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- All Subjects: Environmental sciences
- Creators: Krajmalnik-Brown, Rosa
- Creators: Fraser, Matthew
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
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
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
Atmospheric deposition of iron (Fe) can limit primary productivity and carbon dioxide uptake in some marine ecosystems. Recent modeling studies suggest that biomass burning aerosols may contribute a significant amount of soluble Fe to the surface ocean. Existing studies of burn-induced trace element mobilization have often collected both entrained soil particles along with material from biomass burning, making it difficult to determine the actual source of aerosolized trace metals.
In order to better constrain the importance of biomass versus entrained soil as a source of trace metals in burn aerosols, small-scale burn experiments were conducted using soil-free foliage representative of a variety of fire-impacted ecosystems. The resulting burn aerosols were collected in two stages (PM > 2.5 μm and PM < 2.5 μm) on cellulose filters using a high-volume air sampler equipped with an all-Teflon impactor. Unburned foliage and burn aerosols were analyzed for Fe and other trace metals using inductively coupled plasma mass spectrometry (ICP-MS).
Results of this analysis show that less than 2% of Fe in plant biomass is likely mobilized as atmospheric aerosols during biomass burning events. The results of this study and estimates of annual global wildfire area were used to estimate the impact of biomass burning aerosols on total atmospheric Fe flux to the ocean. I estimate that foliage-derived Fe contributes 114 ± 57 Gg annually. Prior studies, which implicitly include both biomass and soil-derived Fe, concluded that biomass burning contributes approximately 690 Gg of Fe. Together, these studies suggest that fire-entrained soil particles contribute 83% (576 Gg) of Fe in biomass burning emissions, while plant derived iron only accounts for at most 17%.
In order to better constrain the importance of biomass versus entrained soil as a source of trace metals in burn aerosols, small-scale burn experiments were conducted using soil-free foliage representative of a variety of fire-impacted ecosystems. The resulting burn aerosols were collected in two stages (PM > 2.5 μm and PM < 2.5 μm) on cellulose filters using a high-volume air sampler equipped with an all-Teflon impactor. Unburned foliage and burn aerosols were analyzed for Fe and other trace metals using inductively coupled plasma mass spectrometry (ICP-MS).
Results of this analysis show that less than 2% of Fe in plant biomass is likely mobilized as atmospheric aerosols during biomass burning events. The results of this study and estimates of annual global wildfire area were used to estimate the impact of biomass burning aerosols on total atmospheric Fe flux to the ocean. I estimate that foliage-derived Fe contributes 114 ± 57 Gg annually. Prior studies, which implicitly include both biomass and soil-derived Fe, concluded that biomass burning contributes approximately 690 Gg of Fe. Together, these studies suggest that fire-entrained soil particles contribute 83% (576 Gg) of Fe in biomass burning emissions, while plant derived iron only accounts for at most 17%.
ContributorsSherry, Alyssa M (Author) / Anbar, Ariel D (Thesis advisor) / Herckes, Pierre (Thesis advisor) / Hartnett, Hilairy E (Committee member) / Fraser, Matthew (Committee member) / Arizona State University (Publisher)
Created2019
Description
Obesity is a worldwide epidemic accompanied by multiple comorbidities. Bariatric surgery is currently the most efficient treatment for morbid obesity and its comorbidities. The etiology of obesity is unknown, although genetic, environmental, and most recently, microbiome elements have been recognized as contributors to this rising epidemic. The role of the gut microbiome in weight-loss or weight-gain warrants investigation, and bariatric surgery provides a good model to study influences of the microbiome on host metabolism. The underlying goals of my research were to analyze (i) the factors that change the microbiome after bariatric surgery, (ii) the effects of different types of bariatric surgeries on the gut microbiome and metabolism, (iii) the role of the microbiome on the success of bariatric surgery, and (iv) temporal and spatial changes of the microbiome after bariatric surgery.
Roux-en-Y gastric bypass (RYGB) rearranges the gastrointestinal tract and reduces gastric acid secretions. Therefore, pH could be one of the factors that change microbiome after RYGB. Using mixed-cultures and co-cultures of species enriched after RYGB, I showed that as small as 0.5 units higher gut pH can aid in the survival of acid-sensitive microorganisms after RYGB and alter gut microbiome function towards the production of weight loss-associated metabolites. By comparing microbiome after two different bariatric surgeries, RYGB and laparoscopic adjustable gastric banding (LAGB), I revealed that gut microbiome structure and metabolism after RYGB are remarkably different than LAGB, and LAGB change microbiome minimally. Given the distinct RYGB alterations to the microbiome, I examined the contribution of the microbiome to weight loss. Analyses revealed that Fusobacterium might lessen the success of RYGB by producing putrescine, which may enhance weight-gain and could serve as biomarker for unsuccessful RYGB.
Finally, I showed that RYGB alters the luminal and the mucosal microbiome. Changes in gut microbial metabolic products occur in the short-term and persist over the long-term. Overall, the work in this dissertation provides insight into how the gut microbiome structure and function is altered after bariatric surgery, and how these changes potentially affect the host metabolism. These findings will be helpful in subsequent development of microbiome-based therapeutics to treat obesity.
Roux-en-Y gastric bypass (RYGB) rearranges the gastrointestinal tract and reduces gastric acid secretions. Therefore, pH could be one of the factors that change microbiome after RYGB. Using mixed-cultures and co-cultures of species enriched after RYGB, I showed that as small as 0.5 units higher gut pH can aid in the survival of acid-sensitive microorganisms after RYGB and alter gut microbiome function towards the production of weight loss-associated metabolites. By comparing microbiome after two different bariatric surgeries, RYGB and laparoscopic adjustable gastric banding (LAGB), I revealed that gut microbiome structure and metabolism after RYGB are remarkably different than LAGB, and LAGB change microbiome minimally. Given the distinct RYGB alterations to the microbiome, I examined the contribution of the microbiome to weight loss. Analyses revealed that Fusobacterium might lessen the success of RYGB by producing putrescine, which may enhance weight-gain and could serve as biomarker for unsuccessful RYGB.
Finally, I showed that RYGB alters the luminal and the mucosal microbiome. Changes in gut microbial metabolic products occur in the short-term and persist over the long-term. Overall, the work in this dissertation provides insight into how the gut microbiome structure and function is altered after bariatric surgery, and how these changes potentially affect the host metabolism. These findings will be helpful in subsequent development of microbiome-based therapeutics to treat obesity.
ContributorsIlhan, Zehra Esra (Author) / Krajmalnik-Brown, Rosa (Thesis advisor) / DiBaise, John K. (Committee member) / Cadillo-Quiroz, Hinsby (Committee member) / Rittmann, Bruce E. (Committee member) / Arizona State University (Publisher)
Created2016
Description
N-Nitrosodimethylamine (NDMA), a probable human carcinogen, has been found in clouds and fogs at concentration up to 500 ng/L and in drinking water as disinfection by-product. NDMA exposure to the general public is not well understood because of knowledge gaps in terms of occurrence, formation and fate both in air and water. The goal of this dissertation was to contribute to closing these knowledge gaps on potential human NDMA exposure through contributions to atmospheric measurements and fate as well as aqueous formation processes.
Novel, sensitive methods of measuring NDMA in air were developed based on Solid Phase Extraction (SPE) and Solid Phase Microextraction (SPME) coupled to Gas Chromatography-Mass Spectrometry (GC-MS). The two measuring techniques were evaluated in laboratory experiments. SPE-GC-MS was applicable in ambient air sampling and NDMA in ambient air was found in the 0.1-13.0 ng/m3 range.
NDMA photolysis, the main degradation atmospheric pathway, was studied in the atmospheric aqueous phase. Water soluble organic carbon (WSOC) was found to have more impact than inorganic species on NDMA photolysis by competing with NDMA for photons and therefore could substantially increase the NDMA lifetime in the atmosphere. The optical properties of atmospheric WSOC were investigated in aerosol, fog and cloud samples and showed WSOC from atmospheric aerosols has a higher mass absorption efficiency (MAE) than organic matter in fog and cloud water, resulting from a different composition, especially in regards of volatile species, that are not very absorbing but abundant in fogs and clouds.
NDMA formation kinetics during chloramination were studied in aqueous samples including wastewater, surface water and ground water, at two monochloramine concentrations. A simple second order NDMA formation model was developed using measured NDMA and monochloramine concentrations at select reaction times. The model fitted the NDMA formation well (R2 >0.88) in all water matrices. The proposed model was then optimized and applied to fit the data of NDMA formation from natural organic matter (NOM) and model precursors in previously studies. By determining the rate constants, the model was able to describe the effect of water conditions such as DOC and pH on NDMA formation.
Novel, sensitive methods of measuring NDMA in air were developed based on Solid Phase Extraction (SPE) and Solid Phase Microextraction (SPME) coupled to Gas Chromatography-Mass Spectrometry (GC-MS). The two measuring techniques were evaluated in laboratory experiments. SPE-GC-MS was applicable in ambient air sampling and NDMA in ambient air was found in the 0.1-13.0 ng/m3 range.
NDMA photolysis, the main degradation atmospheric pathway, was studied in the atmospheric aqueous phase. Water soluble organic carbon (WSOC) was found to have more impact than inorganic species on NDMA photolysis by competing with NDMA for photons and therefore could substantially increase the NDMA lifetime in the atmosphere. The optical properties of atmospheric WSOC were investigated in aerosol, fog and cloud samples and showed WSOC from atmospheric aerosols has a higher mass absorption efficiency (MAE) than organic matter in fog and cloud water, resulting from a different composition, especially in regards of volatile species, that are not very absorbing but abundant in fogs and clouds.
NDMA formation kinetics during chloramination were studied in aqueous samples including wastewater, surface water and ground water, at two monochloramine concentrations. A simple second order NDMA formation model was developed using measured NDMA and monochloramine concentrations at select reaction times. The model fitted the NDMA formation well (R2 >0.88) in all water matrices. The proposed model was then optimized and applied to fit the data of NDMA formation from natural organic matter (NOM) and model precursors in previously studies. By determining the rate constants, the model was able to describe the effect of water conditions such as DOC and pH on NDMA formation.
ContributorsZhang, Jinwei (Author) / Herckes, Pierre (Thesis advisor) / Westerhoff, Paul (Thesis advisor) / Fraser, Matthew (Committee member) / Shock, Everett (Committee member) / Arizona State University (Publisher)
Created2016
Description
The atmosphere contains a substantial amount of water soluble organic material, yet despite years of efforts, little is known on the structure, composition and properties of this organic matter. Aqueous phase processing by fogs and clouds of the gas and particulate organic material is poorly understood despite the importance for air pollution and climate. On one hand, gas phase species can be processed by fog/cloud droplets to form lower volatility species, which upon droplet evaporation lead to new aerosol mass, while on the other hand larger nonvolatile material can be degraded by in cloud oxidation to smaller molecular weight compounds and eventually CO2.
In this work High Performance Size Exclusion Chromatography coupled with inline organic carbon detection (SEC-DOC), Diffusion-Ordered Nuclear Magnetic Resonance spectroscopy (DOSY-NMR) and Fluorescence Excitation-Emission Matrices (EEM) were used to characterize molecular weight distribution, functionality and optical properties of atmospheric organic matter. Fogs, aerosols and clouds were studied in a variety of environments including Central Valley of California (Fresno, Davis), Pennsylvania (Selinsgrove), British Columbia (Whistler) and three locations in Norway. The molecular weight distributions using SEC-DOC showed smaller molecular sizes for atmospheric organic matter compared to surface waters and a smaller material in fogs and clouds compared to aerosol particles, which is consistent with a substantial fraction of small volatile gases that partition into the aqueous phase. Both, cloud and aerosol samples presented a significant fraction (up to 21% of DOC) of biogenic nanoscale material. The results obtained by SEC-DOC were consistent with DOSY-NMR observations.
Cloud processing of organic matter has also been investigated by combining field observations (sample time series) with laboratory experiments under controlled conditions. Observations revealed no significant effect of aqueous phase chemistry on molecular weight distributions overall although during cloud events, substantial differences were apparent between organic material activated into clouds compared to interstitial material. Optical properties on the other hand showed significant changes including photobleaching and an increased humidification of atmospheric material by photochemical aging. Overall any changes to atmospheric organic matter during cloud processing were small in terms of bulk carbon properties, consistent with recent reports suggesting fogs and clouds are too dilute to substantially impact composition.
In this work High Performance Size Exclusion Chromatography coupled with inline organic carbon detection (SEC-DOC), Diffusion-Ordered Nuclear Magnetic Resonance spectroscopy (DOSY-NMR) and Fluorescence Excitation-Emission Matrices (EEM) were used to characterize molecular weight distribution, functionality and optical properties of atmospheric organic matter. Fogs, aerosols and clouds were studied in a variety of environments including Central Valley of California (Fresno, Davis), Pennsylvania (Selinsgrove), British Columbia (Whistler) and three locations in Norway. The molecular weight distributions using SEC-DOC showed smaller molecular sizes for atmospheric organic matter compared to surface waters and a smaller material in fogs and clouds compared to aerosol particles, which is consistent with a substantial fraction of small volatile gases that partition into the aqueous phase. Both, cloud and aerosol samples presented a significant fraction (up to 21% of DOC) of biogenic nanoscale material. The results obtained by SEC-DOC were consistent with DOSY-NMR observations.
Cloud processing of organic matter has also been investigated by combining field observations (sample time series) with laboratory experiments under controlled conditions. Observations revealed no significant effect of aqueous phase chemistry on molecular weight distributions overall although during cloud events, substantial differences were apparent between organic material activated into clouds compared to interstitial material. Optical properties on the other hand showed significant changes including photobleaching and an increased humidification of atmospheric material by photochemical aging. Overall any changes to atmospheric organic matter during cloud processing were small in terms of bulk carbon properties, consistent with recent reports suggesting fogs and clouds are too dilute to substantially impact composition.
ContributorsWang, Youliang (Author) / Herckes, Pierre (Thesis advisor) / Fraser, Matthew (Committee member) / Anbar, Ariel (Committee member) / Arizona State University (Publisher)
Created2014