Matching Items (19)
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- All Subjects: Environmental engineering
- Creators: Halden, Rolf U.
- Creators: Fraser, Matthew
- Member of: ASU Electronic Theses and Dissertations
Description
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
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, 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
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 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
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 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
Analysis and modeling of residual compounds in process streams from U.S. wastewater treatment plants
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 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
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, 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
Description
Vapor intrusion (VI), can pose health risks to building occupants. Assessment and mitigation at VI impacted sites have been guided by a site conceptual model (SCM) in which vapors originate from subsurface sources, diffuse through soil matrix and enter into a building by gas flow across foundation cracks. Alternative VI pathways and groundwater table fluctuations are not often considered.
Alternative VI pathways, involving vapor transport along sewer lines and other subsurface infrastructure, have recently been found to be significant contributors to VI impacts at some sites. This study evaluated approaches for identifying and characterizing the significance of alternative VI pathways and assessed the effectiveness of conventional mitigation at a site with an alternative VI pathway that can be manipulated to be on or off. The alternative pathway could not be identified using conventional pathway assessment procedures and can only be discovered under controlled pressure method (CPM) conditions. Measured emission rates were two orders of magnitude greater than screening model estimates and sub-foundation vertical soil gas profiles changed and were no longer consistent with the conventional VI conceptual model when the CPM test was conducted. The pipe flow VI pathway reduced the vacuum performance of the sub-slab depressurization (SSD) VI mitigation system, but the SSD system still provided sufficient protection to the house.
The relationship between groundwater table fluctuations and subsurface vapor emissions and transport is examined using multi-year data from the field site, and is studied in the laboratory. In addition, a broader range of conditions is examined through use of modeling validated with the experimental data. The results indicate that fluctuating groundwater tables will lead to amplified volatile organic chemical (VOC) emissions from groundwater to soil surface relative to steady water table elevation, however, the magnitude of this amplification is less concerned when long-term water fluctuation present. No clear correlations were found between VOC emissions and water table changes at the study site where annual water table fluctuations of about 0.3 m existed. Significant VOC emission amplifications by water table fluctuation would be expected under shallow groundwater conditions according to model analysis results.
Alternative VI pathways, involving vapor transport along sewer lines and other subsurface infrastructure, have recently been found to be significant contributors to VI impacts at some sites. This study evaluated approaches for identifying and characterizing the significance of alternative VI pathways and assessed the effectiveness of conventional mitigation at a site with an alternative VI pathway that can be manipulated to be on or off. The alternative pathway could not be identified using conventional pathway assessment procedures and can only be discovered under controlled pressure method (CPM) conditions. Measured emission rates were two orders of magnitude greater than screening model estimates and sub-foundation vertical soil gas profiles changed and were no longer consistent with the conventional VI conceptual model when the CPM test was conducted. The pipe flow VI pathway reduced the vacuum performance of the sub-slab depressurization (SSD) VI mitigation system, but the SSD system still provided sufficient protection to the house.
The relationship between groundwater table fluctuations and subsurface vapor emissions and transport is examined using multi-year data from the field site, and is studied in the laboratory. In addition, a broader range of conditions is examined through use of modeling validated with the experimental data. The results indicate that fluctuating groundwater tables will lead to amplified volatile organic chemical (VOC) emissions from groundwater to soil surface relative to steady water table elevation, however, the magnitude of this amplification is less concerned when long-term water fluctuation present. No clear correlations were found between VOC emissions and water table changes at the study site where annual water table fluctuations of about 0.3 m existed. Significant VOC emission amplifications by water table fluctuation would be expected under shallow groundwater conditions according to model analysis results.
ContributorsGuo, Yuanming (Author) / Johnson, Paul C (Thesis advisor) / Fraser, Matthew (Committee member) / Westerhoff, Paul (Committee member) / Arizona State University (Publisher)
Created2015
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 (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
Description
Vapor intrusion (VI) pathway assessment often involves the collection and analysis of groundwater, soil gas, and indoor air data. There is temporal variability in these data, but little is understood about the characteristics of that variability and how it influences pathway assessment decision-making. This research included the first-ever collection of a long-term high-frequency indoor air data set at a house with VI impacts overlying a dilute chlorinated solvent groundwater plume. It also included periodic synoptic snapshots of groundwater and soil gas data and high-frequency monitoring of building conditions and environmental factors. Indoor air trichloroethylene (TCE) concentrations varied over three orders-of-magnitude under natural conditions, with the highest daily VI activity during fall, winter, and spring months. These data were used to simulate outcomes from common sampling strategies, with the result being that there was a high probability (up to 100%) of false-negative decisions and poor characterization of long-term exposure. Temporal and spatial variability in subsurface data were shown to increase as the sampling point moves from source depth to ground surface, with variability of an order-of-magnitude or more for sub-slab soil gas. It was observed that indoor vapor sources can cause subsurface vapor clouds and that it can take days to weeks for soil gas plumes created by indoor sources to dissipate following indoor source removal. A long-term controlled pressure method (CPM) test was conducted to assess its utility as an alternate approach for VI pathway assessment. Indoor air concentrations were similar to maximum concentrations under natural conditions (9.3 μg/m3 average vs. 13 μg/m3 for 24 h TCE data) with little temporal variability. A key outcome was that there were no occurrences of false-negative results. Results suggest that CPM tests can produce worst-case exposure conditions at any time of the year. The results of these studies highlight the limitations of current VI pathway assessment approaches and demonstrate the need for robust alternate diagnostic tools, such as CPM, that lead to greater confidence in data interpretation and decision-making.
ContributorsHolton, Chase Weston (Author) / Johnson, Paul C (Thesis advisor) / Fraser, Matthew (Committee member) / Forzani, Erica (Committee member) / Arizona State University (Publisher)
Created2015
Description
Up to 25 percent of the operating budget for contaminated site restoration projects is spent on site characterization, including long-term monitoring of contaminant concentrations. The sensitivity, selectivity, and reproducibility of analytical methods have improved to the point where sampling techniques bear the primary responsibility for the accuracy and precision of the data. Most samples represent discrete concentrations in time and space; with sampling points frequently limited in both dimensions, sparse data sets are heavily extrapolated and the quality of data further limited.
Methods are presented for characterizing contaminants in water (groundwater and surface waters) and indoor air. These techniques are integrative, providing information averaged over time and/or space, as opposed to instantaneous point measurements. Contaminants are concentrated from the environment, making these methods applicable to trace contaminants. These methods have the potential to complement existing techniques, providing the practitioner with opportunities to reduce costs and improve the quality of the data used in decision making.
A conceptual model for integrative sampling of environmental waters is developed and a literature review establishes an advantage in precision for active samplers. A programmable sampler was employed to measure the concentration of chromate in a shallow aquifer exhibiting time-dependent contaminant concentrations, providing a unique data set and sustainability benefits. The analysis of heat exchanger condensate, a waste stream generated by air conditioning, is demonstrated in a non-intrusive method for indoor air quality assessment. In sum, these studies present new opportunities for effective, sustainable environmental characterization.
Methods are presented for characterizing contaminants in water (groundwater and surface waters) and indoor air. These techniques are integrative, providing information averaged over time and/or space, as opposed to instantaneous point measurements. Contaminants are concentrated from the environment, making these methods applicable to trace contaminants. These methods have the potential to complement existing techniques, providing the practitioner with opportunities to reduce costs and improve the quality of the data used in decision making.
A conceptual model for integrative sampling of environmental waters is developed and a literature review establishes an advantage in precision for active samplers. A programmable sampler was employed to measure the concentration of chromate in a shallow aquifer exhibiting time-dependent contaminant concentrations, providing a unique data set and sustainability benefits. The analysis of heat exchanger condensate, a waste stream generated by air conditioning, is demonstrated in a non-intrusive method for indoor air quality assessment. In sum, these studies present new opportunities for effective, sustainable environmental characterization.
ContributorsRoll, Isaac B (Author) / Halden, Rolf U. (Thesis advisor) / Johnson, Paul C (Committee member) / Kavazanjian, Edward (Committee member) / Arizona State University (Publisher)
Created2015