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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
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
Stable isotopes were measured in the groundwaters of the Salt River Valley basin in central Arizona to explore the utility of stable isotopes for sourcing recharge waters and engineering better well designs. Delta values for the sampled groundwaters range from -7.6‰ to -10‰ in 18O and -60‰ to -91‰ in

Stable isotopes were measured in the groundwaters of the Salt River Valley basin in central Arizona to explore the utility of stable isotopes for sourcing recharge waters and engineering better well designs. Delta values for the sampled groundwaters range from -7.6‰ to -10‰ in 18O and -60‰ to -91‰ in D and display displacements off the global meteoric water line indicative of surficial evaporation during river transport into the area. Groundwater in the basin is all derived from top-down river recharge; there is no evidence of ancient playa waters even in the playa deposits. The Salt and Verde Rivers are the dominant source of groundwater for the East Salt River valley- the Agua Fria River also contributes significantly to the West Salt River Valley. Groundwater isotopic compositions are generally more depleted in 18O and D with depth, indicating past recharge in cooler climates, and vary within subsurface aquifer layers as sampled during well drilling. When isotopic data were evaluated together with geologic and chemical analyses and compared with data from the final well production water it was often possible to identify: 1) which horizons are the primary producers of groundwater flow and how that might change with time, 2) the chemical exchange of cations and anions via water-rock interaction during top-down mixing of recharge water with older waters, 3) how much well production might be lost if arsenic-contributing horizons were sealed off, and 4) the extent to which replacement wells tap different subsurface water sources. In addition to identifying sources of recharge, stable isotopes offer a new and powerful approach for engineering better and more productive water wells.
ContributorsBond, Angela Nicole (Author) / Knauth, Paul (Thesis advisor) / Hartnett, Hilairy (Committee member) / Shock, Everett (Committee member) / Arizona State University (Publisher)
Created2010
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Description
Arsenic (As) and chromium (Cr) occur naturally in AZ surface and groundwaters, pose different health impacts, and exhibit different treatment efficacies. Hexavalent chromium (Cr(VI)) has newly recognized human health concerns, and State and Federal agencies are evaluating a low Cr(VI)-specific maximum contaminant level (MCL) for drinking water. Occurrence of Cr

Arsenic (As) and chromium (Cr) occur naturally in AZ surface and groundwaters, pose different health impacts, and exhibit different treatment efficacies. Hexavalent chromium (Cr(VI)) has newly recognized human health concerns, and State and Federal agencies are evaluating a low Cr(VI)-specific maximum contaminant level (MCL) for drinking water. Occurrence of Cr and As in municipal drinking waters and industrial cooling tower waters was quantified by grab samples and compared with sampling results obtained from a new passive sampler developed specifically for Cr(VI). Cr(VI) and As concentrations in groundwater used for cooling tower make-up water concentrations were ~3 ppb and ~4 ppb, respectively, and were concentrated significantly in blowdown water (~20 ppb and ~40 ppb). Based upon pending Cr(VI), As, and other metal regulations, these blowdown waters will need routine monitoring and treatment. Cr(VI) concentrations in a water treatment plant (WTP) raw and finished water samples varied from 0.5 and 2 ppb for grab samples collected every 4 hours for 7 consecutive days using an ISCO sampler. The development of an ion exchange (IX) based passive sampler was validated in the field at the WTP and yielded an average exposure within 1 standard deviation of ISCO sampler grab data. Sampling at both the WTP and cooling towers suggested sources of Cr(III) from treatment chemicals or wood preservatives may exist. Since both facilities use chlorine oxidants, I quantified the apparent (pH=5) second-order rate constant for aqueous chlorine (HOCl/OCl-) with Cr(III) to form Cr(VI) as 0.7 M-1s-1. Under typical conditions (2 ppb Cr(III) ; 2 mg/L Cl2) the half-life for the conversion of Cr(III) to the more toxic form Cr(VI) is 4.7 hours. The occurrence studies in AZ and CA show the Cr(VI) and As treatment of groundwaters will be required to meet stringent Cr(VI) regulations. IX technologies, both strong base anion (SBA) and weak base anion (WBA) resin types were screened (and compared) for Cr removal. The SBA IX process for As removal was optimized by utilizing a reactive iron coagulation and filtration (RCF) process to treat spent IX brine, which was then reused to for SBA resin regeneration.
ContributorsBowen, Alexandra (Author) / Paul, Westerhoff K. (Thesis advisor) / Hristovski, Kiril (Committee member) / Halden, Rolf (Committee member) / Arizona State University (Publisher)
Created2014
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Description
With the projected population growth, the need to produce higher agricultural yield to meet projected demand is hindered by water scarcity. Out of many the approaches that could be implemented to meet the water gap, intensification of agriculture through adoption of advanced agricultural irrigation techniques is the focus for this

With the projected population growth, the need to produce higher agricultural yield to meet projected demand is hindered by water scarcity. Out of many the approaches that could be implemented to meet the water gap, intensification of agriculture through adoption of advanced agricultural irrigation techniques is the focus for this research. Current high water consumption by agricultural sector in Arizona is due to historical dominance in the state economy and established water rights. Efficiency gained in agricultural water use in Arizona has the most potential to reduce the overall water consumption. This research studies the agricultural sector and water management of several counties in Arizona (Maricopa, Pinal, and Yuma). Several research approaches are employed: modeling of agricultural technology adoption using replicator dynamics, interview with water managers and farmers, and Arizona water management law and history review. Using systems thinking, the components of the local farming environment are documented through socio-ecological system/robustness lenses. The replicator dynamics model is employed to evaluate possible conditions in which water efficient agricultural irrigation systems proliferate. The evaluation of conditions that promote the shift towards advanced irrigation technology is conducted through a combination of literature review, interview data, and model analysis. Systematic shift from the currently dominant flood irrigation toward a more water efficient irrigation technologies could be attributed to the followings: the increase in advanced irrigation technology yield efficiency; the reduction of advanced irrigation technology implementation and maintenance cost; the change in growing higher value crop; and the change in growing/harvesting time where there is less competition from other states. Insights learned will further the knowledge useful for this arid state's agricultural policy decision making that will both adhere to the water management goals and meet the projected food production and demand gap.
ContributorsBudiyanto, Yoshi (Author) / Muneepeerakul, Rachata (Thesis advisor) / Smith, Karen (Committee member) / Abbott, Joshua (Committee member) / Arizona State University (Publisher)
Created2014
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Description
The goal of the study was twofold: (i) to investigate the synthesis of hematite-impregnated granular activated carbon (Fe-GAC) by hydrolysis of Fe (III) and (ii) to assess the effectiveness of the fabricated media in removal of arsenic from water. Fe-GAC was synthesized by hydrolysis of Fe(III) salts under two Fe

The goal of the study was twofold: (i) to investigate the synthesis of hematite-impregnated granular activated carbon (Fe-GAC) by hydrolysis of Fe (III) and (ii) to assess the effectiveness of the fabricated media in removal of arsenic from water. Fe-GAC was synthesized by hydrolysis of Fe(III) salts under two Fe (III) initial dosages (0.5M and 2M) and two hydrolysis periods (24 hrs and 72 hrs). The iron content of the fabricated Fe-GAC media ranged from 0.9% to 4.4% Fe/g of the dry media. Pseudo-equilibrium batch test data at pH = 7.7±0.2 in 1mM NaHCO3 buffered ultrapure water and challenge groundwater representative of the Arizona Mexico border region were fitted to a Freundlich isotherm model. The findings suggested that the arsenic adsorption capacity of the metal (hydr)oxide modified GAC media is primarily controlled by the surface area of the media, while the metal content exhibited lesser effect. The adsorption capacity of the media in the model Mexican groundwater matrix was significantly lower for all adsorbent media. Continuous flow short bed adsorber tests (SBA) demonstrated that the adsorption capacity for arsenic in the challenge groundwater was reduced by a factor of 3 to 4 as a result of the mass transport effects. When compared on metal basis, the iron (hydr)oxide modified media performed comparably well as existing commercial media for treatment of arsenic. On dry mass basis, the fabricated media in this study removed less arsenic than their commercial counterparts because the metal content of the commercial media was significantly higher.
ContributorsJain, Arti (Author) / Hristovski, Kiril (Thesis advisor) / Olson, Larry (Committee member) / Madar, David (Committee member) / Edwards, David (Committee member) / Arizona State University (Publisher)
Created2011
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ABSTRACT Water resources in many parts of the world are subject to increasing stress because of (a) the growth in demand caused by population increase and economic development, (b) threats to supply caused by climate and land cover change, and (c) a heightened awareness of the importance of maintaining water

ABSTRACT Water resources in many parts of the world are subject to increasing stress because of (a) the growth in demand caused by population increase and economic development, (b) threats to supply caused by climate and land cover change, and (c) a heightened awareness of the importance of maintaining water supplies to other parts of the ecosystem. An additional factor is the quality of water management. The United States-Mexican border provides an example of poor water management combined with increasing demand for water resources that are both scarce and uncertain. This dissertation focuses on the problem of water management in the border city of Ciudad Juarez, Chihuahua. The city has attracted foreign investment during the last few decades, largely due to relatively low environmental and labor costs, and to a range of tax incentives and concessions. This has led to economic and population growth, but also to higher demand for public services such as water which leads to congestion and scarcity. In particular, as water resources have become scarce, the cost of water supply has increased. The dissertation analyzes the conditions that allow for the efficient use of water resources at sustainable levels of economic activity--i.e., employment and investment. In particular, it analyzes the water management strategies that lead to an efficient and sustainable use of water when the source of water is either an aquifer, or there is conjunctive use of ground and imported water. The first part of the dissertation constructs a model of the interactive effects of water supply, wage rates, inward migration of labor and inward investment of capital. It shows how growing water scarcity affects population growth through the impact it has on real wage rates, and how this erodes the comparative advantage of Ciudad Juarez--low wages--to the point where foreign investment stops. This reveals the very close connection between water management and the level of economic activity in Ciudad Juarez. The second part of the dissertation examines the effect of sustainable and efficient water management strategies on population and economic activity levels under two different settings. In the first Ciudad Juarez relies exclusively on ground water to meet demand--this reflects the current situation of Ciudad Juarez. In the second Ciudad Juarez is able both to import water and to draw on aquifers to meet demand. This situation is motivated by the fact that Ciudad Juarez is considering importing water from elsewhere to maintain its economic growth and mitigate the overdraft of the Bolson del Hueco aquifer. Both models were calibrated on data for Ciudad Juarez, and then used to run experiments with respect to different environmental and economic conditions, and different water management options. It is shown that for a given set of technological, institutional and environmental conditions, the way water is managed in a desert environment determines the long run equilibrium levels of employment, investment and output. It is also shown that the efficiency of water management is consistent with the sustainability of water use and economic activity. Importing water could allow the economy to operate at higher levels of activity than where it relies solely on local aquifers. However, at some scale, water availability will limit the level of economic activity, and the disposable income of the residents of Ciudad Juarez.
ContributorsGarduno Angeles, Gustavo Leopoldo (Author) / Perrings, Charles (Thesis advisor) / Holway, Jim (Thesis advisor) / Aggarwal, Rimjhim (Committee member) / Arizona State University (Publisher)
Created2011
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Description
The structural design of pavements in both highways and airfields becomes complex when one considers environmental effects and ground water table variation. Environmental effects have been incorporated on the new Mechanistic-Empirical Pavement Design Guide (MEPDG) but little has been done to incorporate environmental effects on airfield design. This work presents

The structural design of pavements in both highways and airfields becomes complex when one considers environmental effects and ground water table variation. Environmental effects have been incorporated on the new Mechanistic-Empirical Pavement Design Guide (MEPDG) but little has been done to incorporate environmental effects on airfield design. This work presents a developed code produced from this research study called ZAPRAM, which is a mechanistically based pavement model based upon Limiting Strain Criteria in airfield HMA pavement design procedures. ZAPRAM is capable of pavement and airfield design analyses considering environmental effects. The program has been coded in Visual Basic and implemented in an event-driven, user-friendly educational computer program, which runs in Excel environment. Several studies were conducted in order to insure the validity of the analysis as well as the efficiency of the software. The first study yielded the minimum threshold number of computational points the user should use at a specific depth within the pavement system. The second study was completed to verify the correction factor for the Odemark's transformed thickness equation. Default correction factors were included in the code base on a large comparative study between Odemark's and MLET. A third study was conducted to provide a comparison of flexible airfield pavement design thicknesses derived from three widely accepted design procedures used in practice today: the Asphalt Institute, Shell Oil, and the revised Corps of Engineering rutting failure criteria to calculate the thickness requirements necessary for a range of design input variables. The results of the comparative study showed that there is a significant difference between the pavement thicknesses obtained from the three design procedures, with the greatest deviation found between the Shell Oil approach and the other two criteria. Finally, a comprehensive sensitivity study of environmental site factors and the groundwater table depth upon flexible airfield pavement design and performance was completed. The study used the newly revised USACE failure criteria for subgrade shear deformation. The methodology utilized the same analytical methodology to achieve real time environmental effects upon unbound layer modulus, as that used in the new AASHTO MEPDG. The results of this effort showed, for the first time, the quantitative impact of the significant effects of the climatic conditions at the design site, coupled with the importance of the depth of the groundwater table, on the predicted design thicknesses. Significant cost savings appear to be quite reasonable by utilizing principles of unsaturated soil mechanics into the new airfield pavement design procedure found in program ZAPRAM.
ContributorsSalim, Ramadan A (Author) / Zapata, Claudia (Thesis advisor) / Witczak, Matthew (Thesis advisor) / Kaloush, Kamil (Committee member) / Arizona State University (Publisher)
Created2011
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Description
Arsenic (As) is a naturally occurring element that poses a health risk when continually consumed at levels exceeding the Environmental Protection Agencies (EPA) maximum contaminant level (MCL) of 10 ppb. With the Arizona Department of Water Resources considering reliance on other sources of water other than just solely surface water,

Arsenic (As) is a naturally occurring element that poses a health risk when continually consumed at levels exceeding the Environmental Protection Agencies (EPA) maximum contaminant level (MCL) of 10 ppb. With the Arizona Department of Water Resources considering reliance on other sources of water other than just solely surface water, groundwater proves a reliable, supplemental source. The Salt River Project (SRP) wants to effectively treat their noncompliance groundwater sources to meet EPA compliance. Rapid small-scale column tests (RSSCTs) of two SRP controlled groundwater wells along the Eastern Canal and Consolidated Canal were designed to assist SRP in selection and future design of full-scale packed bed adsorbent media. Main concerns for column choice is effectiveness, design space at groundwater wells, and simplicity. Two adsorbent media types were tested for effective treatment of As to below the MCL: a synthetic iron oxide, Bayoxide E33, and a strong base anion exchange resin, SBG-1. Both media have high affinity toward As and prove effective at treating As from these groundwater sources. Bayoxide E33 RSSCT performance indicated that As treatment lasted to near 60,000 bed volumes (BV) in both water sources and still showed As adsorption extending past this operation ranging from several months to a year. SBG-1 RSSCT performance indicated As, treatment lasted to 500 BV, with the added benefit of being regenerated. At 5%, 13%, and 25% brine regeneration concentrations, regeneration showed that 5% brine is effective, yet would complicate overall design and footprint. Bayoxide E33 was selected as the best adsorbent media for SRP use in full-scale columns at groundwater wells due to its simplistic design and high efficiency.
ContributorsLesan, Dylan (Author) / Westerhoff, Paul (Thesis advisor) / Hristovski, Kiril (Committee member) / Fraser, Matthew (Committee member) / Arizona State University (Publisher)
Created2015
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Description
Population growth within drylands is occurring faster than growth in any other ecologic zone, putting pressure on already stressed water resources. Because the availability of surface water supplies in drylands tends to be highly variable, many of these populations rely on groundwater. A critical process contributing to groundwater recharge is

Population growth within drylands is occurring faster than growth in any other ecologic zone, putting pressure on already stressed water resources. Because the availability of surface water supplies in drylands tends to be highly variable, many of these populations rely on groundwater. A critical process contributing to groundwater recharge is the interaction between ephemeral channels and groundwater aquifers. Generally, it has been found that ephemeral channels contribute to groundwater recharge when streamflow infiltrates into the sandy bottoms of channels. This process has traditionally been studied in channels that drain large areas (10s to 100s km2). In this dissertation, I study the interactions between surface water and groundwater via ephemeral channels in a first-order watershed located on an arid piedmont slope within the Jornada Experimental Range (JER) in the Chihuahuan Desert. To achieve this, I utilize a combination of high-resolution observations and computer simulations using a modified hydrologic model to quantify groundwater recharge and shed light on the geomorphic and ecologic processes that affect the rate of recharge. Observational results indicate that runoff generated within the piedmont slope contributes significantly to deep percolation. During the short-term (6 yr) study period, we estimated 385 mm of total percolation, 62 mm/year, or a ratio of percolation to rainfall of 0.25. Based on the instrument network, we identified that percolation occurs inside channel areas when these receive overland sheetflow from hillslopes. By utilizing a modified version of the hydrologic model, TIN-based Real-time Integrated Basin Simulator (tRIBS), that was calibrated and validated using the observational dataset, I quantified the effects of changing watershed properties on groundwater recharge. Distributed model simulations quantify how deep percolation is produced during the streamflow generation process, and indicate that it plays a significant role in moderating the production of streamflow. Sensitivity analyses reveal that hillslope properties control the amount of rainfall necessary to initiate percolation while channel properties control the partitioning of hillslope runoff into streamflow and deep percolation. Synthetic vegetation experiments show that woody plant encroachment leads to increases in both deep percolation and streamflow. Further woody plant encroachment may result in the unexpected enhancement of dryland aquifer sustainability.
ContributorsSchreiner-McGraw, Adam P (Author) / Vivoni, Enrique R. (Thesis advisor) / Whipple, Kelin X. (Committee member) / Mascaro, Giuseppe (Committee member) / Throop, Heather L. (Committee member) / Sala, Osvaldo E. (Committee member) / Arizona State University (Publisher)
Created2017