Matching Items (32)

Simplifying Functional Assays for Partitioning of Nanoparticles in Immiscible Phases

Description

Conventional functional assays (FAs), which are used to describe the behaviors and assess the impacts of engineered nanomaterials (ENMs), have extensive human factor related errors (i.e. extraction process errors due

Conventional functional assays (FAs), which are used to describe the behaviors and assess the impacts of engineered nanomaterials (ENMs), have extensive human factor related errors (i.e. extraction process errors due to human laboratory skills), and consume considerable amounts of laboratory material. Consequently, there is a need and opportunity to improve conventional FAs by minimizing the potential for human factor related errors, reducing the usage of ENMs and reagents, and increase experimental reproducibility. The goal of this study was to simplify the conventional FAs and evaluate the feasibility and reproducibility of the simplified FAs. The underlying hypothesis implies that simplified FAs could quickly quantify the partitioning of nanoparticles between immiscible phases with minimum human factor related errors, low usage of ENMs, and high experimental reproducibility. Three different FAs were studied for this project: octanol-water assay, distribution to sediment assay, and cloud point extraction (CPE) assay. Three widely applied ENMs were selected: silver nanoparticles (AgNPs) coated with citrate, magnetite nanoparticles (Fe3O4) capped with polyvinyl pyrrolidone (PVP), and multiwall carbon nanotubes (MWCNTS) dispersed in an organic solution. Removal efficiency was the selected parameter used to describe the distribution of ENMs. Based on the variability and the t-tests on the removal efficiencies of conventional and simplified FAs, it is conclusive that the conventional octanol-water FAs on Fe3O4, the sediment FAs on Fe3O4, and the CPE FAs on MWCNTs and Fe3O4 can be simplified. The conventional octanol-water on AgNPs and the sediment FAs on AgNPs and MWCNTs cannot be simplified. It is inconclusive that the conventional octanol-water FAs on MWCNTs and the CPE FAs on AgNPs can be simplified, due to the uncertain causes and consistency of the differences on the removal efficiencies.

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Date Created
  • 2017-05

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Enhancing American Resilience: Testing An Alternative Evaluation Method For Governmental Contingency Planning

Description

As the frequency of US-based disasters increases, so does the need for effective governmental contingency planning and improvement. The current, external evaluation method presents several opportunities for improvement, including cost,

As the frequency of US-based disasters increases, so does the need for effective governmental contingency planning and improvement. The current, external evaluation method presents several opportunities for improvement, including cost, efficacy of results, and turnaround time for results. Utilizing a tabletop exercise as it's model, this study designed a self-evaluation tool to test if the data provided by such a tool is similar to the data provided by an external evaluator. After testing it in a government-sanctioned tabletop exercise, the tool showed its ability to be utilized in an exercise and evaluate the participants, based off their perceived success in the exercise. The results of the study indicate a strong, positive correlation between the results of the participant and evaluator populations surveyed as well as statistical equality between the two groups.

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Date Created
  • 2017-05

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Maricopa County particulate matter source study

Description

Maricopa County has exceeded the 24 hour National Ambient Air Quality Standard (NAAQS) for Particulate Matter 10 micrometers in diameter or smaller (PM-10) of 150 micrograms per meter cubed (μg/m3)

Maricopa County has exceeded the 24 hour National Ambient Air Quality Standard (NAAQS) for Particulate Matter 10 micrometers in diameter or smaller (PM-10) of 150 micrograms per meter cubed (μg/m3) since 1990. Construction and construction related activities have been recognized as the highest contributors to high PM-10 levels. An analysis of days exceeding 150 μg/m3 for four of Maricopa County‟s monitors that most frequently exceed this level during the years 2007, 2008, and 2009 has been performed. Noted contributors to PM-10 levels have been identified in the study, including earthmoving permits, stationary source permits, vacant lots, and agriculture on two mile radius maps around each monitor. PM-10 levels and wind speeds for each date exceeding 225 μg/m3 were reviewed to find specific weather or anthropogenic sources for the high PM-10 levels. Weather patterns for days where multiple monitors exceed 150 μg/m3 were reviewed to find correlations between daily weather and high PM-10 levels. It was found that areas with more earthmoving permits had fewer days exceeding 150 μg/m3 than areas with more stationary permits, vacant lots, or agriculture. The Higley and Buckeye monitors showed increases in PM-10 levels when winds came from areas covered by agricultural land. West 43rd Avenue and Durango monitors saw PM-10 rise when the winds came in over large stationary sources, like aggregate plants. A correlation between weather events and PM-10 exceedances was also found on multiple monitors for dates both in 2007, and 2009.

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Date Created
  • 2011

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Interaction between organophosphorus and oxide surface for air pollution control

Description

The release of organophosphorus compounds (OPs) and subsequent exposure to these compounds is of concern to humans and the environment. The goal of this work was to control the

The release of organophosphorus compounds (OPs) and subsequent exposure to these compounds is of concern to humans and the environment. The goal of this work was to control the concentrations of gaseous OPs through interaction with sorbent oxides. Experimental and computational methods were employed to assess the interactions of dimethyl phosphite (DMHP), dimethyl methylphosphonate (DMMP), dimethyl ethylphosphonate (DMEP), diethyl ethylphosphonate (DEEP), and triethyl phosphate (TEP) with amorphous silica (a-silica), ã-alumina, and monoclinic zirconia (m-zirconia) for applications in air pollution control. Interactions of the selected OPs with a-silica were chosen as a baseline to determine the applicability of the computational predictions. Based on the a-silica results, computational methods were deemed valid for predicting the trends among materials with comparable interactions (e.g. -OH functionality of a-silica interacting with the phosphonyl O atoms of the OPs). Computational evaluations of the interactions with the OPs were extended to the oxide material, m-zirconia, and compared with the results for ã-alumina. It was hypothesized that m-zirconia had the potential to provide for the effective sorption of OPs in a manner superior to that of the a-silica and the ã-alumina surfaces due to the surface charges of the zirconium Lewis acid sites when coordinated in the oxidized form. Based on the computational study, the predicted heats of adsorption for the selected OPs onto m-zirconia were more favorable than those that were predicted for ã-alumina and a-silica. Experimental studies were carried out to confirm these computational results. M-zirconia nanoparticles were synthesized to determine if the materials could be utilized for the adsorption of the selected OPs. M-zirconia was shown to adsorb the OPs, and the heats of adsorption were stronger than those determined for commercial samples of a-silica. However, water interfered with the adsorption of the OPs onto m-zirconia, thus leading to heats of adsorption that were much weaker than those predicted computationally. Nevertheless, this work provides a first investigation of m-zirconia as a viable sorbent material for the ambient control of the selected gaseous OPs. Additionally, this work represents the first comparative study between computational predictions and experimental determination of thermodynamic properties for the interactions of the selected OPs and oxide surfaces.

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Date Created
  • 2011

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An analysis of the impacts and non-attainment risks of the revised sulfur dioxide national ambient air quality standard on the Toledo core based statistical area using the American Meteorological Society-Environmental Protection Agency regulatory model

Description

The Toledo Core Based Statistical Area (CBSA) presents an interesting case study for the new sulfur dioxide (SO2) one hour standard. Since no SO2 monitor within 75 miles to estimate

The Toledo Core Based Statistical Area (CBSA) presents an interesting case study for the new sulfur dioxide (SO2) one hour standard. Since no SO2 monitor within 75 miles to estimate the attainment status of the area, American Meteorological Society/Environmental Protection Agency Regulatory Model (AERMOD) was used in this study to predict potential problems associated with the newly revised standard. The Toledo CBSA is home to two oil refineries, a glass making industry, several coal fired lime kilns, and a sulfuric acid regeneration plant, The CBSA 3 has coal fired power plants within a 30 mile radius of its center. Additionally, Toledo is a major Great Lakes shipping port visited by both lake and ocean going vessels. As a transportation hub, the area is also traversed by several rail lines which feed four rail switching yards. Impacts of older generation freighters, or "steamers", utilizing high sulfur "Bunker C" fuel oil in the area is also an issue. With the unique challenges presented by an SO2 one hour standard, this study attempted to estimate potential problem areas in advance of any monitoring data being gathered. Based on the publicly available data as inputs, it appears that a significant risk of non-attainment may exist in the Toledo CBSA. However, future on-the-books controls and currently proposed regulatory actions appear to drive the risk below significance by 2015. Any designation as non-attainment should be self-correcting and without need for controls other than those used in these models. The outcomes of this screening study are intended for use as a basis for assessments for other mid-sized, industrial areas without SO2 monitors. The results may also be utilized by industries and planning groups within the Toledo CBSA to address potential issues in advance of monitoring system deployment to lower the risk of attaining long term or perpetual non-attainment status.

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Date Created
  • 2011

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Fabrication and evaluation of hematite modified granular activated carbon (GAC) media for arsenic removal from groundwater

Description

The goal of the study was twofold: (i) to investigate the synthesis of hematite-impregnated granular activated carbon (Fe-GAC) by hydrolysis of Fe (III) and (ii) to assess the effectiveness of

The goal of the study was twofold: (i) to investigate the synthesis of hematite-impregnated granular activated carbon (Fe-GAC) by hydrolysis of Fe (III) and (ii) to assess the effectiveness of the fabricated media in removal of arsenic from water. Fe-GAC was synthesized by hydrolysis of Fe(III) salts under two Fe (III) initial dosages (0.5M and 2M) and two hydrolysis periods (24 hrs and 72 hrs). The iron content of the fabricated Fe-GAC media ranged from 0.9% to 4.4% Fe/g of the dry media. Pseudo-equilibrium batch test data at pH = 7.7±0.2 in 1mM NaHCO3 buffered ultrapure water and challenge groundwater representative of the Arizona Mexico border region were fitted to a Freundlich isotherm model. The findings suggested that the arsenic adsorption capacity of the metal (hydr)oxide modified GAC media is primarily controlled by the surface area of the media, while the metal content exhibited lesser effect. The adsorption capacity of the media in the model Mexican groundwater matrix was significantly lower for all adsorbent media. Continuous flow short bed adsorber tests (SBA) demonstrated that the adsorption capacity for arsenic in the challenge groundwater was reduced by a factor of 3 to 4 as a result of the mass transport effects. When compared on metal basis, the iron (hydr)oxide modified media performed comparably well as existing commercial media for treatment of arsenic. On dry mass basis, the fabricated media in this study removed less arsenic than their commercial counterparts because the metal content of the commercial media was significantly higher.

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Date Created
  • 2011

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TiO2 nanomaterials: human exposure and environmental release

Description

Titanium dioxide (TiO2) nanomaterial use is becoming more prevalent as is the likelihood of human exposure and environmental release. The goal of this thesis is to develop analytical techniques to

Titanium dioxide (TiO2) nanomaterial use is becoming more prevalent as is the likelihood of human exposure and environmental release. The goal of this thesis is to develop analytical techniques to quantify the level of TiO2 in complex matrices to support environmental, health, and safety research of TiO2 nanomaterials. A pharmacokinetic model showed that the inhalation of TiO2 nanomaterials caused the highest amount to be absorbed and distributed throughout the body. Smaller nanomaterials (< 5nm) accumulated in the kidneys before clearance. Nanoparticles of 25 nm diameter accumulated in the liver and spleen and were cleared from the body slower than smaller nanomaterials. A digestion method using nitric acid, hydrofluoric acid, and hydrogen peroxide was found to digest organic materials and TiO2 with a recovery of >80%. The samples were measured by inductively coupled plasma-mass spectrometry (ICP-MS) and the method detection limit was 600 ng of Ti. An intratracheal instillation study of TiO2 nanomaterials in rats found anatase TiO2 nanoparticles in the caudal lung lobe of rats 1 day post instillation at a concentration of 1.2 ug/mg dry tissue, the highest deposition rate of any TiO2 nanomaterial. For all TiO2 nanomaterial morphologies the concentrations in the caudal lobes were significantly higher than those in the cranial lobes. In a study of TiO2 concentration in food products, white colored foods or foods with a hard outer shell had higher concentrations of TiO2. Hostess Powdered Donettes were found to have the highest Ti mass per serving with 200 mg Ti. As much as 3.8% of the total TiO2 mass was able to pass through a 0.45 um indicating that some of the TiO2 is likely nanosized. In a study of TiO2 concentrations in personal care products and paints, the concentration of TiO2 was as high as 117 ug/mg in Benjamin Moore white paint and 70 ug/mg in a Neutrogena sunscreen. Greater than 6% of Ti in one sunscreen was able to pass through a 0.45 um filter. The nanosized TiO2 in food products and personal care products may release as much as 16 mg of nanosized TiO2 per individual per day to wastewater.

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Date Created
  • 2011

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Hexavalent chromium removal using ultraviolet photocatalytic reactor

Description

Hexavalant chromium (Cr(VI)) poses an emerging concern in drinking water treatment with stricter regulations on the horizon. Photocatalytic reduction of Cr(VI) was investigated as an engineering scale option to remove

Hexavalant chromium (Cr(VI)) poses an emerging concern in drinking water treatment with stricter regulations on the horizon. Photocatalytic reduction of Cr(VI) was investigated as an engineering scale option to remove hexavalent chromium from drinking or industrial waters via a UV/titanium dioxide (TiO2) process. Using an integrated UV lamp/ceramic membrane system to recirculate TiO2, both hexavalent and total chromium levels were reduced through photocatalytic processes without additional chemicals. Cr(VI) removal increased as a function of higher energy input and TiO2 dosage, achieving above 90% removal for a 1g/L dose of TiO2. Surface analysis of effluent TiO2 confirmed the presence of chromium species.

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Date Created
  • 2013

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Environmentally responsible use of nanomaterials for the photocatalytic reduction of nitrate in water

Description

Nitrate is the most prevalent water pollutant limiting the use of groundwater as a potable water source. The overarching goal of this dissertation was to leverage advances in nanotechnology to

Nitrate is the most prevalent water pollutant limiting the use of groundwater as a potable water source. The overarching goal of this dissertation was to leverage advances in nanotechnology to improve nitrate photocatalysis and transition treatment to the full-scale. The research objectives were to (1) examine commercial and synthesized photocatalysts, (2) determine the effect of water quality parameters (e.g., pH), (3) conduct responsible engineering by ensuring detection methods were in place for novel materials, and (4) develop a conceptual framework for designing nitrate-specific photocatalysts. The key issues for implementing photocatalysis for nitrate drinking water treatment were efficient nitrate removal at neutral pH and by-product selectivity toward nitrogen gases, rather than by-products that pose a human health concern (e.g., nitrite). Photocatalytic nitrate reduction was found to follow a series of proton-coupled electron transfers. The nitrate reduction rate was limited by the electron-hole recombination rate, and the addition of an electron donor (e.g., formate) was necessary to reduce the recombination rate and achieve efficient nitrate removal. Nano-sized photocatalysts with high surface areas mitigated the negative effects of competing aqueous anions. The key water quality parameter impacting by-product selectivity was pH. For pH < 4, the by-product selectivity was mostly N-gas with some NH4+, but this shifted to NO2- above pH = 4, which suggests the need for proton localization to move beyond NO2-. Co-catalysts that form a Schottky barrier, allowing for localization of electrons, were best for nitrate reduction. Silver was optimal in heterogeneous systems because of its ability to improve nitrate reduction activity and N-gas by-product selectivity, and graphene was optimal in two-electrode systems because of its ability to shuttle electrons to the working electrode. "Environmentally responsible use of nanomaterials" is to ensure that detection methods are in place for the nanomaterials tested. While methods exist for the metals and metal oxides examined, there are currently none for carbon nanotubes (CNTs) and graphene. Acknowledging that risk assessment encompasses dose-response and exposure, new analytical methods were developed for extracting and detecting CNTs and graphene in complex organic environmental (e.g., urban air) and biological matrices (e.g. rat lungs).

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Date Created
  • 2013

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Overcoming the impacts of extreme weather and dissolved organic matter on the treatability of water using ozone

Description

The influence of climate variability and reclaimed wastewater on the water supply necessitates improved understanding of the treatability of trace and bulk organic matter. Dissolved organic matter (DOM) mobilized during

The influence of climate variability and reclaimed wastewater on the water supply necessitates improved understanding of the treatability of trace and bulk organic matter. Dissolved organic matter (DOM) mobilized during extreme weather events and in treated wastewater includes natural organic matter (NOM), contaminants of emerging concern (CECs), and microbial extracellular polymeric substances (EPS). The goal of my dissertation was to quantify the impacts of extreme weather events on DOM in surface water and downstream treatment processes, and to improve membrane filtration efficiency and CECs oxidation efficiency during water reclamation with ozone. Surface water quality, air quality and hydrologic flow rate data were used to quantify changes in DOM and turbidity following dust storms, flooding, or runoff from wildfire burn areas in central Arizona. The subsequent impacts to treatment processes and public perception of water quality were also discussed. Findings showed a correlation between dust storm events and change in surface water turbidity (R2=0.6), attenuation of increased DOM through reservoir systems, a 30-40% increase in organic carbon and a 120-600% increase in turbidity following severe flooding, and differing impacts of upland and lowland wildfires. The use of ozone to reduce membrane fouling caused by vesicles (a subcomponent of EPS) and oxidize CECs through increased hydroxyl radical (HO●) production was investigated. An "ozone dose threshold" was observed above which addition of hydrogen peroxide increased HO● production; indicating the presence of ambient promoters in wastewater. Ozonation of CECs in secondary effluent over titanium dioxide or activated carbon did not increase radial production. Vesicles fouled ultrafiltration membranes faster (20 times greater flux decline) than polysaccharides, fatty acids, or NOM. Based upon the estimated carbon distribution of secondary effluent, vesicles could be responsible for 20-60% of fouling during ultrafiltration and may play a vital role in other environmental processes as well. Ozone reduced vesicle-caused membrane fouling that, in conjunction with the presence of ambient promoters, helps to explain why low ozone dosages improve membrane flux during full-scale water reclamation.

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Date Created
  • 2014