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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
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
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
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
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
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Description
As selenium is toxic at low levels, treatment methods to remove selenium from industrial waste waters are needed. In this work, three groups of sorbent materials were investigated in detail for their effectiveness for selenium and arsenic removal from water: 1) nanostructured carbon-based materials, 2) layered double hydroxide (LDH)-based materials,

As selenium is toxic at low levels, treatment methods to remove selenium from industrial waste waters are needed. In this work, three groups of sorbent materials were investigated in detail for their effectiveness for selenium and arsenic removal from water: 1) nanostructured carbon-based materials, 2) layered double hydroxide (LDH)-based materials, and 3) biopolymer-based sorbents. The materials were investigated in spiked de-ionized water and waters collected from different locations at Salt River Project’s (SRP) Santan Generating Station in Gilbert, AZ. The results show that nanostructured carbon-based materials removed ~80% and up to 100% selenium and arsenic, respectively in spiked DI water. Heat treated layered double hydroxides removed close to 100% removal in selenium and arsenic spiked DI water. Isotherms conducted in spiked DI water fit the Langmuir model and showed a maximum selenate adsorption capacity of 67 mg/g for the calcined LDH powder. Results from SRP waters showed that certain LDH sorbents were effective for removing the selenium, but that higher pH and existence of competing ions affected the removal efficiencies. The functionalized biopolymer sorbent from Crystal Clear Technologies: CCT-149/OCI-B showed good removal efficiencies for both selenate and selenite in DI water. Isotherms conducted in spiked DI water for CCT-149 fit the Langmuir model and showed a maximum selenate adsorption capacity of 90.9 mg/g. Column tests using spiked DI water and waters obtained from SRP wells were investigated using both LDH and CCT-149/OCI-B. Removal of sulfate using chemical pre-treatment of the water with barium chloride resulted in about three times higher selenate loading onto the granular LDH and doubled the water volume that can be treated using CCT-149/OCI-B. The results from the column tests are being used to guide the pilot testing investigating the implementation of LDH sorbents at pilot scale at the Santan plant. The good results in the cooling tower #5 blowdown water and combined discharge waste water of SRP provide valuable information about the efficacy and efficiency of adsorptive media for the removal of selenium. Composites comprising LDH nanosheets with different substrates were successfully synthesized that were able to retain the performance in removing selenate of nanosheet LDH.
ContributorsLi, Man (Author) / Chan, Candace (Thesis advisor) / Lind, Mary Laura (Committee member) / Perreault, Francois (Committee member) / Arizona State University (Publisher)
Created2017
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Description
Contamination of drinking water supplies from oxo-anion pollutants necessitates treatment prior to potable use. This dissertation aims to inform and improve light delivery (emission spectra, radiant intensity, reactor configuration) in order to enhance the photocatalytic reduction of hexavalent chromium (Cr(VI)) and nitrate, two common oxo-anions in drinking water, and photocatalytic

Contamination of drinking water supplies from oxo-anion pollutants necessitates treatment prior to potable use. This dissertation aims to inform and improve light delivery (emission spectra, radiant intensity, reactor configuration) in order to enhance the photocatalytic reduction of hexavalent chromium (Cr(VI)) and nitrate, two common oxo-anions in drinking water, and photocatalytic oxidation of two model organic pollutants (methylene blue, (MB) and para-chlorobenzoic acid (pCBA)). By varying the photon fluence dose, two metrics (contaminant quantum yield (Φ), and electrical energy per order (EEO)) were used to assess photocatalytic reactor performance. A detailed literature review and experimental results demonstrated how different irradiance sources with variable intensity and emission spectra synergistically enhanced contaminant removal by a coupled photolytic/photocatalytic reaction mechanism. Cr(VI) was photocatalytically reduced on TiO2 and formed Cr(OH)3(s) in a large-scale slurry reactor, but Cr(III) was then photolyzed and reformed Cr(VI). UV light also led to photo-aggregation of TiO2 which improved its recovery by the ceramic membrane within the reactor. For nitrate reduction, light source emission spectra and fluence dose delineate the preferred pathways as intermediates were reduced via wavelength-dependent mechanisms. HONO was identified as a key nitrate reduction intermediate, which was reduced photocatalytically (UV wavelengths) and/or readily photolyzed at 365nm, to yield nitrogen gases. Photocatalytic nitrate reduction efficiency was higher for discrete wavelength irradiation than polychromatic irradiation. Light delivery through aqueous media to the catalyst surface limits efficiency of slurry-based photocatalysts because absorption and scattering of light in nanomaterial slurries decreases effective photon transmittance and minimizes photolytic reactions. The use of optical fibers coupled to light emitting diodes (OF-LED) with immobilized catalyst demonstrated higher performance compared to slurry systems. OF-LED increased Φ for MB degradation by increasing direct photon delivery to the photocatalyst. Design of OF-LED reactors using bundled optical fibers demonstrated photocatalytic pCBA removal with high Φ and reduced EEO due to increased surface area and catalytic sites compared to single OF/LED couples. This work advances light delivery as well as the suspension and attachment of nanoparticles in photocatalytic water treatment for selective transformation of oxo-anions and organic compounds to innocuous species.
ContributorsTugaoen, Heather O'Neal (Author) / Westerhoff, Paul (Thesis advisor) / Hristovski, Kiril (Thesis advisor) / Chan, Candace (Committee member) / Arizona State University (Publisher)
Created2017
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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 hexavalent chromium from drinking or industrial waters via a UV/titanium dioxide (TiO2) process. Using an integrated UV lamp/ceramic membrane system

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.
ContributorsStancl, Heather O'Neal (Author) / Westerhoff, Paul K (Thesis advisor) / Chan, Candace (Committee member) / Hristovski, Kiril (Committee member) / Arizona State University (Publisher)
Created2013
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Description
De facto potable reuse (DFR) occurs when surface water sources at drinking water treatment plants (DWTPs) contain treated effluents from upstream wastewater treatment plants (WWTPs). Contaminants of emerging concerns (CECs) originate from treated effluents (e.g., unregulated disinfection by-products, pathogenic microorganisms as Cryptosporidium oocyst, Giardia cyst, and Norovirus) can be present

De facto potable reuse (DFR) occurs when surface water sources at drinking water treatment plants (DWTPs) contain treated effluents from upstream wastewater treatment plants (WWTPs). Contaminants of emerging concerns (CECs) originate from treated effluents (e.g., unregulated disinfection by-products, pathogenic microorganisms as Cryptosporidium oocyst, Giardia cyst, and Norovirus) can be present in surface water and pose human health risks linked to CECs. Previously developed De facto Reuse Incidence in our Nations Consumable Supply (DRINCS) model predicted DFR for the national largest DWTPs that serve >10,000 people (N = 2,056 SW intakes at 1,210 DWTPs). The dissertation aims to quantify DFR at all surface water intakes for smaller DWTPs serving ≤10,000 people across the United States and develop a programmed ArcGIS tool for proximity analysis between upstream WWTPs and DWTPs. The tested hypothesis is whether DWTPs serving ≤10,000 people are more likely to be impacted by DFR than larger systems serving > 10,000 people.The original DRINCS model was expanded to include all smaller DWTPs (N = 6,045 SW intakes at 3,984 DWTPs) in the U.S. First, results for Texas predicted that two-thirds of all SW intakes were impacted by at least one WWTP upstream. The level of DFR at SW intakes in Texas ranged between 1% to 20% under average flow and exceeded 90% during mild droughts. Smaller DWTPs in Texas had a higher frequency of DFR than larger systems while < 10% of these DWTPs employed advanced technology (AT) capable of removing CECs. Second, nationally over 40% of surface water intakes at all DWTPs were impacted by DFR under average flow (2,917 of 6,826). Smaller DWTPs had a higher frequency (1,504 and 1,413, respectively) of being impacted by upstream WWTP discharges than larger DWTPs. Third, the difference in DFR levels at smaller versus larger DWTPs was statistically unclear (t-test, p = 0.274). Smaller communities could have high risks to CECs as they rely on surface water from lower-order streams impacted by DFR. Furthermore, smaller DWTPs lack more than twice as advanced unit processes as larger DWTPs with 52.1% and 23%, respectively. DFR levels for DWTPs serving > 10,000 people were statistically higher on mid-size order streams (3, 5, and 8) than those for smaller DWTPs. Finally, DWTPs serving > 10,000 people could pose risks to a population impacted by DFR > 1% as 40 times as those served by smaller DWTPs with 71 million and 1.7 million people, respectively. The total exposed population to risks of CECs served by DWTPs impacted by upstream WWTP discharges (DFR >10%) was estimated at 12.3 million people in the United States. Future studies can use DRINCS results to conduct an epidemiological risk assessment for impacted communities and identify communities that would benefit from advanced technology to remove CECs.
ContributorsNguyen, Thuy Thi Thu (Author) / Westerhoff, Paul K (Thesis advisor) / Hristovski, Kiril (Committee member) / Fox, Peter (Committee member) / Muenich, Rebecca (Committee member) / Quay, Ray (Committee member) / Arizona State University (Publisher)
Created2020