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Description
Adenoviruses cause gastrointestinal illnesses and have been listed on the U.S. EPA’s Contaminant Candidate Lists (CCL). They are highly resistant to ultraviolet (UV) inactivation. Advanced oxidation processes (AOPs) are known to improve inactivation of microorganisms and simultaneously oxidize organics. The bacteriophage P22 was selected as a surrogate for adenoviruses due

Adenoviruses cause gastrointestinal illnesses and have been listed on the U.S. EPA’s Contaminant Candidate Lists (CCL). They are highly resistant to ultraviolet (UV) inactivation. Advanced oxidation processes (AOPs) are known to improve inactivation of microorganisms and simultaneously oxidize organics. The bacteriophage P22 was selected as a surrogate for adenoviruses due to their physical and genetic similarities.

The main objective of this study was to compare the synergic disinfection potential of titanium dioxide (TiO2) or peracetic acid (PAA) with UV for viruses and bacteria in water.

Both bench-scale and pilot-scale evaluation was done. A bench-scale collimated beam was included to evaluate the inactivation of P22 and E. coli by UV with and without TiO2 or PAA. A Purifics Photo-Cat system which is an integrated UV/ceramic membrane reactor was used for the pilot-scale TiO2-UV AOP experiments. For pilot-scale PAA-UV AOP experiments, an in-line D222 UV reactor unit provided by NeoTech Aqua Solutions, Inc. was used.

TiO2 doses of 1, 10, and 40 mg/L were applied in the collimated beam and the Photo-Cat system. Higher TiO2 doses resulted in a higher inactivation in the Photo-Cat and lower inactivation in the collimated beam apparatus. Adding 40 mg/L of TiO2 in the photo-Cat system improved P22 inactivation by 25% while it slightly decreased P22 inactivation in collimated beam apparatus.

PAA doses of 0.25 or 0.5 ppm were continuously injected upstream of the UV light and a 53% or 90% increase in inactivation was observed for E. coli, respectively, as compared to UV alone. However, P22 required higher dose with PAA-UV AOP and PAA concentrations of 1 or 10 ppm resulted in an 18% and 70% increase in the inactivation respectively, as compared to UV alone. Interestingly, when the same condition was applied to water with more organics (UVT 79%), E. coli exhibited the same level of susceptibility to PAA-UV AOP while P22 inactivation decreased.

The results provide new insight on the effectiveness and applicability of adding AOP to UV for microbial inactivation in water. PAA-UV AOP can potentially enhance existing UV disinfection systems with minimal chemical addition, and a simple retrofit to existing UV units.
ContributorsNikougoftar Zarif, Majid (Author) / Abbaszadegan, Morteza (Thesis advisor) / Fox, Peter (Committee member) / Conroy-Ben, Otakuye (Committee member) / Arizona State University (Publisher)
Created2017
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Description
Radioactive cesium (137Cs), released from nuclear power plants and nuclear accidental releases, is a problem due to difficulties regarding its removal. Efforts have been focused on removing cesium and the remediation of the contaminated environment. Traditional treatment techniques include Prussian blue and nano zero-valent ion (nZVI) and nano-Fe/Cu particles to

Radioactive cesium (137Cs), released from nuclear power plants and nuclear accidental releases, is a problem due to difficulties regarding its removal. Efforts have been focused on removing cesium and the remediation of the contaminated environment. Traditional treatment techniques include Prussian blue and nano zero-valent ion (nZVI) and nano-Fe/Cu particles to remove Cs from water; however, they are not efficient at removing Cs when present at low concentrations of about 10 parts-per-billion (ppb), typical of concentrations found in the radioactive contaminated sites.

The objective of this study was to develop an innovative and simple method to remove Cs+ present at low concentrations by engineering a proteoliposome transporter composed of an uptake protein reconstituted into a liposome vesicle. To achieve this, the uptake protein, Kup, from E. coli, was isolated through protein extraction and purification procedures. The new and simple extraction methodology developed in this study was highly efficient and resulted in purified Kup at ~1 mg/mL. A new method was also developed to insert purified Kup protein into the bilayers of liposome vesicles. Finally, removal of CsCl (10 and 100 ppb) was demonstrated by spiking the constructed proteoliposome in lab-fortified water, followed by incubation and ultracentrifugation, and measuring Cs+ with inductively coupled plasma mass spectrometry (ICP-MS).

The ICP-MS results from testing water contaminated with 100 ppb CsCl, revealed that adding 0.1 – 8 mL of Kup proteoliposome resulted in 0.29 – 12.7% Cs removal. Addition of 0.1 – 2 mL of proteoliposome to water contaminated with 10 ppb CsCl resulted in 0.65 – 3.43% Cs removal. These removal efficiencies were greater than the control, liposome with no protein.

A linear relationship was observed between the amount of proteoliposome added to the contaminated water and removal percentage. Consequently, by adding more volumes of proteoliposome, removal can be simply improved. This suggests that with ~ 60-70 mL of proteoliposome, removal of about 90% can be achieved. The novel technique developed herein is a contribution to emerging technologies in the water and wastewater treatment industry.
ContributorsHakim Elahi, Sepideh (Author) / Conroy-Ben, Otakuye (Thesis advisor) / Abbaszadegan, Morteza (Committee member) / Fox, Peter (Committee member) / Arizona State University (Publisher)
Created2018
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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

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
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Description
Widespread use of chlorinated solvents for commercial and industrial purposes makes co-occurring contamination by 1,1,1-trichloroethane (TCA), trichloroethene (TCE), and 1,4-dioxane (1,4-D) a serious problem for groundwater. TCE and TCA often are treated by reductive dechlorination, while 1,4-D resists reductive treatment. Aerobic bacteria are able to oxidize 1,4-D, but

Widespread use of chlorinated solvents for commercial and industrial purposes makes co-occurring contamination by 1,1,1-trichloroethane (TCA), trichloroethene (TCE), and 1,4-dioxane (1,4-D) a serious problem for groundwater. TCE and TCA often are treated by reductive dechlorination, while 1,4-D resists reductive treatment. Aerobic bacteria are able to oxidize 1,4-D, but the biological oxidation of 1,4-D could be inhibited TCA, TCE, and their reductive transformation products. To overcome the challenges from co-occurring contamination, I propose a two-stage synergistic system. First, anaerobic reduction of the chlorinated hydrocarbons takes place in a H2-based hollow-fiber “X-film” (biofilm or catalyst-coated film) reactor (MXfR), where “X-film” can be a “bio-film” (MBfR) or an abiotic “palladium-film” (MPfR). Then, aerobic removal of 1,4-D and other organic compounds takes place in an O2-based MBfR. For the reductive part, I tested reductive bio-dechlorination of TCA and TCE simultaneously in an MBfR. I found that the community of anaerobic bacteria can rapidly reduce TCE to cis-dichloroethene (cis-DCE), but further reductions of cis-DCE to vinyl chloride (VC) and VC to ethene were inhibited by TCA. Also, it took months to grow a strong biofilm that could reduce TCA and TCE. Another problem with reductive dechlorination in the MBfR is that mono-chloroethane (MCA) was not reduced to ethane. In contrast, a film of palladium nano-particles (PdNPs), i.e., an MPfR, could the simultaneous reductions of TCA and TCE to mainly ethane, with only small amounts of intermediates: 1,1-dichloroethane (DCA) (~3% of total influent TCA and TCE) and MCA (~1%) in continuous operation. For aerobic oxidation, I enriched an ethanotrophic culture that could oxidize 1,4-D with ethane as the primary electron donor. An O2-based MBfR, inoculated with the enriched ethanotrophic culture, achieved over 99% 1,4-D removal with ethane as the primary electron donor in continuous operation. Finally, I evaluated two-stage treatment with a H2-based MPfR followed by an O2-MBfR. The two-stage system gave complete removal of TCA, TCE, and 1,4-D in continuous operation.
ContributorsLuo, Yihao (Author) / Rittmann, Bruce E. (Committee member) / Krajmalnik-Brown, Rosa (Committee member) / Zhou, Chen (Committee member) / Arizona State University (Publisher)
Created2018
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Description
Activated Carbon has been used for decades to remove organics from water at large scale in municipal water treatment as well as at small scale in Point of Use (POU) and Point of Entry (POE) water treatment. This study focused on Granular Activated Carbon (GAC) and also activated Carbon Block

Activated Carbon has been used for decades to remove organics from water at large scale in municipal water treatment as well as at small scale in Point of Use (POU) and Point of Entry (POE) water treatment. This study focused on Granular Activated Carbon (GAC) and also activated Carbon Block (CB) were studied.

This thesis has three related elements for organics control in drinking water. First, coagulation chemistry for Alum and Aluminum Chlorohydrate (ACH) was optimized for significant organics removal to address membrane fouling issue at a local municipal water treatment plant in Arizona. Second, Rapid Small Scale Column Tests were conducted for removal of Perfluorinated compounds (PFC), PFC were present in groundwater at a local site in Arizona at trace levels with combined concentration of Perfluorooctaneoic Acid (PFOA) and Perfloorooctanesulfonic Acid (PFOS) up to 245 ng/L. Groundwater from the concerned site is used as drinking water source by a private utility. PFC Removal was evaluated for different GAC, influent concentrations and particle sizes. Third, a new testing protocol (Mini Carbon Block (MCB)) for bench scale study of POU water treatment device, specifically carbon block filter was developed and evaluated. The new bench scale decreased the hydraulic requirements by 60 times approximately, which increases the feasibility to test POU at a lab scale. It was evaluated for a common POU organic contaminant: Chloroform, and other model contaminants.

10 mg/L of ACH and 30 mg/L of Alum with pH adjustment were determined as optimal coagulant doses. Bituminous coal based GAC was almost three times better than coconut shell based GAC for removing PFC. Multiple tests with MCB suggested no short circuiting and consistent performance for methylene blue though chloroform removal tests underestimated full scale carbon block performance but all these tests creates a good theoretical and practical fundament for this new approach and provides directions for future researchers.
ContributorsAshani, Harsh Satishbhai (Author) / Westerhoff, Paul (Thesis advisor) / Hristovski, Kiril (Committee member) / Conroy-Ben, Otakuye (Committee member) / Arizona State University (Publisher)
Created2017
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Description
This dissertation applies wastewater-based epidemiology (WBE) to aqueous process flows to gauge the public health status concerning exposure and potential abuse of pharmaceuticals, antimicrobials, and narcotics. The masses of emerging contaminants emitted into Indian aquatic and terrestrial environments were the highest for open defecation (17 ± 12 mt/d), with non-steroidal

This dissertation applies wastewater-based epidemiology (WBE) to aqueous process flows to gauge the public health status concerning exposure and potential abuse of pharmaceuticals, antimicrobials, and narcotics. The masses of emerging contaminants emitted into Indian aquatic and terrestrial environments were the highest for open defecation (17 ± 12 mt/d), with non-steroidal anti-inflammatory drugs dominating environmental loading (14 ± 10 mt/d), followed by antibiotics, antimicrobials, phthalates and miscellaneous pharmaceuticals (Chapter 2). Fourteen wastewater treatment plants sampled across the U.S. had a combined average mass loading of 71 ± 12 µg/d/capita for the antimicrobials triclosan and triclocarban, with paraben compounds contributing 19 ± 5 µg/d/US capita. Risk models showed unfavorable hazard quotients (HQ>1) for sensitive aquatic organisms (algae, zebra fish and rainbow trout) from predicted exposures to antimicrobials of alternative use, i.e., chlorhexidine and benzalkonium chloride (Chapter 3). Substances subject to licit and illicit use, monitored by WBE in a medium-sized southwestern U.S. city before and during COVID-19-related lockdowns, showed the highest mass loads for cocaine and its major metabolite benzoylecgonine (2,207 total), methadone and its major metabolite 2-Ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine (197), parent mitragynine (60), oxycodone and its major metabolite noroxycodone (48), heroin and its major metabolite 6-acetylmorphine (45), and parent codeine (37) in mg/1,000 capita/day. Heroin use during the lockdown increased ~10-fold relative to the pre-lockdown baseline, whereas oxycodone and codeine mass loading decreased 5-fold and 2.5-fold, respectively (Chapter 4). Experiments elucidating the stability of stress hormones and their metabolites as a function of temperature and in-sewer residence time revealed a rapid degradation to completion over 24 hours at 35°C, whereas lower temperatures of 25°C and 15°C were found to allow for successful tracking of indicators of stress at the population level; statistically significant differences in stress hormone decay rates were observed due to geographic locations at 25°C (p=0.009) but not due to redox conditions in the sewer pipe (Chapter 5). This thesis demonstrated the successful application of WBE for studying population health frequently and inexpensively, with the limitation that a lack of centralized wastewater infrastructure in developing countries may create barriers for at-risk populations to access and utilize this novel technology (Chapter 6).
ContributorsKelkar, Varun Pushkaraj (Author) / Halden, Rolf U (Thesis advisor) / Hamilton, Kerry A (Committee member) / Conroy-Ben, Otakuye (Committee member) / Arizona State University (Publisher)
Created2021
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Description
This dissertation focused on studying risks associated with emerging drinking water contaminants and tradeoffs related to water management interventions. The built environment impacts health, as humans on average spend ~90% of their time indoors. Federal regulations generally focus on drinking water at the water treatment plant and within the distribution

This dissertation focused on studying risks associated with emerging drinking water contaminants and tradeoffs related to water management interventions. The built environment impacts health, as humans on average spend ~90% of their time indoors. Federal regulations generally focus on drinking water at the water treatment plant and within the distribution system as opposed to when it enters buildings after crossing the property line. If drinking water is not properly managed in buildings, it can be a source or amplifier of microbial and chemical contaminants. Unlike regulations for chemical contaminants that are risk-based, for pathogens, regulations are either based on recommended treatment technologies or designated as zero, which is not achievable in practice. Practice-based judgments are typically made at the building level to maintain water quality. This research focuses on two drinking water opportunistic pathogens of public health concern, Legionella pneumophila and Mycobacterium avium complex (MAC). Multiple aspects of drinking water quality in two green buildings were monitored in tandem with water management interventions. Additionally, a quantitative microbial risk assessment framework was used to predict risk-based critical concentrations of MAC for drinking water-related exposures in the indoor environment corresponding to a 1 in 10,000 annual infection target risk benchmark. The overall goal of this work was to inform the development of water management plans and guidelines for buildings that will improve water quality in the built environment and promote better public health. It was determined that a whole building water softening system with ion exchange softening resin and expansion tanks were unexplored reservoirs for the colonization of L. pneumophila. Furthermore, it was observed that typical water management interventions such as flushing and thermal disinfection did not always mitigate water quality issues. Thus, there was a need to implement several atypical interventions such as equipment replacement to improve the building water quality. This work has contributed comprehensive field studies and models that have highlighted the need for additional niches, facility management challenges, and risk tradeoffs for focus in water safety plans. The work also informs additional risk-based water quality policy approaches for reducing drinking water risks.
ContributorsJoshi, Sayalee (Author) / Hamilton, Kerry A (Thesis advisor) / Abbaszadegan, Morteza (Committee member) / Conroy-Ben, Otakuye (Committee member) / Halden, Rolf (Committee member) / Arizona State University (Publisher)
Created2023
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Description
Hydrophobic ionizable organic compounds (HIOCs) like per- and polyfluoroalkyl substances (PFAS), certain pharmaceuticals, and surfactants have been detected in groundwater, wastewater, and drinking water. Anion exchange resin treatment is an effective process for removal of anionic contaminants from water. Spent anion exchange resins are conventionally regenerated with high alcohol by

Hydrophobic ionizable organic compounds (HIOCs) like per- and polyfluoroalkyl substances (PFAS), certain pharmaceuticals, and surfactants have been detected in groundwater, wastewater, and drinking water. Anion exchange resin treatment is an effective process for removal of anionic contaminants from water. Spent anion exchange resins are conventionally regenerated with high alcohol by volume (ABV) methanol in solution with brine. While effective for regeneration of resins saturated with inorganic anions such as sulfate, nitrate, and perchlorate, HIOCs prove more resistant to regeneration. This research investigated the efficacy of using novel cosolvent solutions with brine to regenerate resins saturated with organic carboxylate and sulfonate anions to understand the effects cosolvent properties have on regenerative ability. Experiments were conducted on six PFAS compounds to evaluate trends in regeneration for three alcohols. For all PFAS species, equivalent ABV and brine solutions showed greatest regeneration with 1-propanol over ethanol and methanol. Experiments with the pharmaceutical sodium diclofenac were conducted showing similar regeneration of 75% methanol and 25% 1-propanol for equivalent salt concentrations and higher regeneration with 1-propanol than ethanol and methanol for equivalent ABV. A series of experiments with surfactant dodecylbenzene sulfonate determined that the key parameters to determine regeneration of the resin for an alcohol cosolvent solution were cosolvent volume fraction, molar mass, Kow value, solution ionic strength, and dielectric constant. Individual assessments on the cost-effectiveness, flammability, and sustainability of cosolvent solutions point to possible future experiments and opportunities for recycled distillery waste streams as regenerative solutions for anion exchange resin.
ContributorsGraham, Cole David (Author) / Boyer, Treavor H (Thesis advisor) / Conroy-Ben, Otakuye (Committee member) / Garcia Segura, Sergio (Committee member) / Arizona State University (Publisher)
Created2022
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Description
Although anion exchange resins (AERs) have been implemented for a wide range of aqueous contaminants including notorious perfluoroalkyl acids (PFAAs) that are of human health concern, the potential benefits and underlying chemistry of weak-base (WB) AERs are overlooked. To fill these key gaps in the literature, this research evaluated the

Although anion exchange resins (AERs) have been implemented for a wide range of aqueous contaminants including notorious perfluoroalkyl acids (PFAAs) that are of human health concern, the potential benefits and underlying chemistry of weak-base (WB) AERs are overlooked. To fill these key gaps in the literature, this research evaluated the removal and regeneration efficiency of WB-AER (IRA 67 and IRA 96) with strong-base (SB) AER as the baseline. Batch equilibrium tests were first conducted for the removal of nitrate, sulfate, 3-phenylpropionic acid, and six legacy PFAAs with contrasting properties at different solution pH using polyacrylic and polystyrene chloride-form AERs. In ambient (pH 7) and acidic (pH 4) solutions, the polymer composition was the controlling factor followed by the length of alkyl chain of the resin while AER basicity did not influence the selectivity for the selected contaminants. WB resin had higher capacity than SB analogs based on quantitative analysis using isotherm model parameters. Batch and column adsorption experiments showed significantly greater removal of PFAAs by polystyrene than polyacrylic AERs regardless of resin basicity, with the order of decreasing polyacrylic resin selectivity of PFOS >> PFHxS ≈ PFOA > PFBS > PFHxA ≈ PFBA. The removal performance of WB-AER was reversible, declining drastically at basic conditions and gradually regained once below the pKa of the resin due to the pH-dependent nature of amine groups. This was not the case for IRA 96 (i.e., polystyrene) which exhibited high removal of PFAAs irrelevant of pH because of the nonpolar character of polystyrene matrix. The non-hydrophobic IRA 67 (i.e., polyacrylic) had a satisfactory regeneration using non-toxic salt-only solutions comprising 1% NaOH and 0.5% NaOH + 0.5% NaCl, while IRA 96 was only amenable to brine/methanol regeneration. Important caveats on the validity of isotherm modeling in batch adsorption tests were discussed. Results for batch and column experiments using chloride-form and free-base form WB-AER, respectively, provide insights for industrial applications.
ContributorsKassar, Christian (Author) / Boyer, Treavor H. (Thesis advisor) / Westerhoff, Paul K. (Committee member) / Conroy-Ben, Otakuye (Committee member) / Arizona State University (Publisher)
Created2022
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Description

Widespread use of halogenated organic compounds for commercial and industrial purposes makes halogenated organic pollutants (HOPs) a global challenge for environmental quality. Current wastewater treatment plants (WWTPs) are successful at reducing chemical oxygen demand (COD), but the removal of HOPs often is poor. Since HOPs are xenobiotics, the biodegradation of

Widespread use of halogenated organic compounds for commercial and industrial purposes makes halogenated organic pollutants (HOPs) a global challenge for environmental quality. Current wastewater treatment plants (WWTPs) are successful at reducing chemical oxygen demand (COD), but the removal of HOPs often is poor. Since HOPs are xenobiotics, the biodegradation of HOPs is usually limited in the WWTPs. The current methods for HOPs treatments (e.g., chemical, photochemical, electrochemical, and biological methods) do have their limitations for practical applications. Therefore, a combination of catalytic and biological treatment methods may overcome the challenges of HOPs removal.This dissertation investigated a novel catalytic and biological synergistic platform to treat HOPs. 4-chlorophenol (4-CP) and halogenated herbicides were used as model pollutants for the HOPs removal tests. The biological part of experiments documented successful co-oxidation of HOPs and analog non-halogenated organic pollutants (OPs) (as the primary substrates) in the continuous operation of O2-based membrane biofilm reactor (O2-MBfR). In the first stage of the synergistic platform, HOPs were reductively dehalogenated to less toxic and more biodegradable OPs during continuous operation of a H2-based membrane catalytic-film reactor (H2-MCfR). The synergistic platform experiments demonstrated that OPs generated in the H2-MCfR were used as the primary substrates to support the co-oxidation of HOPs in the subsequent O2-MBfR. Once at least 90% conversation of HOPs to OPs was achieved in the H2-MCfR, the products (OPs to HOPs mole ratio >9) in the effluent could be completely mineralized through co-oxidation in O2-MBfR. By using H2 gas as the primary substrate, instead adding the analog OP, the synergistic platform greatly reduced chemical costs and carbon-dioxide emissions during HOPs co-oxidation.

ContributorsLuo, Yihao (Author) / Rittmann, Bruce (Thesis advisor) / Krajmalnik-Brown, Rosa (Committee member) / Torres, Cesar (Committee member) / Arizona State University (Publisher)
Created2022