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As the use of engineered nanomaterials (ENMs) in consumer products becomes more common, the amount of ENMs entering wastewater treatment plants (WWTPs) increases. Investigating the fate of ENMs in WWTPs is critical for risk assessment and pollution control. The objectives of this dissertation were to (1) quantify and characterize titanium

As the use of engineered nanomaterials (ENMs) in consumer products becomes more common, the amount of ENMs entering wastewater treatment plants (WWTPs) increases. Investigating the fate of ENMs in WWTPs is critical for risk assessment and pollution control. The objectives of this dissertation were to (1) quantify and characterize titanium (Ti) in full-scale wastewater treatment plants, (2) quantify sorption of different ENMs to wastewater biomass in laboratory-scale batch reactors, (3) evaluate the use of a standard, soluble-pollutant sorption test method for quantifying ENM interaction with wastewater biomass, and (4) develop a mechanistic model of a biological wastewater treatment reactor to serve as the basis for modeling nanomaterial fate in WWTPs. Using titanium (Ti) as a model material for the fate of ENMs in WWTPs, Ti concentrations were measured in 10 municipal WWTPs. Ti concentrations in pant influent ranged from 181 to 3000 µg/L, and more than 96% of Ti was removed, with effluent Ti concentrations being less than 25 µg/L. Ti removed from wastewater accumulated in solids at concentrations ranging from 1 to 6 µg Ti/mg solids. Using transmission electron microscopy, spherical titanium oxide nanoparticles with diameters ranging from 4 to 30 nm were found in WWTP effluents, evidence that some nanoscale particles will pass through WWTPs and enter aquatic systems. Batch experiments were conducted to quantify sorption of different ENM types to activated sludge. Percentages of sorption to 400 mg TSS/L biomass ranged from about 10 to 90%, depending on the ENM material and functionalization. Natural organic matter, surfactants, and proteins had a stabilizing effect on most of the ENMs tested. The United States Environmental Protection Agency's standard sorption testing method (OPPTS 835.1110) used for soluble compounds was found to be inapplicable to ENMs, as freeze-dried activated sludge transforms ENMs into stable particles in suspension. In conjunction with experiments, we created a mechanistic model of the microbiological processes in membrane bioreactors to predict MBR, extended and modified this model to predict the fate of soluble micropollutants, and then discussed how the micropollutant fate model could be used to predict the fate of nanomaterials in wastewater treatment plants.
ContributorsKiser, Mehlika Ayla (Author) / Westerhoff, Paul K (Thesis advisor) / Rittmann, Bruce E. (Committee member) / Hristovski, Kiril D (Committee member) / Arizona State University (Publisher)
Created2011
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Description

A recent joint study by Arizona State University and the Arizona Department of Transportation (ADOT) was conducted to evaluate certain Warm Mix Asphalt (WMA) properties in the laboratory. WMA material was taken from an actual ADOT project that involved two WMA sections. The first section used a foamed-based WMA admixture,

A recent joint study by Arizona State University and the Arizona Department of Transportation (ADOT) was conducted to evaluate certain Warm Mix Asphalt (WMA) properties in the laboratory. WMA material was taken from an actual ADOT project that involved two WMA sections. The first section used a foamed-based WMA admixture, and the second section used a chemical-based WMA admixture. The rest of the project included control hot mix asphalt (HMA) mixture. The evaluation included testing of field-core specimens and laboratory compacted specimens. The laboratory specimens were compacted at two different temperatures; 270 °F (132 °C) and 310 °F (154 °C). The experimental plan included four laboratory tests: the dynamic modulus (E*), indirect tensile strength (IDT), moisture damage evaluation using AASHTO T-283 test, and the Hamburg Wheel-track Test. The dynamic modulus E* results of the field cores at 70 °F showed similar E* values for control HMA and foaming-based WMA mixtures; the E* values of the chemical-based WMA mixture were relatively higher. IDT test results of the field cores had comparable finding as the E* results. For the laboratory compacted specimens, both E* and IDT results indicated that decreasing the compaction temperatures from 310 °F to 270 °F did not have any negative effect on the material strength for both WMA mixtures; while the control HMA strength was affected to some extent. It was noticed that E* and IDT results of the chemical-based WMA field cores were high; however, the laboratory compacted specimens results didn't show the same tendency. The moisture sensitivity findings from TSR test disagreed with those of Hamburg test; while TSR results indicated relatively low values of about 60% for all three mixtures, Hamburg test results were quite excellent. In general, the results of this study indicated that both WMA mixes can be best evaluated through field compacted mixes/cores; the results of the laboratory compacted specimens were helpful to a certain extent. The dynamic moduli for the field-core specimens were higher than for those compacted in the laboratory. The moisture damage findings indicated that more investigations are needed to evaluate moisture damage susceptibility in field.

ContributorsAlossta, Abdulaziz (Author) / Kaloush, Kamil (Thesis advisor) / Witczak, Matthew W. (Committee member) / Mamlouk, Michael S. (Committee member) / Arizona State University (Publisher)
Created2011
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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 quantify the level of TiO2 in complex matrices to support environmental, health, and safety research of TiO2 nanomaterials. A pharmacokinetic

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.
ContributorsWeir, Alex Alan (Author) / Westerhoff, Paul K (Thesis advisor) / Hristovski, Kiril (Committee member) / Herckes, Pierre (Committee member) / Arizona State University (Publisher)
Created2011
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Description

Perpetual Pavements, if properly designed and rehabilitated, it can last longer than 50 years without major structural rehabilitation. Fatigue endurance limit is a key parameter for designing perpetual pavements to mitigate bottom-up fatigue cracking. The endurance limit has not been implemented in the Mechanistic Empirical Pavement Design Guide software, currently

Perpetual Pavements, if properly designed and rehabilitated, it can last longer than 50 years without major structural rehabilitation. Fatigue endurance limit is a key parameter for designing perpetual pavements to mitigate bottom-up fatigue cracking. The endurance limit has not been implemented in the Mechanistic Empirical Pavement Design Guide software, currently known as DARWin-ME. This study was conducted as part of the National Cooperative Highway Research Program (NCHRP) Project 9-44A to develop a framework and mathematical methodology to determine the fatigue endurance limit using the uniaxial fatigue test. In this procedure, the endurance limit is defined as the allowable tensile strains at which a balance takes place between the fatigue damage during loading, and the healing during the rest periods between loading pulses. The viscoelastic continuum damage model was used to isolate time dependent damage and healing in hot mix asphalt from that due to fatigue. This study also included the development of a uniaxial fatigue test method and the associated data acquisition computer programs to conduct the test with and without rest period. Five factors that affect the fatigue and healing behavior of asphalt mixtures were evaluated: asphalt content, air voids, temperature, rest period and tensile strain. Based on the test results, two Pseudo Stiffness Ratio (PSR) regression models were developed. In the first model, the PSR was a function of the five factors and the number of loading cycles. In the second model, air voids, asphalt content, and temperature were replaced by the initial stiffness of the mix. In both models, the endurance limit was defined when PSR is equal to 1.0 (net damage is equal to zero). The results of the first model were compared to the results of a stiffness ratio model developed based on a parallel study using beam fatigue test (part of the same NCHRP 9-44A). The endurance limit values determined from uniaxial and beam fatigue tests showed very good correlation. A methodology was described on how to incorporate the second PSR model into fatigue analysis and damage using the DARWin-ME software. This would provide an effective and efficient methodology to design perpetual flexible pavements.

ContributorsZeiada, Waleed (Author) / Kaloush, Kamil (Thesis advisor) / Witczak, Matthew W. (Thesis advisor) / Zapata, Claudia (Committee member) / Mamlouk, Michael (Committee member) / Arizona State University (Publisher)
Created2012
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Description
Drinking water filtration using reverse osmosis (RO) membranes effectively removes salts and most other inorganic, organic, and microbial pollutants. RO technologies are utilized at both the municipal and residential scale. The formation of biofilms on RO membranes reduces water flux and increases energy consumption. The research conducted for this thesis

Drinking water filtration using reverse osmosis (RO) membranes effectively removes salts and most other inorganic, organic, and microbial pollutants. RO technologies are utilized at both the municipal and residential scale. The formation of biofilms on RO membranes reduces water flux and increases energy consumption. The research conducted for this thesis involves In-Situ coating of silver, a known biocide, on the surface of RO membranes. This research was adapted from a protocol developed for coating flat sheet membranes with silver nanoparticles, and scaled up into spiral-wound membranes that are commonly used at the residential scale in point-of-use (POU) filtration systems. Performance analyses of the silver-coated spiral-wound were conducted in a mobile drinking water treatment system fitted with two POU units for comparison. Five month-long analyses were performed, including a deployment of the mobile system. In addition to flux, salt rejection, and other water quality analyses, additional membrane characterization tests were conducted on pristine and silver-coated membranes.

For flat sheet membranes coated with silver, the surface charge remained negative and contact angle remained below 90. Scaling up to spiral-wound RO membrane configuration was successful, with an average silver-loading of 1.93 g-Ag/cm2. Results showed the flux of water through the membrane ranged from 8 to 13 liters/m2*hr. (LMH) operating at 25% recovery during long-term of operation. The flux was initially decreased due to the silver coating, but no statistically significant differences were observed after 14 days of operation (P < 0.05). The salt rejection was also not effected due to the silver coating (P < 0.05). While 98% of silver was released during long-term studies, the silver release from the spiral-wound membrane was consistently below the secondary MCL of 100 ppb established by the EPA, and was consistently below 5 ppb after two hours of operation. Microbial assays in the form of heterotrophic plate counts suggested there was no statistically significant difference in the prevention of biofouling formation due to the silver coating (P < 0.05). In addition to performance tests and membrane characterizations, a remote data acquisition system was configured to remotely monitor performance and water quality parameters in the mobile system.
ContributorsZimmerman, Sean (Author) / Westerhoff, Paul K (Thesis advisor) / Sinha, Shahnawaz (Committee member) / Perreault, Francois (Committee member) / Arizona State University (Publisher)
Created2017
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Description

The objective of the research is to test the use of 3D printed thermoplastic to produce fixtures which affix instrumentation to asphalt concrete samples used for Simple Performance Testing (SPT). The testing is done as part of materials characterization to obtain properties that will help in future pavement designs. Currently,

The objective of the research is to test the use of 3D printed thermoplastic to produce fixtures which affix instrumentation to asphalt concrete samples used for Simple Performance Testing (SPT). The testing is done as part of materials characterization to obtain properties that will help in future pavement designs. Currently, these fixtures (mounting studs) are made of expensive brass and cumbersome to clean with or without chemicals.

Three types of thermoplastics were utilized to assess the effect of temperature and applied stress on the performance of the 3D printed studs. Asphalt concrete samples fitted with thermoplastic studs were tested according to AASHTO & ASTM standards. The thermoplastics tested are: Polylactic acid (PLA), the most common 3D printing material; Acrylonitrile Butadiene Styrene (ABS), a typical 3D printing material which is less rigid than PLA and has a higher melting temperature; Polycarbonate (PC), a strong, high temperature 3D printing material.

A high traffic volume Marshal mix design from the City of Phoenix was obtained and adapted to a Superpave mix design methodology. The mix design is dense-graded with nominal maximum aggregate size of ¾” inch and a PG 70-10 binder. Samples were fabricated and the following tests were performed: Dynamic Modulus |E*| conducted at five temperatures and six frequencies; Flow Number conducted at a high temperature of 50°C, and axial cyclic fatigue test at a moderate temperature of 18°C.

The results from SPT for each 3D printed material were compared to results using brass mounting studs. Validation or rejection of the concept was determined from statistical analysis on the mean and variance of collected SPT test data.

The concept of using 3D printed thermoplastic for mounting stud fabrication is a promising option; however, the concept should be verified with more extensive research using a variety of asphalt mixes and operators to ensure no bias in the repeatability and reproducibility of test results. The Polycarbonate (PC) had a stronger layer bonding than ABS and PLA while printing. It was recommended for follow up studies.

ContributorsBeGell, Dirk (Author) / Kaloush, Kamil (Thesis advisor) / Mamlouk, Michael (Committee member) / Stempihar, Jeffery (Committee member) / Arizona State University (Publisher)
Created2018
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Description
Engineered nanoparticles (NPs) pose risk potentials, if they exist in water systems at significant concentrations and if they remain reactive to cause toxicity. Three goals guided this study: (1) establishing NP detecting methods with high sensitivity to tackle low concentration and small sizes, (2) achieving assays capable of measuring

Engineered nanoparticles (NPs) pose risk potentials, if they exist in water systems at significant concentrations and if they remain reactive to cause toxicity. Three goals guided this study: (1) establishing NP detecting methods with high sensitivity to tackle low concentration and small sizes, (2) achieving assays capable of measuring NP surface reactivity and identifying surface reaction mechanisms, and (3) understanding the impact of surface adsorption of ions on surface reactivity of NPs in water.

The size detection limit of single particle inductively coupled plasma spectrometry (spICP-MS) was determined for 40 elements, demonstrating the feasibility of spICP-MS to different NP species in water. The K-means Clustering Algorithm was used to process the spICP-MS signals, and achieved precise particle-noise differentiation and quantitative particle size resolution. A dry powder assay based on NP-catalyzed methylene blue (MB) reduction was developed to rapidly and sensitively detect metallic NPs in water by measuring their catalytic reactivity.

Four different wet-chemical-based NP surface reactivity assays were demonstrated: “borohydride reducing methylene blue (BHMB)”, “ferric reducing ability of nanoparticles (FRAN)”, “electron paramagnetic resonance detection of hydroxyl radical (EPR)”, and “UV-illuminated methylene blue degradation (UVMB)”. They gave different reactivity ranking among five NP species, because they targeted for different surface reactivity types (catalytic, redox and photo reactivity) via different reaction mechanisms. Kinetic modeling frameworks on the assay outcomes revealed two surface electron transfer schemes, namely the “sacrificial reducing” and the “electrode discharging”, and separated interfering side reactions from the intended surface reaction.

The application of NPs in chemical mechanical polishing (CMP) was investigated as an industrial case to understand NP surface transformation via adsorbing ions in water. Simulation of wastewater treatment showed CMP NPs were effectively removed (>90%) by lime softening at high pH and high calcium dosage, but 20-40% of them remained in water after biomass adsorption process. III/V ions (InIII, GaIII, and AsIII/V) derived from semiconductor materials showed adsorption potentials to common CMP NPs (SiO2, CeO2 and Al2O3), and a surface complexation model was developed to determine their intrinsic complexation constants for different NP species. The adsorption of AsIII and AsV ions onto CeO2 NPs mitigated the surface reactivity of CeO2 NPs suggested by the FRAN and EPR assays. The impact of the ion adsorption on the surface reactivity of CeO2 NPs was related to the redox state of Ce and As on the surface, but varied with ion species and surface reaction mechanisms.
ContributorsBi, Xiangyu (Author) / Westerhoff, Paul K (Thesis advisor) / Rittmann, Bruce E. (Committee member) / Herckes, Pierre (Committee member) / Richert, Ranko (Committee member) / Arizona State University (Publisher)
Created2018
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Description

The built environment is responsible for a significant portion of global waste generation.

Construction and demolition (C&D) waste requires significant landfill areas and costs

billions of dollars. New business models that reduce this waste may prove to be financially

beneficial and generally more sustainable. One such model is referred to as the “Circular

Economy”

The built environment is responsible for a significant portion of global waste generation.

Construction and demolition (C&D) waste requires significant landfill areas and costs

billions of dollars. New business models that reduce this waste may prove to be financially

beneficial and generally more sustainable. One such model is referred to as the “Circular

Economy” (CE), which promotes the efficient use of materials to minimize waste

generation and raw material consumption. CE is achieved by maximizing the life of

materials and components and by reclaiming the typically wasted value at the end of their

life. This thesis identifies the potential opportunities for using CE in the built environment.

It first calculates the magnitude of C&D waste and its main streams, highlights the top

C&D materials based on weight and value using data from various regions, identifies the

top C&D materials’ current recycling and reuse rates, and finally estimates a potential

financial benefit of $3.7 billion from redirecting C&D waste using the CE concept in the

United States.

ContributorsAldaaja, Mohammad (Author) / El Asmar, Mounir (Thesis advisor) / Buch, Rajesh (Committee member) / Kaloush, Kamil (Committee member) / Arizona State University (Publisher)
Created2019
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Description
Mineral weathering and industrial activities cause elevated concentration of hexavalent chromium (Cr(VI)) in groundwater, and this poses potential health concern (>10 ppb) to southwestern USA. The conversion of Cr(VI) to Cr(III) – a fairly soluble and non-toxic form at typical pH of groundwater is an effective method to control the

Mineral weathering and industrial activities cause elevated concentration of hexavalent chromium (Cr(VI)) in groundwater, and this poses potential health concern (>10 ppb) to southwestern USA. The conversion of Cr(VI) to Cr(III) – a fairly soluble and non-toxic form at typical pH of groundwater is an effective method to control the mobility and carcinogenic effects of Cr(VI). In-situ chemical reduction using SnCl2 was investigated to initiate this redox process using jar testing with buffered ultrapure water and native Arizona groundwater spiked with varying Cr(VI) concentrations. Cr(VI) transformation by SnCl2 is super rapid (<60 seconds) and depends upon the molar dosage of Sn(II) to Cr(VI). Cr(VI) removal improved significantly at higher pH while was independent on Cr(VI) initial concentration and dissolved oxygen (DO) level. Co-existing oxyanions (As and W) competed with Cr(VI) for SnCl2 oxidation and adsorption sites of formed precipitates, thus resulted in lower Cr(VI) removal in the challenge water. SnCl2 reagent grade and commercial grade behaved similarly when freshly prepared, but the reducing strength of the commercial product decreased by 50% over a week after exposing to atmosphere. Equilibrium modeling with Visual MINTEQ suggested redox potential < 400 mV to reach Cr(VI) treatment goal of 10 ppb. Kinetics of Cr(VI) reduction was simulated via the rate expression: r=-k[H+]-0.25[Sn2+]0.5[Cr2O72-]3 with k = 0.146 uM-2.25s-1, which correlated consistently with experimental data under different pH and SnCl2 doses. These results proved SnCl2 reductive treatment is a simple and highly effective method to treat Cr(VI) in groundwater.
ContributorsNguyen, Duong Thanh (Author) / Westerhoff, Paul K (Thesis advisor) / Delgado, Anca G (Committee member) / Sinha, Shahnawaz (Committee member) / Arizona State University (Publisher)
Created2019
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Description
C.C. Cragin Reservoir’s location in the Coconino National Forest, Arizona makes it prone to wild fire. This study focused on the potential impacts of such a wild fire on the reservoir’s annual thermal stratification cycle impacts and water quality. The annual thermal stratification cycle impacted the reservoir’s water

C.C. Cragin Reservoir’s location in the Coconino National Forest, Arizona makes it prone to wild fire. This study focused on the potential impacts of such a wild fire on the reservoir’s annual thermal stratification cycle impacts and water quality. The annual thermal stratification cycle impacted the reservoir’s water quality by increasing hypolimnion concentrations of magnesium, iron, turbidity, and specific ultraviolet absorbance (SUVA) values, as well as resulting in the hypolimnion having decreased dissolved oxygen concentrations during stratified months. The scarification process did not affect the dissolved organic carbon (DOC) concentrations in the reservoir or the total/dissolved nitrogen and phosphorous concentrations. Some general water quality trends that emerged were that phosphorous was the limiting nutrient, secchi disk depth and chlorophyll a concentration are inversely related, and no metals were found to be in concentrations that would violate an EPA drinking water maximum contaminant level (MCL). A carbon mass model was developed and parameterized using DOC measurements, and then using historic reservoir storage and weather data, the model simulated DOC concentrations in the reservoir following four hypothetical wild fire events. The model simulated varying initial reservoir storage volumes, initial flush volumes, and flush DOC concentrations, resulting in reservoir DOC concentrations varying from 17.41 mg/L to 8.82 mg/L.
ContributorsFlatebo, Theodore (Author) / Westerhoff, Paul K (Thesis advisor) / Fox, Peter (Committee member) / Perreault, Francois (Committee member) / Arizona State University (Publisher)
Created2018