A Study of the Aqueous Phase Processing of Organic Aerosols through Stable Isotope Analysis

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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…

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.
Date Created
2018
Agent

Tracking chemical indicators of public health in the urban water environment

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Description
This dissertation focuses on the application of urban metabolism metrology (UMM) to process streams of the natural and built water environment to gauge public health concerning exposure to carcinogenic N-nitrosamines and abuse of narcotics. A survey of sources of exposure…

This dissertation focuses on the application of urban metabolism metrology (UMM) to process streams of the natural and built water environment to gauge public health concerning exposure to carcinogenic N-nitrosamines and abuse of narcotics. A survey of sources of exposure to N-nitrosamines in the U.S. population identified contaminated food products (1,900 ± 380 ng/day) as important drivers of attributable cancer risk (Chapter 2). Freshwater sediments in the proximity of U.S. municipal wastewater treatment plants were shown for the first time to harbor carcinogenic N-nitrosamine congeners, including N-nitrosodibutylamine (0.2-3.3 ng/g dw), N-nitrosodiphenylamine (0.2-4.7 ng/g dw), and N-nitrosopyrrolidine (3.4-19.6 ng/g dw) were, with treated wastewater discharge representing one potential factor contributing to the observed contamination (p=0.42) (Chapter 3). Opioid abuse rates in two small midwestern communities were estimated through the application of wastewater-based epidemiology (WBE). Average concentrations of opioids (City 1; City 2) were highest for morphine (713 ± 38, 306 ± 29 ng/L) and varied by for the remainder of the screened analytes. Furthermore, concentrations of the powerful opioid fentanyl (1.7 ± 0.2, 1.0 ± 0.5 ng/L) in wastewater were reported for the first time in the literature for the U.S. (Chapter 4). To gauge narcotic consumption within college-aged adults the WBE process used in Chapter 4 was applied to wastewater collected from a large university in the Southwestern U.S. Estimated narcotics consumption, in units of mg/day/1,000 persons showed the following rank order: cocaine (470 ± 42), heroin (474 ± 32), amphetamine (302 ± 14) and methylphenidate (236 ± 28). Most parental drugs and their respective metabolites showed detection frequencies in campus wastewater of 80% or more, with the notable exception of fentanyl, norfentanyl, buprenorphine, and norbuprenorphine. Estimated consumption of all narcotics, aside from attention-deficit/hyperactivity disorder medication, were higher than values reported in previous U.S. WBE studies for U.S. campuses (Chapter 5). The analyses presented here have identified variation in narcotic consumption habits across different U.S. communities, which can be gauged through UMM. Application of these techniques should be implemented throughout U.S. communities to provide insight into ongoing substance abuse and health issues within a community.
Date Created
2018
Agent

Streamlining Early Stage Photovoltaic Electrical Subcontracting Scope and Pricing

Description
This paper introduces an excel tool created to improve the accuracy of electrical subcontracting prices for solar photovoltaic energy systems while also minimizing the time needed to create these price estimations. The need for improved precision, specifically during the early…

This paper introduces an excel tool created to improve the accuracy of electrical subcontracting prices for solar photovoltaic energy systems while also minimizing the time needed to create these price estimations. The need for improved precision, specifically during the early stages of a project, is examined and the paper also goes into detail about the components and pricing method that are incorporated into the excel tool. Lastly, the results of the price estimation tool are compared to real bids and recommendations are made for improvement to the tool.
Date Created
2018-05
Agent

Developing a Tool to Identify Locations for Renewable Energy Potential

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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…

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.
Date Created
2013-05
Agent

Scaling CdTe Solar: Life Cycle Assessment of Te Byproducts from Cu Extraction

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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,…

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.
Date Created
2013-05
Agent

Environmental releases of neonicotinoid and fipronil insecticides via U.S. wastewater infrastructure

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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…

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.
Date Created
2017
Agent

Organic Composition and Source Apportionment of Fine Aerosol at Monterrey, Mexico, Based on Organic Markers

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Description

Primary emissions from anthropogenic and biogenic sources as well as secondary formation are responsible for the pollution levels of ambient air in major urban areas. These sources release fine particles into the air that negatively impact human health and the…

Primary emissions from anthropogenic and biogenic sources as well as secondary formation are responsible for the pollution levels of ambient air in major urban areas. These sources release fine particles into the air that negatively impact human health and the environment. Organic molecular markers, which are compounds that are unique to specific PM2.5 sources, can be utilized to identify the major emission sources in urban areas. In this study, 43 representative PM2.5 samples, for both daytime and nighttime periods, were built from individual samples collected in an urban site of the Monterrey metropolitan area (MMA) during the spring and fall of 2011 and 2012. The samples were analyzed for organic carbon, elemental carbon, and organic molecular markers. Several diagnostic tools were employed for the preliminary identification of emission sources. Organic compounds for eight compound classes were quantified. The n-alkanoic acids were the most abundant, followed by n-alkanes, wood smoke markers, and levoglucosan/alkenoic acids. Polycyclic aromatic hydrocarbons (PAHs) and hopanes were less abundant. The carbon preference index (0.7–2.6) for n-alkanes indicates a major contribution of anthropogenic and mixed sources during the fall and the spring, respectively. Hopanes levels confirmed the contribution from gasoline and diesel engines. In addition, the contribution of gasoline and diesel vehicle exhaust was confirmed and identified by the PAH concentrations in PM2.5. Diagnostic ratios of PAHs showed emissions from burning coal, wood, biomass, and other fossil fuels. The total PAHs and elemental carbon were correlated (r2 =  0.39–0.70) across the monitoring periods, reinforcing that motor vehicles are the major contributors of PAHs. Cholesterol levels remained constant during the spring and fall, showing evidence of the contribution of meat-cooking operations, while the isolated concentrations of levoglucosan suggested occasional biomass burning events. Finally, source attribution results obtained using the CMB (chemical mass balance) model indicate that emissions from motor vehicle exhausts are the most important, accounting for the 64 % of the PM2.5, followed by meat-cooking operations with 31 % The vegetative detritus and biomass burning had the smallest contribution (2.2 % of the PM2.5). To our knowledge, this is only the second study to explore the organic composition and source apportionment of fine organic aerosol based on molecular markers in Mexico and the first for the MMA. Particularly molecular marker were quantified by solvent extraction with dichloromethane, derivatization, and gas chromatography with mass spectrometry (GC/MS).

Date Created
2016-01-26
Agent

Using thermal energy storage to increase photovoltaic penetration at Arizona State University's Tempe Campus

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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…

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%.
Date Created
2016
Agent

Investigations into the occurrence, formation and fate of N-nitrosodimethylamine (NDMA) in air and water

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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…

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.
Date Created
2016
Agent

Vapor intrusion at a site with an alternative pathway and a fluctuating groundwater table

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Description
Vapor intrusion (VI), can pose health risks to building occupants. Assessment and mitigation at VI impacted sites have been guided by a site conceptual model (SCM) in which vapors originate from subsurface sources, diffuse through soil matrix and enter into…

Vapor intrusion (VI), can pose health risks to building occupants. Assessment and mitigation at VI impacted sites have been guided by a site conceptual model (SCM) in which vapors originate from subsurface sources, diffuse through soil matrix and enter into a building by gas flow across foundation cracks. Alternative VI pathways and groundwater table fluctuations are not often considered.

Alternative VI pathways, involving vapor transport along sewer lines and other subsurface infrastructure, have recently been found to be significant contributors to VI impacts at some sites. This study evaluated approaches for identifying and characterizing the significance of alternative VI pathways and assessed the effectiveness of conventional mitigation at a site with an alternative VI pathway that can be manipulated to be on or off. The alternative pathway could not be identified using conventional pathway assessment procedures and can only be discovered under controlled pressure method (CPM) conditions. Measured emission rates were two orders of magnitude greater than screening model estimates and sub-foundation vertical soil gas profiles changed and were no longer consistent with the conventional VI conceptual model when the CPM test was conducted. The pipe flow VI pathway reduced the vacuum performance of the sub-slab depressurization (SSD) VI mitigation system, but the SSD system still provided sufficient protection to the house.

The relationship between groundwater table fluctuations and subsurface vapor emissions and transport is examined using multi-year data from the field site, and is studied in the laboratory. In addition, a broader range of conditions is examined through use of modeling validated with the experimental data. The results indicate that fluctuating groundwater tables will lead to amplified volatile organic chemical (VOC) emissions from groundwater to soil surface relative to steady water table elevation, however, the magnitude of this amplification is less concerned when long-term water fluctuation present. No clear correlations were found between VOC emissions and water table changes at the study site where annual water table fluctuations of about 0.3 m existed. Significant VOC emission amplifications by water table fluctuation would be expected under shallow groundwater conditions according to model analysis results.
Date Created
2015
Agent
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