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Description
Many manmade chemicals used in consumer products are ultimately washed down the drain and are collected in municipal sewers. Efficient chemical monitoring at wastewater treatment (WWT) plants thus may provide up-to-date information on chemical usage rates for epidemiological assessments. The objective of the present study was to extrapolate this concept,

Many manmade chemicals used in consumer products are ultimately washed down the drain and are collected in municipal sewers. Efficient chemical monitoring at wastewater treatment (WWT) plants thus may provide up-to-date information on chemical usage rates for epidemiological assessments. The objective of the present study was to extrapolate this concept, termed 'sewage epidemiology', to include municipal sewage sludge (MSS) in identifying and prioritizing contaminants of emerging concern (CECs). To test this the following specific aims were defined: i) to screen and identify CECs in nationally representative samples of MSS and to provide nationwide inventories of CECs in U.S. MSS; ii) to investigate the fate and persistence in MSS-amended soils, of sludge-borne hydrophobic CECs; and iii) to develop an analytical tool relying on contaminant levels in MSS as an indicator for identifying and prioritizing hydrophobic CECs. Chemicals that are primarily discharged to the sewage systems (alkylphenol surfactants) and widespread persistent organohalogen pollutants (perfluorochemicals and brominated flame retardants) were analyzed in nationally representative MSS samples. A meta-analysis showed that CECs contribute about 0.04-0.15% to the total dry mass of MSS, a mass equivalent of 2,700-7,900 metric tonnes of chemicals annually. An analysis of archived mesocoms from a sludge weathering study showed that 64 CECs persisted in MSS/soil mixtures over the course of the experiment, with half-lives ranging between 224 and >990 days; these results suggest an inherent persistence of CECs that accumulate in MSS. A comparison of the spectrum of chemicals (n=52) analyzed in nationally representative biological specimens from humans and MSS revealed 70% overlap. This observed co-occurrence of contaminants in both matrices suggests that MSS may serve as an indicator for ongoing human exposures and body burdens of pollutants in humans. In conclusion, I posit that this novel approach in sewage epidemiology may serve to pre-screen and prioritize the several thousands of known or suspected CECs to identify those that are most prone to pose a risk to human health and the environment.
ContributorsVenkatesan, Arjunkrishna (Author) / Halden, Rolf U. (Thesis advisor) / Westerhoff, Paul (Committee member) / Fox, Peter (Committee member) / Arizona State University (Publisher)
Created2013
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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 improve nitrate photocatalysis and transition treatment to the full-scale. The research objectives were to (1) examine commercial and synthesized photocatalysts,

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).
ContributorsDoudrick, Kyle (Author) / Westerhoff, Paul (Thesis advisor) / Halden, Rolf (Committee member) / Hristovski, Kiril (Committee member) / Arizona State University (Publisher)
Created2013
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Description
Biofuel from microbial biomass is a viable alternative to current energy production practices that could mitigate greenhouse gas levels and reduce dependency on fossil fuels. Sustainable production of microbial biomass requires efficient utilization of nutrients like phosphorus (P). P is a limited resource which is vital for global food security.

Biofuel from microbial biomass is a viable alternative to current energy production practices that could mitigate greenhouse gas levels and reduce dependency on fossil fuels. Sustainable production of microbial biomass requires efficient utilization of nutrients like phosphorus (P). P is a limited resource which is vital for global food security. This paper seeks to understand the fate of P through biofuel production and proposes a proof-of-concept process to recover P from microbial biomass. The photosynthetic cyanobacterium Synechocystis sp. PCC 6803 is found to contain 1.4% P by dry weight. After the crude lipids are extracted for biofuel processing, 92% of the intercellular P is found within the residual biomass. Most intercellular P is associated with nucleic acids which remain within the cell after lipids are extracted. Phospholipids comprise a small percentage of cellular P. A wet chemical advanced oxidation process of adding 30% hydrogen peroxide followed by 10 min of microwave heating converts 92% of the total cellular P from organic-P and polyphosphate into orthophosphate. P was then isolated and concentrated from the complex digested matrix by use of resins. An anion exchange resin impregnated with iron nanoparticles demonstrates high affinity for P by sorbing 98% of the influent P through 20 bed volumes, but only was able to release 23% of it when regenerated. A strong base anion exchange resin sorbed 87% of the influent P through 20 bed volumes then released 50% of it upon regeneration. The overall P recovery process was able to recover 48% of the starting intercellular P into a pure and concentrated nutrient solution available for reuse. Further optimization of elution could improve P recovery, but this provides a proof-of-concept for converting residual biomass after lipid extraction to a beneficial P source.
ContributorsGifford, James McKay (Author) / Westerhoff, Paul (Thesis advisor) / Rittmann, Bruce (Committee member) / Vannela, Ravindhar (Committee member) / Arizona State University (Publisher)
Created2012
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Description
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
This thesis research focuses on developing a single-cell gene expression analysis method for marine diatom Thalassiosira pseudonana and constructing a chip level tool to realize the single cell RT-qPCR analysis. This chip will serve as a conceptual foundation for future deployable ocean monitoring systems. T. pseudonana, which is a common

This thesis research focuses on developing a single-cell gene expression analysis method for marine diatom Thalassiosira pseudonana and constructing a chip level tool to realize the single cell RT-qPCR analysis. This chip will serve as a conceptual foundation for future deployable ocean monitoring systems. T. pseudonana, which is a common surface water microorganism, was detected in the deep ocean as confirmed by phylogenetic and microbial community functional studies. Six-fold copy number differences between 23S rRNA and 23S rDNA were observed by RT-qPCR, demonstrating the moderate functional activity of detected photosynthetic microbes in the deep ocean including T. pseudonana. Because of the ubiquity of T. pseudonana, it is a good candidate for an early warning system for ocean environmental perturbation monitoring. This early warning system will depend on identifying outlier gene expression at the single-cell level. An early warning system based on single-cell analysis is expected to detect environmental perturbations earlier than population level analysis which can only be observed after a whole community has reacted. Preliminary work using tube-based, two-step RT-qPCR revealed for the first time, gene expression heterogeneity of T. pseudonana under different nutrient conditions. Heterogeneity was revealed by different gene expression activity for individual cells under the same conditions. This single cell analysis showed a skewed, lognormal distribution and helped to find outlier cells. The results indicate that the geometric average becomes more important and representative of the whole population than the arithmetic average. This is in contrast with population level analysis which is limited to arithmetic averages only and highlights the value of single cell analysis. In order to develop a deployable sensor in the ocean, a chip level device was constructed. The chip contains surface-adhering droplets, defined by hydrophilic patterning, that serve as real-time PCR reaction chambers when they are immersed in oil. The chip had demonstrated sensitivities at the single cell level for both DNA and RNA. The successful rate of these chip-based reactions was around 85%. The sensitivity of the chip was equivalent to published microfluidic devices with complicated designs and protocols, but the production process of the chip was simple and the materials were all easily accessible in conventional environmental and/or biology laboratories. On-chip tests provided heterogeneity information about the whole population and were validated by comparing with conventional tube based methods and by p-values analysis. The power of chip-based single-cell analyses were mainly between 65-90% which were acceptable and can be further increased by higher throughput devices. With this chip and single-cell analysis approaches, a new paradigm for robust early warning systems of ocean environmental perturbation is possible.
ContributorsShi, Xu (Author) / Meldrum, Deirdre R. (Thesis advisor) / Zhang, Weiwen (Committee member) / Chao, Shih-hui (Committee member) / Westerhoff, Paul (Committee member) / Arizona State University (Publisher)
Created2013
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Description
Contaminants of emerging concern (CECs) present in wastewater effluent can threat its safe discharge or reuse. Additional barriers of protection can be provided using advanced or natural treatment processes. This dissertation evaluated ozonation and constructed wetlands to remove CECs from wastewater effluent. Organic CECs can be removed by hydroxyl radical

Contaminants of emerging concern (CECs) present in wastewater effluent can threat its safe discharge or reuse. Additional barriers of protection can be provided using advanced or natural treatment processes. This dissertation evaluated ozonation and constructed wetlands to remove CECs from wastewater effluent. Organic CECs can be removed by hydroxyl radical formed during ozonation, however estimating the ozone demand of wastewater effluent is complicated due to the presence of reduced inorganic species. A method was developed to estimate ozone consumption only by dissolved organic compounds and predict trace organic oxidation across multiple wastewater sources. Organic and engineered nanomaterial (ENM) CEC removal in constructed wetlands was investigated using batch experiments and continuous-flow microcosms containing decaying wetland plants. CEC removal varied depending on their physico-chemical properties, hydraulic residence time (HRT) and relative quantities of plant materials in the microcosms. At comparable HRTs, ENM removal improved with higher quantity of plant materials due to enhanced sorption which was verified in batch-scale studies with plant materials. A fate-predictive model was developed to evaluate the role of design loading rates on organic CEC removal. Areal removal rates increased with hydraulic loading rates (HLRs) and carbon loading rates (CLRs) unless photolysis was the dominant removal mechanism (e.g. atrazine). To optimize CEC removal, wetlands with different CLRs can be used in combination without lowering the net HLR. Organic CEC removal in denitrifying conditions of constructed wetlands was investigated and selected CECs (e.g. estradiol) were found to biotransform while denitrification occurred. Although level of denitrification was affected by HRT, similar impact on estradiol was not observed due to a dominant effect from plant biomass quantity. Overall, both modeling and experimental findings suggest considering CLR as an equally important factor with HRT or HLR to design constructed wetlands for CEC removal. This dissertation provided directions to select design parameters for ozonation (ozone dose) and constructed wetlands (design loading rates) to meet organic CEC removal goals. Future research is needed to understand fate of ENMs during ozonation and quantify the contributions from different transformation mechanisms occurring in the wetlands to incorporate in a model and evaluate the effect of wetland design.
ContributorsSharif, Fariya (Author) / Westerhoff, Paul (Thesis advisor) / Halden, Rolf (Committee member) / Fox, Peter (Committee member) / Herckes, Pierre (Committee member) / Arizona State University (Publisher)
Created2013
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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 extreme weather events and in treated wastewater includes natural organic matter (NOM), contaminants of emerging concern (CECs), and microbial extracellular

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.
ContributorsBarry, Michelle (Author) / Barry, Michelle C (Thesis advisor) / Westerhoff, Paul (Committee member) / Fox, Peter (Committee member) / Halden, Rolf (Committee member) / Hristovski, Kiril (Committee member) / Arizona State University (Publisher)
Created2014
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Description
The National Research Council 2011 report lists quantifying the extent of de facto (or unplanned) potable reuse in the U.S. as the top research need associated with assessing the potential for expanding the nations water supply through reuse of municipal wastewater. Efforts to identify the significance and potential health impacts

The National Research Council 2011 report lists quantifying the extent of de facto (or unplanned) potable reuse in the U.S. as the top research need associated with assessing the potential for expanding the nations water supply through reuse of municipal wastewater. Efforts to identify the significance and potential health impacts of de facto water reuse are impeded by out dated information regarding the contribution of municipal wastewater effluent to potable water supplies. This project aims to answer this research need. The overall goal of the this project is to quantify the extent of de facto reuse by developing a model that estimates the amount of wastewater effluent that is present within drinking water treatment plants; and to use the model in conjunction with a survey to help assess public perceptions. The four-step approach to accomplish this goal includes: (1) creating a GIS-based model coupled with Python programming; (2) validating the model with field studies by analyzing sucralose as a wastewater tracer; (3) estimating the percentage of wastewater in raw drinking water sources under varying streamflow conditions; (4) and assessing through a social survey the perceptions of the general public relating to acceptance and occurrence of de facto reuse. The resulting De Facto Reuse in our Nations Consumable Supply (DRINCS) Model, estimates that treated municipal wastewater is present at nearly 50% of drinking water treatment plant intake sites serving greater than 10,000 people (N=2,056). Contrary to the high frequency of occurrence, the magnitude of occurrence is relatively low with 50% of impacted intakes yielding less than 1% de facto reuse under average streamflow conditions. Model estimates increase under low flow conditions (modeled by Q95), in several cases treated wastewater makes up 100% of the water supply. De facto reuse occurs at levels that surpass what is publically perceived in the three cities of Atlanta, GA, Philadelphia, PA, and Phoenix, AZ. Respondents with knowledge of de facto reuse occurrence are 10 times more likely to have a high acceptance (greater than 75%) of treated wastewater at their home tap.
ContributorsRice, Jacelyn (Author) / Westerhoff, Paul (Thesis advisor) / Abbaszadegan, Morteza (Committee member) / Vivoni, Enrique (Committee member) / Wutich, Amber (Committee member) / Arizona State University (Publisher)
Created2014
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Description
Lipids and free fatty acids (FFA) from cyanobacterium Synechocystis can be used for biofuel (e.g. biodiesel or renewable diesel) production. In order to utilize and scale up this technique, downstream processes including culturing and harvest, cell disruption, and extraction were studied. Several solvents/solvent systems were screened for lipid extraction from

Lipids and free fatty acids (FFA) from cyanobacterium Synechocystis can be used for biofuel (e.g. biodiesel or renewable diesel) production. In order to utilize and scale up this technique, downstream processes including culturing and harvest, cell disruption, and extraction were studied. Several solvents/solvent systems were screened for lipid extraction from Synechocystis. Chloroform + methanol-based Folch and Bligh & Dyer methods were proved to be "gold standard" for small-scale analysis due to their highest lipid recoveries that were confirmed by their penetration of the cell membranes, higher polarity, and stronger interaction with hydrogen bonds. Less toxic solvents, such as methanol and MTBE, or direct transesterification of biomass (without pre-extraction step) gave only slightly lower lipid-extraction yields and can be considered for large-scale application. Sustained exposure to high and low temperature extremes severely lowered the biomass and lipid productivity. Temperature stress also triggered changes of lipid quality such as the degree of unsaturation; thus, it affected the productivities and quality of Synechocystis-derived biofuel. Pulsed electric field (PEF) was evaluated for cell disruption prior to lipid extraction. A treatment intensity > 35 kWh/m3 caused significant damage to the plasma membrane, cell wall, and thylakoid membrane, and it even led to complete disruption of some cells into fragments. Treatment by PEF enhanced the potential for the low-toxicity solvent isopropanol to access lipid molecules during subsequent solvent extraction, leading to lower usage of isopropanol for the same extraction efficiency. Other cell-disruption methods also were tested. Distinct disruption effects to the cell envelope, plasma membrane, and thylakoid membranes were observed that were related to extraction efficiency. Microwave and ultrasound had significant enhancement of lipid extraction. Autoclaving, ultrasound, and French press caused significant release of lipid into the medium, which may increase solvent usage and make medium recycling difficult. Production of excreted FFA by mutant Synechocystis has the potential of reducing the complexity of downstream processing. Major problems, such as FFA precipitation and biodegradation by scavengers, account for FFA loss in operation. Even a low concentration of FFA scavengers could consume FFA at a high rate that outpaced FFA production rate. Potential strategies to overcome FFA loss include high pH, adsorptive resin, and sterilization techniques.
ContributorsSheng, Chieh (Author) / Rittmann, Bruce E. (Thesis advisor) / Westerhoff, Paul (Committee member) / Vermaas, Willem (Committee member) / Arizona State University (Publisher)
Created2011
Description
Filtration for microfluidic sample-collection devices is desirable for sample selection, concentration, preprocessing, and downstream manipulation, but microfabricating the required sub-micrometer filtration structure is an elaborate process. This thesis presents a simple method to fabricate polydimethylsiloxane (PDMS) devices with an integrated membrane filter that will sample, lyse, and extract the DNA

Filtration for microfluidic sample-collection devices is desirable for sample selection, concentration, preprocessing, and downstream manipulation, but microfabricating the required sub-micrometer filtration structure is an elaborate process. This thesis presents a simple method to fabricate polydimethylsiloxane (PDMS) devices with an integrated membrane filter that will sample, lyse, and extract the DNA from microorganisms in aqueous environments. An off-the-shelf membrane filter disc was embedded in a PDMS layer and sequentially bound with other PDMS channel layers. No leakage was observed during filtration. This device was validated by concentrating a large amount of cyanobacterium Synechocystis in simulated sample water with consistent performance across devices. After accumulating sufficient biomass on the filter, a sequential electrochemical lysing process was performed by applying 5VDC across the filter. This device was further evaluated by delivering several samples of differing concentrations of cyanobacterium Synechocystis then quantifying the DNA using real-time PCR. Lastly, an environmental sample was run through the device and the amount of photosynthetic microorganisms present in the water was determined. The major breakthroughs in this design are low energy demand, cheap materials, simple design, straightforward fabrication, and robust performance, together enabling wide-utility of similar chip-based devices for field-deployable operations in environmental micro-biotechnology.
ContributorsLecluse, Aurelie (Author) / Meldrum, Deirdre (Thesis advisor) / Chao, Joseph (Thesis advisor) / Westerhoff, Paul (Committee member) / Arizona State University (Publisher)
Created2011