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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
DehaloR^2 is a previously characterized, trichloroethene (TCE)-dechlorinating culture and contains bacteria from the known dechlorinating genus, Dehalococcoides. DehaloR^2 was exposed to three anthropogenic contaminants, Triclocarban (TCC), tris(2-chloroethyl) phosphate (TCEP), and 1,1,1-trichloroethane (TCA) and two biogenic-like halogenated compounds, 2,6-dibromophenol (2,6-DBP) and 2,6-dichlorophenol (2,6-DCP). The effects on TCE dechlorination ability due to 2,6-DBP and 2,6-DCP exposures were also investigated. DehaloR^2 did not dechlorinate TCC or TCEP. After initial exposure to TCA, half of the initial TCA was dechlorinated to 1,1-dichloroethane (DCA), however half of the TCA remained by day 100. Subsequent TCA and TCE re-exposure showed no reductive dechlorination activity for both TCA and TCE by 120 days after the re-exposure. It has been hypothesized that the microbial TCE-dechlorinating ability was developed before TCE became abundant in groundwater. This dechlorinating ability would have existed in the microbial metabolism due to previous exposure to biogenic halogenated compounds. After observing the inability of DehaloR^2 to dechlorinate other anthropogenic compounds, DehaloR^2 was then exposed to two naturally occurring halogenated phenols, 2,6-DBP and 2,6-DCP, in the presence and absence of TCE. DehaloR^2 debrominated 2,6-DBP through the intermediate 2-bromophenol (2-BP) to the end product phenol faster in the presence of TCE. DehaloR^2 dechlorinated 2,6-DCP to 2-CP in the absence of TCE; however, 2,6-DCP dechlorination was incomplete in the presence of TCE. Additionally, when 2,6-DBP was present, complete TCE dechlorination to ethene occurred more quickly than when TCE was present without 2,6-DBP. However, when 2,6-DCP was present, TCE dechlorination to ethene had not completed by day 55. The increased dehalogenation rate of 2,6-DBP and TCE when present together compared to conditions containing only 2,6-DBP or only TCE suggests a possible synergistic relationship between 2,6-DBP and TCE, while the decreased dechlorination rate of 2,6-DCP and TCE when present together compared to conditions containing only 2,6-DCP or only TCE suggests an inhibitory effect.
ContributorsKegerreis, Kylie (Author) / Krajmalnik-Brown, Rosa (Thesis advisor) / Halden, Rolf U. (Committee member) / Torres, César I (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
The overall goal of this dissertation is to advance understanding of biofilm reduction of oxidized contaminants in water and wastewater. Chapter 1 introduces the fundamentals of biological reduction of three oxidized contaminants (nitrate, perchlorate, and trichloriethene (TCE)) using two biofilm processes (hydrogen-based membrane biofilm reactors (MBfR) and packed-bed heterotrophic reactors (PBHR)), and it identifies the research objectives. Chapters 2 through 6 focus on nitrate removal using the MBfR and PBHR, while chapters 7 through 10 investigate simultaneous reduction of nitrate and another oxidized compound (perchlorate, sulfate, or TCE) in the MBfR. Chapter 11 summarizes the major findings of this research. Chapters 2 and 3 demonstrate nitrate removal in a groundwater and identify the maximum nitrate loadings using a pilot-scale MBfR and a pilot-scale PBHR, respectively. Chapter 4 compares the MBfR and the PBHR for denitrification of the same nitrate-contaminated groundwater. The comparison includes the maximum nitrate loading, the effluent water quality of the denitrification reactors, and the impact of post-treatment on water quality. Chapter 5 theoretically and experimentally demonstrates that the nitrate biomass-carrier surface loading, rather than the traditionally used empty bed contact time or nitrate volumetric loading, is the primary design parameter for heterotrophic denitrification. Chapter 6 constructs a pH-control model to predict pH, alkalinity, and precipitation potential in heterotrophic or hydrogen-based autotrophic denitrification reactors. Chapter 7 develops and uses steady-state permeation tests and a mathematical model to determine the hydrogen-permeation coefficients of three fibers commonly used in the MBfR. The coefficients are then used as inputs for the three models in Chapters 8-10. Chapter 8 develops a multispecies biofilm model for simultaneous reduction of nitrate and perchlorate in the MBfR. The model quantitatively and systematically explains how operating conditions affect nitrate and perchlorate reduction and biomass distribution via four mechanisms. Chapter 9 modifies the nitrate and perchlorate model into a nitrate and sulfate model and uses it to identify operating conditions corresponding to onset of sulfate reduction. Chapter 10 modifies the nitrate and perchlorate model into a nitrate and TCE model and uses it to investigate how operating conditions affect TCE reduction and accumulation of TCE reduction intermediates.
ContributorsTang, Youneng (Author) / Rittmann, Bruce E. (Thesis advisor) / Westerhoff, Paul (Committee member) / Krajmalnik-Brown, Rosa (Committee member) / Halden, Rolf (Committee member) / Arizona State University (Publisher)
Created2012
Description
Phytoplankton comprise the base of the marine food web, and, along with heterotrophic protists, they are key players in the biological pump that transports carbon from the surface to the deep ocean. In the world's subtropical oligotrophic gyres, plankton communities exhibit strong seasonality. Winter storms vent deep water into the euphotic zone, triggering a surge in primary productivity in the form of a spring phytoplankton bloom. Although the hydrographic trends of this "boom and bust" cycle have been well studied for decades, community composition and its seasonal and annual variability remains an integral subject of research. It is hypothesized here that proportions of different phytoplankton and protistan taxa vary dramatically between seasons and years, and that picoplankton represent an important component of this community and contributor to carbon in the surface ocean. Monthly samples from the Bermuda Atlantic Time-series Study (BATS) site were analyzed by epifluorescence microscopy, which permits classification by morphology, size, and trophic type. Epifluorescence counts were supplemented with flow cytometric quantification of Synechococcus, Prochlorococcus, and autotrophic pico- and nanoeukaryotes. Results from this study indicate Synechococcus and Prochlorococcus, prymnesiophytes, and hetero- and mixotrophic nano- and dinoflagellates were the major players in the BATS region plankton community. Ciliates, cryptophytes, diatoms, unidentified phototrophs, and other taxa represented rarer groups. Both flow cytometry and epifluorescence microscopy revealed Synechococcus to be most prevalent during the spring bloom. Prymnesiophytes likewise displayed distinct seasonality, with the highest concentrations again being noted during the bloom. Heterotrophic nano- and dinoflagellates, however, were most common in fall and winter. Mixotrophic dinoflagellates, while less abundant than their heterotrophic counterparts, displayed similar seasonality. A key finding of this study was the interannual variability revealed between the two years. While most taxa were more abundant in the first year, prymnesiophytes experienced much greater abundance in the second year bloom. Analyses of integrated carbon revealed further stark contrasts between the two years, both in terms of total carbon and the contributions of different groups. Total integrated carbon varied widely in the first study year but displayed less fluctuation after June 2009, and values were noticeably reduced in the second year.
ContributorsHansen, Amy (Author) / Neuer, Susanne (Thesis advisor) / Krajmalnik-Brown, Rosa (Committee member) / Sommerfeld, Milton (Committee member) / Arizona State University (Publisher)
Created2010
Characterization and Manipulation of Microbiomes From Arid Landfills for Improved Methane Production
Description
Environmentally harmful byproducts from solid waste’s decomposition, including methane (CH4) emissions, are managed through standardized landfill engineering and gas-capture mechanisms. Yet only a limited number of studies have analyzed the development and composition of Bacteria and Archaea involved in CH4 production from landfills. The objectives of this research were to compare microbiomes and bioactivity from CH4-producing communities in contrasting spatial areas of arid landfills and to tests a new technology to biostimulate CH4 production (methanogenesis) from solid waste under dynamic environmental conditions controlled in the laboratory. My hypothesis was that the diversity and abundance of methanogenic Archaea in municipal solid waste (MSW), or its leachate, play an important role on CH4 production partially attributed to the group’s wide hydrogen (H2) consumption capabilities. I tested this hypothesis by conducting complementary field observations and laboratory experiments. I describe niches of methanogenic Archaea in MSW leachate across defined areas within a single landfill, while demonstrating functional H2-dependent activity. To alleviate limited H2 bioavailability encountered in-situ, I present biostimulant feasibility and proof-of-concepts studies through the amendment of zero valent metals (ZVMs). My results demonstrate that older-aged MSW was minimally biostimulated for greater CH4 production relative to a control when exposed to iron (Fe0) or manganese (Mn0), due to highly discernable traits of soluble carbon, nitrogen, and unidentified fluorophores found in water extracts between young and old aged, starting MSW. Acetate and inhibitory H2 partial pressures accumulated in microcosms containing old-aged MSW. In a final experiment, repeated amendments of ZVMs to MSW in a 600 day mesocosm experiment mediated significantly higher CH4 concentrations and yields during the first of three ZVM injections. Fe0 and Mn0 experimental treatments at mesocosm-scale also highlighted accelerated development of seemingly important, but elusive Archaea including Methanobacteriaceae, a methane-producing family that is found in diverse environments. Also, prokaryotic classes including Candidatus Bathyarchaeota, an uncultured group commonly found in carbon-rich ecosystems, and Clostridia; All three taxa I identified as highly predictive in the time-dependent progression of MSW decomposition. Altogether, my experiments demonstrate the importance of H2 bioavailability on CH4 production and the consistent development of Methanobacteriaceae in productive MSW microbiomes.
ContributorsReynolds, Mark Christian (Author) / Cadillo-Quiroz, Hinsby (Thesis advisor) / Krajmalnik-Brown, Rosa (Thesis advisor) / Wang, Xuan (Committee member) / Kavazanjian, Edward (Committee member) / Arizona State University (Publisher)
Created2022
Description
Monitoring human exposure to chemicals posing public health threats is critically important for risk management and for informing regulatory actions. Chemical threats result from both environmental pollutants and elected substance use (e.g., consumption of drugs, alcohol and tobacco). Measuring chemical occurrence and concentrations in environmental matrices can help to pinpoint human exposure routes. For instance, indoor dust, a sink of indoor environmental contaminants, can serve to assess indoor air contamination and associated human exposures. Urban wastewater arriving at treatment plants contains urine and stool from the general population, the analysis of which can provide information on chemical threats in the community and ongoing harmful exposures. Analysis of sewage sludge can serve to reveal the identity and quantity of persistent organic pollutants in cities and inform estimates of toxic body burdens in local populations.
The objective of this dissertation was to investigate the occurrence and quantity of select, potentially harmful, anthropogenic chemicals in various environmental matrices and to explore the diagnostic value of analytical assays for informing public health decision-making. This dissertation (i) is the first to report spatio-temporal variations and estrogenic burdens of five parabens in sewage sludge from at the U.S. nationwide scale; (ii) represents the first China-wide survey to assess the occurrence and toxic emissions of parabens, triclosan, triclocarban, as well as triclocarban metabolites and transformation products contained in Chinese sewage sludge; (iii) documents the first use of a dispersive solid phase extraction method for indoor dust to measure dust-borne parabens, triclosan and triclocarban and estimating associated human exposures from dust ingestion; and (iv) is the first U.S. study to assess population-level alcohol and nicotine consumption in three U.S. communities using wastewater-based epidemiology (WBE). Obtained data on baseline levels of selected emerging contaminants in sewage sludge and indoor dust can serve to inform the future monitoring needs, risk assessment, and policy making. This work showcases the utility of WBE and urban metabolism metrology via dust and sewage sludge analysis to assess human behavior (e.g., drinking and smoking) and exposure risks more rapidly, efficiently and anonymously than traditional approaches can.
The objective of this dissertation was to investigate the occurrence and quantity of select, potentially harmful, anthropogenic chemicals in various environmental matrices and to explore the diagnostic value of analytical assays for informing public health decision-making. This dissertation (i) is the first to report spatio-temporal variations and estrogenic burdens of five parabens in sewage sludge from at the U.S. nationwide scale; (ii) represents the first China-wide survey to assess the occurrence and toxic emissions of parabens, triclosan, triclocarban, as well as triclocarban metabolites and transformation products contained in Chinese sewage sludge; (iii) documents the first use of a dispersive solid phase extraction method for indoor dust to measure dust-borne parabens, triclosan and triclocarban and estimating associated human exposures from dust ingestion; and (iv) is the first U.S. study to assess population-level alcohol and nicotine consumption in three U.S. communities using wastewater-based epidemiology (WBE). Obtained data on baseline levels of selected emerging contaminants in sewage sludge and indoor dust can serve to inform the future monitoring needs, risk assessment, and policy making. This work showcases the utility of WBE and urban metabolism metrology via dust and sewage sludge analysis to assess human behavior (e.g., drinking and smoking) and exposure risks more rapidly, efficiently and anonymously than traditional approaches can.
ContributorsChen, Jing (Author) / Halden, Rolf U. (Thesis advisor) / Borges, Chad R (Committee member) / Abbaszadegan, Morteza (Committee member) / Arizona State University (Publisher)
Created2018
Description
This dissertation critically evaluated methodologies and devices for assessing and protecting the health of human populations, with particular emphasis on groundwater remediation and the use of wastewater-based epidemiology (WBE) to inform population health. A meta-analysis and assessment of laboratory-scale treatability studies for removing chlorinated solvents from groundwater found that sediment microcosms operated as continuous-flow columns are preferable to batch bottles when seeking to emulate with high fidelity the complex conditions prevailing in the subsurface in contaminated aquifers (Chapter 2). Compared to monitoring at the field-scale, use of column microcosms also showed (i) improved chemical speciation, and (ii) qualitative predictability of field parameters (Chapter 3). Monitoring of glucocorticoid hormones in wastewater of a university campus showed (i) elevated stress levels particularly at the start of the semester, (ii) on weekdays relative to weekend days (p = 0.05) (161 ± 42 μg d-1 per person, 122 ± 54 μg d-1 per person; p ≤ 0.05), and (iii) a positive association between levels of stress hormones and nicotine (rs: 0.49) and caffeine (0.63) consumption in this student population (Chapter 4). Also, (i) alcohol consumption determined by WBE was in line with literature estimates for this young sub-population (11.3 ± 7.5 g d-1 per person vs. 10.1 ± 0.8 g d-1 per person), whereas caffeine and nicotine uses were below (114 ± 49 g d-1 per person, 178 ± 19 g d-1 per person; 627 ± 219 g d-1 per person, 927 ± 243 g d-1 per person). The introduction of a novel continuous in situ sampler to WBE brought noted benefits relative to traditional time-integrated sampling, including (i) a higher sample coverage (93% vs. 3%), (ii) an ability to captured short-term analyte pulses (e.g., heroin, fentanyl, norbuprenorphine, and methadone), and (iii) an overall higher mass capture for drugs of abuse like morphine, fentanyl, methamphetamine, amphetamine, and the opioid antagonist metabolite norbuprenorphine (p ≤ 0.01). Methods and devices developed in this work are poised to find applications in the remediation sector and in human health assessments.
ContributorsDriver, Erin Michelle (Author) / Halden, Rolf (Thesis advisor) / Conroy-Ben, Otakuye (Committee member) / Kavazanjian, Edward (Committee member) / Krajmalnik-Brown, Rosa (Committee member) / Arizona State University (Publisher)
Created2018
Description
The occurrence of micro-and nanoplastic (MNP) debris in the environment is a research area of considerable public health concern. Various combinations of methods for extraction, isolation, and quantification of MNP have been applied but literature studies evaluating the appropriateness and efficacy of these protocols are lacking. A meta-analysis of the literature (n=134; years 2010-2017) was conducted to inventory and assess the appropriateness of methodologies employed. Some 30.6% of studies employed visual identification only, which carried a calculated misidentification error of 25.8-74.2%. An additional 6.7% of studies reported counts for particles smaller than the cutoff value of the selected collection pore size, and 9.7% of studies utilized extraction solution densities which exclude some of the polymers commonly occurring in the environments investigated. A composite value of data vulnerability of 43.3% was determined for the sample, indicating considerable weaknesses in the robustness of information available on MNP occurrence and type. Additionally, the oxidizing solutions documented in the literature frequently were deemed unsuccessful in removing interfering organic matter. Whereas nanoplastics measuring <1 µm in diameter are likely principal drivers of health risk, polymer fragments reported on in the literature are much larger, measuring 10+ µm in diameter due to lack of standardized methods. Thus, current inventories of MNP in the environmental MNP feature data quality concerns that should be addressed moving forward by using more robust and standardized techniques for sampling, processing and polymer identification to improve data quality and avoid the risk of misclassification.
ContributorsCook, Cayla R (Author) / Halden, Rolf U. (Thesis advisor) / Hamilton, Kerry (Committee member) / Mascaro, Giuseppe (Committee member) / Arizona State University (Publisher)
Created2018
Description
This dissertation focused on the development and application of state-of-the-art monitoring tools and analysis methods for tracking the fate of trace level contaminants in the natural and built water environments, using fipronil as a model; fipronil and its primary degradates (known collectively as fiproles) are among a group of trace level emerging environmental contaminants that are extremely potent arthropodic neurotoxins. The work further aimed to fill in data gaps regarding the presence and fate of fipronil in engineered water systems, specifically in a wastewater treatment plant (WWTP), and in an engineered wetland. A review of manual and automated “active” water sampling technologies motivated the development of two new automated samplers capable of in situ biphasic extraction of water samples across the bulk water/sediment interface of surface water systems. Combined with an optimized method for the quantification of fiproles, the newly developed In Situ Sampler for Biphasic water monitoring (IS2B) was deployed along with conventional automated water samplers, to study the fate and occurrence of fiproles in engineered water environments; continuous sampling over two days and subsequent analysis yielded average total fiprole concentrations in wetland surface water (9.9 ± 4.6 to 18.1 ± 4.6 ng/L) and wetland sediment pore water (9.1 ± 3.0 to 12.6 ± 2.1 ng/L). A mass balance of the WWTP located immediately upstream demonstrated unattenuated breakthrough of total fiproles through the WWTP with 25 ± 3 % of fipronil conversion to degradates, and only limited removal of total fiproles in the wetland (47 ± 13%). Extrapolation of local emissions (5–7 g/d) suggests nationwide annual fiprole loadings from WWTPs to U.S. surface waters on the order of about one half to three quarters of a metric tonne. The qualitative and quantitative data collected in this work have regulatory implications, and the sampling tools and analysis strategies described in this thesis have broad applicability in the assessment of risks posed by trace level environmental contaminants.
ContributorsSupowit, Samuel (Author) / Halden, Rolf U. (Thesis advisor) / Westerhoff, Paul (Committee member) / Johnson, Paul C (Committee member) / Arizona State University (Publisher)
Created2015