, revealing typical concentrations on the order of 10^4 #/cm3 consistent with other urban environments. During the North American monsoon season, in dust storms, with elevated number concentrations of large particles, particularly in the size range of 1-10 μm, the number concentration of nanoparticles in the size range of 30-100 nm was substantially lower by approximately 55%. These findings provide valuable insights for future assessments of nanoparticle exposure risks and filter capture mechanisms associated with airborne nanoparticles.
ContributorsZhang, Zhaobo (Author) / Herckes, Pierre (Thesis advisor) / Westerhoff, Paul (Committee member) / Shock, Everett (Committee member) / Fraser, Matthew (Committee member) / Arizona State University (Publisher)
Created2023
Description
Atmospheric particulate matter (PM) has a pronounced effect on our climate, and exposure to PM causes negative health outcomes and elevated mortality rates in urban populations. Reactions that occur in fog can form new secondary organic aerosol material from gas-phase species or primary organic aerosols. It is important to understand these reactions, as well as how organic material is scavenged and deposited, so that climate and health effects can be fully assessed. Stable carbon isotopes have been used widely in studying gas- and particle-phase atmospheric chemistry. However, the processing of organic matter by fog has not yet been studied, even though stable isotopes can be used to track all aspects of atmospheric processing, from particle formation, particle scavenging, reactions that form secondary organic aerosol material, and particle deposition. Here, carbon isotope analysis is used for the first time to assess the processing of carbonaceous particles by fog.
This work first compares carbon isotope measurements (δ13C) of particulate matter and fog from locations across the globe to assess how different primary aerosol sources are reflected in the atmosphere. Three field campaigns are then discussed that highlight different aspects of PM formation, composition, and processing. In Tempe, AZ, seasonal and size-dependent differences in the δ13C of total carbon and n-alkanes in PM were studied. δ13C was influenced by seasonal trends, including inversion, transport, population density, and photochemical activity. Variations in δ13C among particle size fractions were caused by sources that generate particles in different size modes.
An analysis of PM from urban and suburban sites in northeastern France shows how both fog and rain can cause measurable changes in the δ13C of PM. The δ13C of PM was consistent over time when no weather events occurred, but particles were isotopically depleted by up to 1.1‰ in the presence of fog due to preferential scavenging of larger isotopically enriched particles. Finally, the δ13C of the dissolved organic carbon in fog collected on the coast of Southern California is discussed. Here, temporal depletion of the δ13C of fog by up to 1.2‰ demonstrates its use in observing the scavenging and deposition of organic PM.
This work first compares carbon isotope measurements (δ13C) of particulate matter and fog from locations across the globe to assess how different primary aerosol sources are reflected in the atmosphere. Three field campaigns are then discussed that highlight different aspects of PM formation, composition, and processing. In Tempe, AZ, seasonal and size-dependent differences in the δ13C of total carbon and n-alkanes in PM were studied. δ13C was influenced by seasonal trends, including inversion, transport, population density, and photochemical activity. Variations in δ13C among particle size fractions were caused by sources that generate particles in different size modes.
An analysis of PM from urban and suburban sites in northeastern France shows how both fog and rain can cause measurable changes in the δ13C of PM. The δ13C of PM was consistent over time when no weather events occurred, but particles were isotopically depleted by up to 1.1‰ in the presence of fog due to preferential scavenging of larger isotopically enriched particles. Finally, the δ13C of the dissolved organic carbon in fog collected on the coast of Southern California is discussed. Here, temporal depletion of the δ13C of fog by up to 1.2‰ demonstrates its use in observing the scavenging and deposition of organic PM.
ContributorsNapolitano, Denise (Author) / Herckes, Pierre (Thesis advisor) / Fraser, Matthew (Committee member) / Shock, Everett (Committee member) / Arizona State University (Publisher)
Created2018