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This dissertation explores the use of bench-scale batch microcosms in remedial design of contaminated aquifers, presents an alternative methodology for conducting such treatability studies, and - from technical, economical, and social perspectives - examines real-world application of this new technology. In situ bioremediation (ISB) is an effective remedial approach for

This dissertation explores the use of bench-scale batch microcosms in remedial design of contaminated aquifers, presents an alternative methodology for conducting such treatability studies, and - from technical, economical, and social perspectives - examines real-world application of this new technology. In situ bioremediation (ISB) is an effective remedial approach for many contaminated groundwater sites. However, site-specific variability necessitates the performance of small-scale treatability studies prior to full-scale implementation. The most common methodology is the batch microcosm, whose potential limitations and suitable technical alternatives are explored in this thesis. In a critical literature review, I discuss how continuous-flow conditions stimulate microbial attachment and biofilm formation, and identify unique microbiological phenomena largely absent in batch bottles, yet potentially relevant to contaminant fate. Following up on this theoretical evaluation, I experimentally produce pyrosequencing data and perform beta diversity analysis to demonstrate that batch and continuous-flow (column) microcosms foster distinctly different microbial communities. Next, I introduce the In Situ Microcosm Array (ISMA), which took approximately two years to design, develop, build and iteratively improve. The ISMA can be deployed down-hole in groundwater monitoring wells of contaminated aquifers for the purpose of autonomously conducting multiple parallel continuous-flow treatability experiments. The ISMA stores all sample generated in the course of each experiment, thereby preventing the release of chemicals into the environment. Detailed results are presented from an ISMA demonstration evaluating ISB for the treatment of hexavalent chromium and trichloroethene. In a technical and economical comparison to batch microcosms, I demonstrate the ISMA is both effective in informing remedial design decisions and cost-competitive. Finally, I report on a participatory technology assessment (pTA) workshop attended by diverse stakeholders of the Phoenix 52nd Street Superfund Site evaluating the ISMA's ability for addressing a real-world problem. In addition to receiving valuable feedback on perceived ISMA limitations, I conclude from the workshop that pTA can facilitate mutual learning even among entrenched stakeholders. In summary, my doctoral research (i) pinpointed limitations of current remedial design approaches, (ii) produced a novel alternative approach, and (iii) demonstrated the technical, economical and social value of this novel remedial design tool, i.e., the In Situ Microcosm Array technology.
ContributorsKalinowski, Tomasz (Author) / Halden, Rolf U. (Thesis advisor) / Johnson, Paul C (Committee member) / Krajmalnik-Brown, Rosa (Committee member) / Bennett, Ira (Committee member) / Arizona State University (Publisher)
Created2013
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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
In situ remediation of contaminated aquifers, specifically in situ bioremediation (ISB), has gained popularity over pump-and-treat operations. It represents a more sustainable approach that can also achieve complete mineralization of contaminants in the subsurface. However, the subsurface reality is very complex, characterized by hydrodynamic groundwater movement, geological heterogeneity, and mass-transfer

In situ remediation of contaminated aquifers, specifically in situ bioremediation (ISB), has gained popularity over pump-and-treat operations. It represents a more sustainable approach that can also achieve complete mineralization of contaminants in the subsurface. However, the subsurface reality is very complex, characterized by hydrodynamic groundwater movement, geological heterogeneity, and mass-transfer phenomena governing contaminant transport and bioavailability. These phenomena cannot be properly studied using commonly conducted laboratory batch microcosms lacking realistic representation of the processes named above. Instead, relevant processes are better understood by using flow-through systems (sediment columns). However, flow-through column studies are typically conducted without replicates. Due to additional sources of variability (e.g., flow rate variation between columns and over time), column studies are expected to be less reproducible than simple batch microcosms. This was assessed through a comprehensive statistical analysis of results from multiple batch and column studies. Anaerobic microbial biotransformations of trichloroethene and of perchlorate were chosen as case studies. Results revealed that no statistically significant differences were found between reproducibility of batch and column studies. It has further been recognized that laboratory studies cannot accurately reproduce many phenomena encountered in the field. To overcome this limitation, a down-hole diagnostic device (in situ microcosm array - ISMA) was developed, that enables the autonomous operation of replicate flow-through sediment columns in a realistic aquifer setting. Computer-aided design (CAD), rapid prototyping, and computer numerical control (CNC) machining were used to create a tubular device enabling practitioners to conduct conventional sediment column studies in situ. A case study where two remediation strategies, monitored natural attenuation and bioaugmentation with concomitant biostimulation, were evaluated in the laboratory and in situ at a perchlorate-contaminated site. Findings demonstrate the feasibility of evaluating anaerobic bioremediation in a moderately aerobic aquifer. They further highlight the possibility of mimicking in situ remediation strategies on the small-scale in situ. The ISMA is the first device offering autonomous in situ operation of conventional flow-through sediment microcosms and producing statistically significant data through the use of multiple replicates. With its sustainable approach to treatability testing and data gathering, the ISMA represents a versatile addition to the toolbox of scientists and engineers.
ContributorsMcClellan, Kristin (Author) / Halden, Rolf U. (Thesis advisor) / Johnson, Paul C (Committee member) / Krajmalnik-Brown, Rosa (Committee member) / Arizona State University (Publisher)
Created2013
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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
Contamination by chlorinated ethenes is widespread in groundwater aquifers, sediment, and soils worldwide. The overarching objectives of my research were to understand how the bacterial genus Dehalococcoides function optimally to carry out reductive dechlorination of chlorinated ethenes in a mixed microbial community and then apply this knowledge to manage dechlorinating

Contamination by chlorinated ethenes is widespread in groundwater aquifers, sediment, and soils worldwide. The overarching objectives of my research were to understand how the bacterial genus Dehalococcoides function optimally to carry out reductive dechlorination of chlorinated ethenes in a mixed microbial community and then apply this knowledge to manage dechlorinating communities in the hydrogen-based membrane biofilm reactor (MBfR). The MBfR is used for the biological reduction of oxidized contaminants in water using hydrogen supplied as the electron donor by diffusion through gas-transfer fibers. First, I characterized a new anaerobic dechlorinating community developed in our laboratory, named DehaloR^2, in terms of chlorinated ethene turnover rates and assessed its microbial community composition. I then carried out an experiment to correlate performance and community structure for trichloroethene (TCE)-fed microbial consortia. Fill-and-draw reactors inoculated with DehaloR^2 demonstrated a direct correlation between microbial community function and structure as the TCE-pulsing rate was increased. An electron-balance analysis predicted the community structure based on measured concentrations of products and constant net yields for each microorganism. The predictions corresponded to trends in the community structure based on pyrosequencing and quantitative PCR up to the highest TCE pulsing rate, where deviations to the trend resulted from stress by the chlorinated ethenes. Next, I optimized a method for simultaneous detection of chlorinated ethenes and ethene at or below the Environmental Protection Agency maximum contaminant levels for groundwater using solid phase microextraction in a gas chromatograph with a flame ionization detector. This method is ideal for monitoring biological reductive dechlorination in groundwater, where ethene is the ultimate end product. The major advantage of this method is that it uses a small sample volume of 1 mL, making it ideally suited for bench-scale feasibility studies, such as the MBfR. Last, I developed a reliable start-up and operation strategy for TCE reduction in the MBfR. Successful operation relied on controlling the pH-increase effects of methanogenesis and homoacetogenesis, along with creating hydrogen limitation during start-up to allow dechlorinators to compete against other microorgansims. Methanogens were additionally minimized during continuous flow operation by a limitation in bicarbonate resulting from strong homoacetogenic activity.
ContributorsZiv-El, Michal (Author) / Rittmann, Bruce E. (Thesis advisor) / Krajmalnik-Brown, Rosa (Thesis advisor) / Halden, Rolf U. (Committee member) / Arizona State University (Publisher)
Created2012
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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
The presence of compounds such as pharmaceuticals and personal care products (PPCPs) in the environment is a cause for concern as they exhibit secondary effects on non-target organisms and are also indicative of incomplete removal by wastewater treatment plants (WWTPs) during water reclamation. Analytical methods and predictive models can hel

The presence of compounds such as pharmaceuticals and personal care products (PPCPs) in the environment is a cause for concern as they exhibit secondary effects on non-target organisms and are also indicative of incomplete removal by wastewater treatment plants (WWTPs) during water reclamation. Analytical methods and predictive models can help inform on the rates at which these contaminants enter the environment via biosolids use or wastewater effluent release to estimate the risk of adverse effects. The goals of this research project were to integrate the results obtained from the two different methods of risk assessment, (a) in silico modeling and (b) experimental analysis. Using a previously published empirical model, influent and effluent concentration ranges were predicted for 10 sterols and validated with peer-reviewed literature. The in silico risk assessment analysis performed for sterols and hormones in biosolids concluded that hormones possess high leaching potentials and that particularly 17-α-ethinyl estradiol (EE2) can pose significant threat to fathead minnows (P. promelas) via leaching from terrestrial depositions of biosolids. Six mega-composite biosolids samples representative of 94 WWTPs were analyzed for a suite of 120 PPCPs using the extended U.S. EPA Method 1694 protocol. Results indicated the presence of 26 previously unmonitored PPCPs in the samples with estimated annual release rates of 5-15 tons yr-1 via land application of biosolids. A mesocosm sampling analysis that was included in the study concluded that four compounds amitriptyline, paroxetine, propranolol and sertraline warrant further monitoring due to their high release rates from land applied biosolids and their calculated extended half-lives in soils. There is a growing interest in the scientific community towards the development of new analytical protocols for analyzing solid matrices such as biosolids for the presence of PPCPs and other established and emerging contaminants of concern. The two studies presented here are timely and an important addition to the increasing base of scientific articles regarding environmental release of PPCPs and exposure risks associated with biosolids land application. This research study emphasizes the need for coupling experimental results with predictive analytical modeling output in order to more fully assess the risks posed by compounds detected in biosolids.
ContributorsPrakash Chari, Bipin (Author) / Halden, Rolf U. (Thesis advisor) / Westerhoff, Paul (Committee member) / Fox, Peter (Committee member) / Arizona State University (Publisher)
Created2012
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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
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

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