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Hydrocarbon spill site cleanup is challenging when contaminants are present in lower permeability layers. These are difficult to remediate and may result in long-term groundwater impacts. The research goal is to investigate strategies for long-term reduction of contaminant emissions from sources in low permeability layers through partial source treatment at

Hydrocarbon spill site cleanup is challenging when contaminants are present in lower permeability layers. These are difficult to remediate and may result in long-term groundwater impacts. The research goal is to investigate strategies for long-term reduction of contaminant emissions from sources in low permeability layers through partial source treatment at higher/lower permeability interfaces. Conceptually, this provides a clean/reduced concentration zone near the interface, and consequently a reduced concentration gradient and flux from the lower permeability layer. Treatment by in-situ chemical oxidation (ISCO) was evaluated using hydrogen peroxide (H2O2) and sodium persulfate (Na2S2O8). H2O2 studies included lab and field-scale distribution studies and lab emission reduction experiments. The reaction rate of H2O2 in soils was so fast it did not travel far (<1 m) from delivery points under typical flow conditions. Oxygen gas generated and partially trapped in soil pores served as a dissolved oxygen (DO) source for >60 days in field and lab studies. During that period, the laboratory studies had reduced hydrocarbon impacts, presumably from aerobic biodegradation, which rebounded once the O2 source depleted. Therefore field monitoring should extend beyond the post-treatment elevated DO. Na2S2O8 use was studied in two-dimensional tanks (122-cm tall, 122-cm wide, and 5-cm thick) containing two contrasting permeability layers (three orders of magnitude difference). The lower permeability layer initially contained a dissolved-sorbed contaminant source throughout this layer, or a 10-cm thick non-aqueous phase liquid (NAPL)-impacted zone below the higher/lower permeability interface. The dissolved-sorbed source tank was actively treated for 14 d. Two hundred days after treatment, the emission reduction of benzene, toluene, ethylbenzene, and p-xylene (BTEX) were 95-99% and methyl tert-butyl ether (MTBE) was 63%. The LNAPL-source tank had three Na2S2O8 and two sodium hydroxide (NaOH) applications for S2O82- base activation. The resulting emission reductions for BTEX, n-propylbenzene, and 1,3,5 trymethylbenzene were 55-73%. While less effective at reducing emissions from LNAPL sources, the 14-d treatment delivered sufficient S2O82- though diffusion to remediate BTEX from the 60 cm dissolved-sorbed source. The overall S2O82- utilization in the dissolved source experiment was calculated by mass balance to be 108-125 g S2O82-/g hydrocarbon treated.
ContributorsCavanagh, Bridget (Author) / Johnson, Paul C (Thesis advisor) / Westerhoff, Paul (Committee member) / Kavazanjian, Edward (Committee member) / Bruce, Cristin (Committee member) / Arizona State University (Publisher)
Created2014
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Description
Characterization of petroleum spill site source zones directly influences the selection of corrective action plans and frequently affects the success of remediation efforts. For example, simply knowing whether or not nonaqueous phase liquid (NAPL) is present, or if there is chemical storage in less hydraulically accessible regions, will influence corrective

Characterization of petroleum spill site source zones directly influences the selection of corrective action plans and frequently affects the success of remediation efforts. For example, simply knowing whether or not nonaqueous phase liquid (NAPL) is present, or if there is chemical storage in less hydraulically accessible regions, will influence corrective action planning. The overarching objective of this study was to assess if macroscopic source zone features can be inferred from dissolved concentration vs. time data. Laboratory-scale physical model studies were conducted for idealized sources; defined as Type-1) NAPL-impacted high permeability zones, Type-2) NAPL-impacted lower permeability zones, and Type-3) dissolved chemical matrix storage in lower permeability zones. Aquifer source release studies were conducted using two-dimensional stainless steel flow-through tanks outfitted with sampling ports for the monitoring of effluent concentrations and flow rates. An idealized NAPL mixture of key gasoline components was used to create the NAPL source zones, and dissolved sources were created using aqueous solutions having concentrations similar to water in equilibrium with the NAPL sources. The average linear velocity was controlled by pumping to be about 2 ft/d, and dissolved effluent concentrations were monitored daily. The Type-1 experiment resulted in a source signature similar to that expected for a relatively well-mixed NAPL source, with dissolved concentrations dependent on chemical solubility and initial mass fraction. The Type-2 and Type-3 experiments were conducted for 320 d and 190 d respectively. Unlike the Type-1 experiment, the concentration vs. time behavior was similar for all chemicals, for both source types. The magnitudes of the effluent concentrations varied between the Type-2 and Type-3 experiments, and were related to the hydrocarbon source mass. A fourth physical model experiment was performed to identify differences between ideal equilibrium behavior and the source concentration vs. time behavior observed in the tank experiments. Screening-level mathematical models predicted the general behavior observed in the experiments. The results of these studies suggest that dissolved concentration vs. time data can be used to distinguish between Type-1 sources in transmissive zones and Type-2 and Type-3 sources in lower permeability zones, provided that many years to decades of data are available. The results also suggest that concentration vs. time data alone will be insufficient to distinguish between NAPL and dissolved-phase storage sources in lower permeability regions.
ContributorsWilson, Sean Tomas (Author) / Johnson, Paul (Thesis advisor) / Kavazanjian, Edward (Committee member) / Fox, Peter (Committee member) / Arizona State University (Publisher)
Created2014
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Description
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
It is estimated that wind induced soil transports more than 500 x 106 metric tons of fugitive dust annually. Soil erosion has negative effects on human health, the productivity of farms, and the quality of surface waters. A variety of different polymer stabilizers are available on the market for fugitive

It is estimated that wind induced soil transports more than 500 x 106 metric tons of fugitive dust annually. Soil erosion has negative effects on human health, the productivity of farms, and the quality of surface waters. A variety of different polymer stabilizers are available on the market for fugitive dust control. Most of these polymer stabilizers are expensive synthetic polymer products. Their adverse effects and expense usually limits their use. Biopolymers provide a potential alternative to synthetic polymers. They can provide dust abatement by encapsulating soil particles and creating a binding network throughout the treated area. This research into the effectiveness of biopolymers for fugitive dust control involved three phases. Phase I included proof of concept tests. Phase II included carrying out the tests in a wind tunnel. Phase III consisted of conducting the experiments in the field. Proof of concept tests showed that biopolymers have the potential to reduce soil erosion and fugitive dust transport. Wind tunnel tests on two candidate biopolymers, xanthan and chitosan, showed that there is a proportional relationship between biopolymer application rates and threshold wind velocities. The wind tunnel tests also showed that xanthan gum is more successful in the field than chitosan. The field tests showed that xanthan gum was effective at controlling soil erosion. However, the chitosan field data was inconsistent with the xanthan data and field data on bare soil.
ContributorsAlsanad, Abdullah (Author) / Kavazanjian, Edward (Thesis advisor) / Edwards, David (Committee member) / Zapata, Claudia (Committee member) / Arizona State University (Publisher)
Created2011
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Description
In this work, the vapor transport and aerobic bio-attenuation of compounds from a multi-component petroleum vapor mixture were studied for six idealized lithologies in 1.8-m tall laboratory soil columns. Columns representing different geological settings were prepared using 20-40 mesh sand (medium-grained) and 16-minus mesh crushed granite (fine-grained). The contaminant vapor

In this work, the vapor transport and aerobic bio-attenuation of compounds from a multi-component petroleum vapor mixture were studied for six idealized lithologies in 1.8-m tall laboratory soil columns. Columns representing different geological settings were prepared using 20-40 mesh sand (medium-grained) and 16-minus mesh crushed granite (fine-grained). The contaminant vapor source was a liquid composed of twelve petroleum hydrocarbons common in weathered gasoline. It was placed in a chamber at the bottom of each column and the vapors diffused upward through the soil to the top where they were swept away with humidified gas. The experiment was conducted in three phases: i) nitrogen sweep gas; ii) air sweep gas; iii) vapor source concentrations decreased by ten times from the original concentrations and under air sweep gas. Oxygen, carbon dioxide and hydrocarbon concentrations were monitored over time. The data allowed determination of times to reach steady conditions, effluent mass emissions and concentration profiles. Times to reach near-steady conditions were consistent with theory and chemical-specific properties. First-order degradation rates were highest for straight-chain alkanes and aromatic hydrocarbons. Normalized effluent mass emissions were lower for lower source concentration and aerobic conditions. At the end of the study, soil core samples were taken every 6 in. Soil moisture content analyses showed that water had redistributed in the soil during the experiment. The soil at the bottom of the columns generally had higher moisture contents than initial values, and soil at the top had lower moisture contents. Profiles of the number of colony forming units of hydrocarbon-utilizing bacteria/g-soil indicated that the highest concentrations of degraders were located at the vertical intervals where maximum degradation activity was suggested by CO2 profiles. Finally, the near-steady conditions of each phase of the study were simulated using a three-dimensional transient numerical model. The model was fit to the Phase I data by adjusting soil properties, and then fit to Phase III data to obtain compound-specific first-order biodegradation rate constants ranging from 0.0 to 5.7x103 d-1.
ContributorsEscobar Melendez, Elsy (Author) / Johnson, Paul C. (Thesis advisor) / Andino, Jean (Committee member) / Forzani, Erica (Committee member) / Krajmalnik-Brown, Rosa (Committee member) / Kavazanjian, Edward (Committee member) / Arizona State University (Publisher)
Created2012
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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
Volatile Organic Compounds (VOCs) are central to atmospheric chemistry and have significant impacts on the environment. The reaction of oxygenated VOCs with OH radicals was first studied to understand the fate of oxygenated VOCs. The rate constants of the gas-phase reaction of OH radicals with trans-2-hexenal, trans-2-octenal, and trans-2 nonenal

Volatile Organic Compounds (VOCs) are central to atmospheric chemistry and have significant impacts on the environment. The reaction of oxygenated VOCs with OH radicals was first studied to understand the fate of oxygenated VOCs. The rate constants of the gas-phase reaction of OH radicals with trans-2-hexenal, trans-2-octenal, and trans-2 nonenal were determined using the relative rate technique. Then the interactions between VOCs and ionic liquid surfaces were studied. The goal was to find a material to selectively detect alcohol compounds. Computational chemistry calculations were performed to investigate the interactions of ionic liquids with different classes of VOCs. The thermodynamic data suggest that 1-butyl-3-methylimindazolium chloride (C4mimCl) preferentially interacts with alcohols as compared to other classes of VOCs. Fourier transform infrared spectroscopy was used to probe the ionic liquid surface before and after exposure to the VOCs that were tested. New spectral features were detected after exposure of C4mimCl to various alcohols and a VOC mixture with an alcohol in it. The new features are characteristic of the alcohols tested. No new IR features were detected after exposure of the C4mimCl to the aldehyde, ketone, alkane, alkene, alkyne or aromatic compounds. The experimental results demonstrated that C4mimCl is selective to alcohols, even in complex mixtures. The kinetic study of the association and dissociation of alcohols with C4minCl surfaces was performed. The findings in this work provide information for future gas-phase alcohol sensor design. CO2 is a major contributor to global warming. An ionic liquid functionalized reduced graphite oxide (IL-RGO)/ TiO2 nanocomposite was synthesized and used to reduce CO2 to a hydrocarbon in the presence of H2O vapor. The SEM image revealed that IL-RGO/TiO2 contained separated reduced graphite oxide flakes with TiO2 nanoparticles. Diffuse Reflectance Infrared Fourier Transform Spectroscopy was used to study the conversion of CO2 and H2O vapor over the IL-RGO/TiO2 catalyst. Under UV-Vis irradiation, CH4 was found to form after just 40 seconds of irradiation. The concentration of CH4 continuously increased under longer irradiation time. This research is particularly important since it seems to suggest the direct, selective formation of CH4 as opposed to CO.
ContributorsGao, Tingting (Author) / Andino, Jean M (Thesis advisor) / Forzani, Erica (Committee member) / Kavazanjian, Edward (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
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

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.
ContributorsGushgari, Adam Jon (Author) / Halden, Rolf U. (Thesis advisor) / Kavazanjian, Edward (Committee member) / Fraser, Matthew (Committee member) / Venkatesan, Arjun (Committee member) / Mascaro, Giuseppe (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