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- All Subjects: Environmental engineering
- Creators: Halden, Rolf
- Creators: Kavazanjian, Edward
- Resource Type: Text
Description
Nitrate is the most prevalent water pollutant limiting the use of groundwater as a potable water source. The overarching goal of this dissertation was to leverage advances in nanotechnology to improve nitrate photocatalysis and transition treatment to the full-scale. The research objectives were to (1) examine commercial and synthesized photocatalysts, (2) determine the effect of water quality parameters (e.g., pH), (3) conduct responsible engineering by ensuring detection methods were in place for novel materials, and (4) develop a conceptual framework for designing nitrate-specific photocatalysts. The key issues for implementing photocatalysis for nitrate drinking water treatment were efficient nitrate removal at neutral pH and by-product selectivity toward nitrogen gases, rather than by-products that pose a human health concern (e.g., nitrite). Photocatalytic nitrate reduction was found to follow a series of proton-coupled electron transfers. The nitrate reduction rate was limited by the electron-hole recombination rate, and the addition of an electron donor (e.g., formate) was necessary to reduce the recombination rate and achieve efficient nitrate removal. Nano-sized photocatalysts with high surface areas mitigated the negative effects of competing aqueous anions. The key water quality parameter impacting by-product selectivity was pH. For pH < 4, the by-product selectivity was mostly N-gas with some NH4+, but this shifted to NO2- above pH = 4, which suggests the need for proton localization to move beyond NO2-. Co-catalysts that form a Schottky barrier, allowing for localization of electrons, were best for nitrate reduction. Silver was optimal in heterogeneous systems because of its ability to improve nitrate reduction activity and N-gas by-product selectivity, and graphene was optimal in two-electrode systems because of its ability to shuttle electrons to the working electrode. "Environmentally responsible use of nanomaterials" is to ensure that detection methods are in place for the nanomaterials tested. While methods exist for the metals and metal oxides examined, there are currently none for carbon nanotubes (CNTs) and graphene. Acknowledging that risk assessment encompasses dose-response and exposure, new analytical methods were developed for extracting and detecting CNTs and graphene in complex organic environmental (e.g., urban air) and biological matrices (e.g. rat lungs).
ContributorsDoudrick, Kyle (Author) / Westerhoff, Paul (Thesis advisor) / Halden, Rolf (Committee member) / Hristovski, Kiril (Committee member) / Arizona State University (Publisher)
Created2013
Description
Hydrocarbon spill site cleanup is challenging when contaminants are present in lower permeability layers. These are difficult to remediate and may result in long-term groundwater impacts. The research goal is to investigate strategies for long-term reduction of contaminant emissions from sources in low permeability layers through partial source treatment at higher/lower permeability interfaces. Conceptually, this provides a clean/reduced concentration zone near the interface, and consequently a reduced concentration gradient and flux from the lower permeability layer. Treatment by in-situ chemical oxidation (ISCO) was evaluated using hydrogen peroxide (H2O2) and sodium persulfate (Na2S2O8). H2O2 studies included lab and field-scale distribution studies and lab emission reduction experiments. The reaction rate of H2O2 in soils was so fast it did not travel far (<1 m) from delivery points under typical flow conditions. Oxygen gas generated and partially trapped in soil pores served as a dissolved oxygen (DO) source for >60 days in field and lab studies. During that period, the laboratory studies had reduced hydrocarbon impacts, presumably from aerobic biodegradation, which rebounded once the O2 source depleted. Therefore field monitoring should extend beyond the post-treatment elevated DO. Na2S2O8 use was studied in two-dimensional tanks (122-cm tall, 122-cm wide, and 5-cm thick) containing two contrasting permeability layers (three orders of magnitude difference). The lower permeability layer initially contained a dissolved-sorbed contaminant source throughout this layer, or a 10-cm thick non-aqueous phase liquid (NAPL)-impacted zone below the higher/lower permeability interface. The dissolved-sorbed source tank was actively treated for 14 d. Two hundred days after treatment, the emission reduction of benzene, toluene, ethylbenzene, and p-xylene (BTEX) were 95-99% and methyl tert-butyl ether (MTBE) was 63%. The LNAPL-source tank had three Na2S2O8 and two sodium hydroxide (NaOH) applications for S2O82- base activation. The resulting emission reductions for BTEX, n-propylbenzene, and 1,3,5 trymethylbenzene were 55-73%. While less effective at reducing emissions from LNAPL sources, the 14-d treatment delivered sufficient S2O82- though diffusion to remediate BTEX from the 60 cm dissolved-sorbed source. The overall S2O82- utilization in the dissolved source experiment was calculated by mass balance to be 108-125 g S2O82-/g hydrocarbon treated.
ContributorsCavanagh, Bridget (Author) / Johnson, Paul C (Thesis advisor) / Westerhoff, Paul (Committee member) / Kavazanjian, Edward (Committee member) / Bruce, Cristin (Committee member) / Arizona State University (Publisher)
Created2014
Description
Contaminants of emerging concern (CECs) present in wastewater effluent can threat its safe discharge or reuse. Additional barriers of protection can be provided using advanced or natural treatment processes. This dissertation evaluated ozonation and constructed wetlands to remove CECs from wastewater effluent. Organic CECs can be removed by hydroxyl radical formed during ozonation, however estimating the ozone demand of wastewater effluent is complicated due to the presence of reduced inorganic species. A method was developed to estimate ozone consumption only by dissolved organic compounds and predict trace organic oxidation across multiple wastewater sources. Organic and engineered nanomaterial (ENM) CEC removal in constructed wetlands was investigated using batch experiments and continuous-flow microcosms containing decaying wetland plants. CEC removal varied depending on their physico-chemical properties, hydraulic residence time (HRT) and relative quantities of plant materials in the microcosms. At comparable HRTs, ENM removal improved with higher quantity of plant materials due to enhanced sorption which was verified in batch-scale studies with plant materials. A fate-predictive model was developed to evaluate the role of design loading rates on organic CEC removal. Areal removal rates increased with hydraulic loading rates (HLRs) and carbon loading rates (CLRs) unless photolysis was the dominant removal mechanism (e.g. atrazine). To optimize CEC removal, wetlands with different CLRs can be used in combination without lowering the net HLR. Organic CEC removal in denitrifying conditions of constructed wetlands was investigated and selected CECs (e.g. estradiol) were found to biotransform while denitrification occurred. Although level of denitrification was affected by HRT, similar impact on estradiol was not observed due to a dominant effect from plant biomass quantity. Overall, both modeling and experimental findings suggest considering CLR as an equally important factor with HRT or HLR to design constructed wetlands for CEC removal. This dissertation provided directions to select design parameters for ozonation (ozone dose) and constructed wetlands (design loading rates) to meet organic CEC removal goals. Future research is needed to understand fate of ENMs during ozonation and quantify the contributions from different transformation mechanisms occurring in the wetlands to incorporate in a model and evaluate the effect of wetland design.
ContributorsSharif, Fariya (Author) / Westerhoff, Paul (Thesis advisor) / Halden, Rolf (Committee member) / Fox, Peter (Committee member) / Herckes, Pierre (Committee member) / Arizona State University (Publisher)
Created2013
Description
The influence of climate variability and reclaimed wastewater on the water supply necessitates improved understanding of the treatability of trace and bulk organic matter. Dissolved organic matter (DOM) mobilized during extreme weather events and in treated wastewater includes natural organic matter (NOM), contaminants of emerging concern (CECs), and microbial extracellular polymeric substances (EPS). The goal of my dissertation was to quantify the impacts of extreme weather events on DOM in surface water and downstream treatment processes, and to improve membrane filtration efficiency and CECs oxidation efficiency during water reclamation with ozone. Surface water quality, air quality and hydrologic flow rate data were used to quantify changes in DOM and turbidity following dust storms, flooding, or runoff from wildfire burn areas in central Arizona. The subsequent impacts to treatment processes and public perception of water quality were also discussed. Findings showed a correlation between dust storm events and change in surface water turbidity (R2=0.6), attenuation of increased DOM through reservoir systems, a 30-40% increase in organic carbon and a 120-600% increase in turbidity following severe flooding, and differing impacts of upland and lowland wildfires. The use of ozone to reduce membrane fouling caused by vesicles (a subcomponent of EPS) and oxidize CECs through increased hydroxyl radical (HO●) production was investigated. An "ozone dose threshold" was observed above which addition of hydrogen peroxide increased HO● production; indicating the presence of ambient promoters in wastewater. Ozonation of CECs in secondary effluent over titanium dioxide or activated carbon did not increase radial production. Vesicles fouled ultrafiltration membranes faster (20 times greater flux decline) than polysaccharides, fatty acids, or NOM. Based upon the estimated carbon distribution of secondary effluent, vesicles could be responsible for 20-60% of fouling during ultrafiltration and may play a vital role in other environmental processes as well. Ozone reduced vesicle-caused membrane fouling that, in conjunction with the presence of ambient promoters, helps to explain why low ozone dosages improve membrane flux during full-scale water reclamation.
ContributorsBarry, Michelle (Author) / Barry, Michelle C (Thesis advisor) / Westerhoff, Paul (Committee member) / Fox, Peter (Committee member) / Halden, Rolf (Committee member) / Hristovski, Kiril (Committee member) / Arizona State University (Publisher)
Created2014
Description
Arsenic (As) and chromium (Cr) occur naturally in AZ surface and groundwaters, pose different health impacts, and exhibit different treatment efficacies. Hexavalent chromium (Cr(VI)) has newly recognized human health concerns, and State and Federal agencies are evaluating a low Cr(VI)-specific maximum contaminant level (MCL) for drinking water. Occurrence of Cr and As in municipal drinking waters and industrial cooling tower waters was quantified by grab samples and compared with sampling results obtained from a new passive sampler developed specifically for Cr(VI). Cr(VI) and As concentrations in groundwater used for cooling tower make-up water concentrations were ~3 ppb and ~4 ppb, respectively, and were concentrated significantly in blowdown water (~20 ppb and ~40 ppb). Based upon pending Cr(VI), As, and other metal regulations, these blowdown waters will need routine monitoring and treatment. Cr(VI) concentrations in a water treatment plant (WTP) raw and finished water samples varied from 0.5 and 2 ppb for grab samples collected every 4 hours for 7 consecutive days using an ISCO sampler. The development of an ion exchange (IX) based passive sampler was validated in the field at the WTP and yielded an average exposure within 1 standard deviation of ISCO sampler grab data. Sampling at both the WTP and cooling towers suggested sources of Cr(III) from treatment chemicals or wood preservatives may exist. Since both facilities use chlorine oxidants, I quantified the apparent (pH=5) second-order rate constant for aqueous chlorine (HOCl/OCl-) with Cr(III) to form Cr(VI) as 0.7 M-1s-1. Under typical conditions (2 ppb Cr(III) ; 2 mg/L Cl2) the half-life for the conversion of Cr(III) to the more toxic form Cr(VI) is 4.7 hours. The occurrence studies in AZ and CA show the Cr(VI) and As treatment of groundwaters will be required to meet stringent Cr(VI) regulations. IX technologies, both strong base anion (SBA) and weak base anion (WBA) resin types were screened (and compared) for Cr removal. The SBA IX process for As removal was optimized by utilizing a reactive iron coagulation and filtration (RCF) process to treat spent IX brine, which was then reused to for SBA resin regeneration.
ContributorsBowen, Alexandra (Author) / Paul, Westerhoff K. (Thesis advisor) / Hristovski, Kiril (Committee member) / Halden, Rolf (Committee member) / Arizona State University (Publisher)
Created2014
Description
Characterization of petroleum spill site source zones directly influences the selection of corrective action plans and frequently affects the success of remediation efforts. For example, simply knowing whether or not nonaqueous phase liquid (NAPL) is present, or if there is chemical storage in less hydraulically accessible regions, will influence corrective action planning. The overarching objective of this study was to assess if macroscopic source zone features can be inferred from dissolved concentration vs. time data. Laboratory-scale physical model studies were conducted for idealized sources; defined as Type-1) NAPL-impacted high permeability zones, Type-2) NAPL-impacted lower permeability zones, and Type-3) dissolved chemical matrix storage in lower permeability zones. Aquifer source release studies were conducted using two-dimensional stainless steel flow-through tanks outfitted with sampling ports for the monitoring of effluent concentrations and flow rates. An idealized NAPL mixture of key gasoline components was used to create the NAPL source zones, and dissolved sources were created using aqueous solutions having concentrations similar to water in equilibrium with the NAPL sources. The average linear velocity was controlled by pumping to be about 2 ft/d, and dissolved effluent concentrations were monitored daily. The Type-1 experiment resulted in a source signature similar to that expected for a relatively well-mixed NAPL source, with dissolved concentrations dependent on chemical solubility and initial mass fraction. The Type-2 and Type-3 experiments were conducted for 320 d and 190 d respectively. Unlike the Type-1 experiment, the concentration vs. time behavior was similar for all chemicals, for both source types. The magnitudes of the effluent concentrations varied between the Type-2 and Type-3 experiments, and were related to the hydrocarbon source mass. A fourth physical model experiment was performed to identify differences between ideal equilibrium behavior and the source concentration vs. time behavior observed in the tank experiments. Screening-level mathematical models predicted the general behavior observed in the experiments. The results of these studies suggest that dissolved concentration vs. time data can be used to distinguish between Type-1 sources in transmissive zones and Type-2 and Type-3 sources in lower permeability zones, provided that many years to decades of data are available. The results also suggest that concentration vs. time data alone will be insufficient to distinguish between NAPL and dissolved-phase storage sources in lower permeability regions.
ContributorsWilson, Sean Tomas (Author) / Johnson, Paul (Thesis advisor) / Kavazanjian, Edward (Committee member) / Fox, Peter (Committee member) / Arizona State University (Publisher)
Created2014
Description
It is estimated that wind induced soil transports more than 500 x 106 metric tons of fugitive dust annually. Soil erosion has negative effects on human health, the productivity of farms, and the quality of surface waters. A variety of different polymer stabilizers are available on the market for fugitive dust control. Most of these polymer stabilizers are expensive synthetic polymer products. Their adverse effects and expense usually limits their use. Biopolymers provide a potential alternative to synthetic polymers. They can provide dust abatement by encapsulating soil particles and creating a binding network throughout the treated area. This research into the effectiveness of biopolymers for fugitive dust control involved three phases. Phase I included proof of concept tests. Phase II included carrying out the tests in a wind tunnel. Phase III consisted of conducting the experiments in the field. Proof of concept tests showed that biopolymers have the potential to reduce soil erosion and fugitive dust transport. Wind tunnel tests on two candidate biopolymers, xanthan and chitosan, showed that there is a proportional relationship between biopolymer application rates and threshold wind velocities. The wind tunnel tests also showed that xanthan gum is more successful in the field than chitosan. The field tests showed that xanthan gum was effective at controlling soil erosion. However, the chitosan field data was inconsistent with the xanthan data and field data on bare soil.
ContributorsAlsanad, Abdullah (Author) / Kavazanjian, Edward (Thesis advisor) / Edwards, David (Committee member) / Zapata, Claudia (Committee member) / Arizona State University (Publisher)
Created2011
Description
In this work, the vapor transport and aerobic bio-attenuation of compounds from a multi-component petroleum vapor mixture were studied for six idealized lithologies in 1.8-m tall laboratory soil columns. Columns representing different geological settings were prepared using 20-40 mesh sand (medium-grained) and 16-minus mesh crushed granite (fine-grained). The contaminant vapor source was a liquid composed of twelve petroleum hydrocarbons common in weathered gasoline. It was placed in a chamber at the bottom of each column and the vapors diffused upward through the soil to the top where they were swept away with humidified gas. The experiment was conducted in three phases: i) nitrogen sweep gas; ii) air sweep gas; iii) vapor source concentrations decreased by ten times from the original concentrations and under air sweep gas. Oxygen, carbon dioxide and hydrocarbon concentrations were monitored over time. The data allowed determination of times to reach steady conditions, effluent mass emissions and concentration profiles. Times to reach near-steady conditions were consistent with theory and chemical-specific properties. First-order degradation rates were highest for straight-chain alkanes and aromatic hydrocarbons. Normalized effluent mass emissions were lower for lower source concentration and aerobic conditions. At the end of the study, soil core samples were taken every 6 in. Soil moisture content analyses showed that water had redistributed in the soil during the experiment. The soil at the bottom of the columns generally had higher moisture contents than initial values, and soil at the top had lower moisture contents. Profiles of the number of colony forming units of hydrocarbon-utilizing bacteria/g-soil indicated that the highest concentrations of degraders were located at the vertical intervals where maximum degradation activity was suggested by CO2 profiles. Finally, the near-steady conditions of each phase of the study were simulated using a three-dimensional transient numerical model. The model was fit to the Phase I data by adjusting soil properties, and then fit to Phase III data to obtain compound-specific first-order biodegradation rate constants ranging from 0.0 to 5.7x103 d-1.
ContributorsEscobar Melendez, Elsy (Author) / Johnson, Paul C. (Thesis advisor) / Andino, Jean (Committee member) / Forzani, Erica (Committee member) / Krajmalnik-Brown, Rosa (Committee member) / Kavazanjian, Edward (Committee member) / Arizona State University (Publisher)
Created2012
Description
Intimate coupling of Ti2 photocatalysis and biodegradation (ICPB) offers potential for degrading biorecalcitrant and toxic organic compounds much better than possible with conventional wastewater treatments. This study reports on using a novel sponge-type, Ti2-coated biofilm carrier that shows significant adherence of Ti2 to its exterior and the ability to accumulate biomass in its interior (protected from UV light and free radicals). First, this carrier was tested for ICPB in a continuous-flow photocatalytic circulating-bed biofilm reactor (PCBBR) to mineralize biorecalcitrant organic: 2,4,5-trichlorophenol (TCP). Four mechanisms possibly acting of ICPB were tested separately: TCP adsorption, UV photolysis/photocatalysis, and biodegradation. The carrier exhibited strong TCP adsorption, while photolysis was negligible. Photocatalysis produced TCP-degradation products that could be mineralized and the strong adsorption of TCP to the carrier enhanced biodegradation by relieving toxicity. Validating the ICPB concept, biofilm was protected inside the carriers from UV light and free radicals. ICPB significantly lowered the diversity of the bacterial community, but five genera known to biodegrade chlorinated phenols were markedly enriched. Secondly, decolorization and mineralization of reactive dyes by ICPB were investigated on a refined Ti2-coated biofilm carrier in a PCBBR. Two typical reactive dyes: Reactive Black 5 (RB5) and Reactive Yellow 86 (RY86), showed similar first-order kinetics when being photocatalytically decolorized at low pH (~4-5), which was inhibited at neutral pH in the presence of phosphate or carbonate buffer, presumably due to electrostatic repulsion from negatively charged surface sites on Ti2, radical scavenging by phosphate or carbonate, or both. In the PCBBR, photocatalysis alone with Ti2-coated carriers could remove RB5 and COD by 97% and 47%, respectively. Addition of biofilm inside macroporous carriers maintained a similar RB5 removal efficiency, but COD removal increased to 65%, which is evidence of ICPB despite the low pH. A proposed ICPB pathway for RB5 suggests that a major intermediate, a naphthol derivative, was responsible for most of the residual COD. Finally, three low-temperature sintering methods, called O, D and DN, were compared based on photocatalytic efficiency and Ti2 adherence. The DN method had the best Ti2-coating properties and was a successful carrier for ICPB of RB5 in a PCBBR.
ContributorsLi, Guozheng (Author) / Rittmann, Bruce E. (Thesis advisor) / Halden, Rolf (Committee member) / Krajmalnik-Brown, Rosa (Committee member) / Arizona State University (Publisher)
Created2011
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