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- All Subjects: Environmental engineering
- Genre: Academic theses
- Creators: Hristovski, Kiril
- Creators: Torres, César I
Description
The goal of the study was twofold: (i) to investigate the synthesis of hematite-impregnated granular activated carbon (Fe-GAC) by hydrolysis of Fe (III) and (ii) to assess the effectiveness of the fabricated media in removal of arsenic from water. Fe-GAC was synthesized by hydrolysis of Fe(III) salts under two Fe (III) initial dosages (0.5M and 2M) and two hydrolysis periods (24 hrs and 72 hrs). The iron content of the fabricated Fe-GAC media ranged from 0.9% to 4.4% Fe/g of the dry media. Pseudo-equilibrium batch test data at pH = 7.7±0.2 in 1mM NaHCO3 buffered ultrapure water and challenge groundwater representative of the Arizona Mexico border region were fitted to a Freundlich isotherm model. The findings suggested that the arsenic adsorption capacity of the metal (hydr)oxide modified GAC media is primarily controlled by the surface area of the media, while the metal content exhibited lesser effect. The adsorption capacity of the media in the model Mexican groundwater matrix was significantly lower for all adsorbent media. Continuous flow short bed adsorber tests (SBA) demonstrated that the adsorption capacity for arsenic in the challenge groundwater was reduced by a factor of 3 to 4 as a result of the mass transport effects. When compared on metal basis, the iron (hydr)oxide modified media performed comparably well as existing commercial media for treatment of arsenic. On dry mass basis, the fabricated media in this study removed less arsenic than their commercial counterparts because the metal content of the commercial media was significantly higher.
ContributorsJain, Arti (Author) / Hristovski, Kiril (Thesis advisor) / Olson, Larry (Committee member) / Madar, David (Committee member) / Edwards, David (Committee member) / Arizona State University (Publisher)
Created2011
Description
Local municipalities in the Phoenix Metropolitan Area have voiced an interest in purchasing alternate source water with lower DBP precursors. Along the primary source is a hydroelectric dam in which water will be diverted from. This project is an assessment of optimizing the potential blends of source water to a water treatment plant in an effort to enable them to more readily meet DBP regulations. To perform this analysis existing water treatment models were used in conjunction with historic water quality sampling data to predict chemical usage necessary to meet DBP regulations. A retrospective analysis was performed for the summer months of 2007 regarding potential for the WTP to reduce cost through optimizing the source water by an average of 30% over the four-month period, accumulating to overall treatment savings of $154 per MG ($82 per AF).
ContributorsRice, Jacelyn (Author) / Westerhoff, Paul (Thesis advisor) / Fox, Peter (Committee member) / Hristovski, Kiril (Committee member) / Arizona State University (Publisher)
Created2011
Description
Titanium dioxide (TiO2) nanomaterial use is becoming more prevalent as is the likelihood of human exposure and environmental release. The goal of this thesis is to develop analytical techniques to quantify the level of TiO2 in complex matrices to support environmental, health, and safety research of TiO2 nanomaterials. A pharmacokinetic model showed that the inhalation of TiO2 nanomaterials caused the highest amount to be absorbed and distributed throughout the body. Smaller nanomaterials (< 5nm) accumulated in the kidneys before clearance. Nanoparticles of 25 nm diameter accumulated in the liver and spleen and were cleared from the body slower than smaller nanomaterials. A digestion method using nitric acid, hydrofluoric acid, and hydrogen peroxide was found to digest organic materials and TiO2 with a recovery of >80%. The samples were measured by inductively coupled plasma-mass spectrometry (ICP-MS) and the method detection limit was 600 ng of Ti. An intratracheal instillation study of TiO2 nanomaterials in rats found anatase TiO2 nanoparticles in the caudal lung lobe of rats 1 day post instillation at a concentration of 1.2 ug/mg dry tissue, the highest deposition rate of any TiO2 nanomaterial. For all TiO2 nanomaterial morphologies the concentrations in the caudal lobes were significantly higher than those in the cranial lobes. In a study of TiO2 concentration in food products, white colored foods or foods with a hard outer shell had higher concentrations of TiO2. Hostess Powdered Donettes were found to have the highest Ti mass per serving with 200 mg Ti. As much as 3.8% of the total TiO2 mass was able to pass through a 0.45 um indicating that some of the TiO2 is likely nanosized. In a study of TiO2 concentrations in personal care products and paints, the concentration of TiO2 was as high as 117 ug/mg in Benjamin Moore white paint and 70 ug/mg in a Neutrogena sunscreen. Greater than 6% of Ti in one sunscreen was able to pass through a 0.45 um filter. The nanosized TiO2 in food products and personal care products may release as much as 16 mg of nanosized TiO2 per individual per day to wastewater.
ContributorsWeir, Alex Alan (Author) / Westerhoff, Paul K (Thesis advisor) / Hristovski, Kiril (Committee member) / Herckes, Pierre (Committee member) / Arizona State University (Publisher)
Created2011
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
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
Hexavalant chromium (Cr(VI)) poses an emerging concern in drinking water treatment with stricter regulations on the horizon. Photocatalytic reduction of Cr(VI) was investigated as an engineering scale option to remove hexavalent chromium from drinking or industrial waters via a UV/titanium dioxide (TiO2) process. Using an integrated UV lamp/ceramic membrane system to recirculate TiO2, both hexavalent and total chromium levels were reduced through photocatalytic processes without additional chemicals. Cr(VI) removal increased as a function of higher energy input and TiO2 dosage, achieving above 90% removal for a 1g/L dose of TiO2. Surface analysis of effluent TiO2 confirmed the presence of chromium species.
ContributorsStancl, Heather O'Neal (Author) / Westerhoff, Paul K (Thesis advisor) / Chan, Candace (Committee member) / Hristovski, Kiril (Committee member) / Arizona State University (Publisher)
Created2013
Description
As engineered nanomaterials (NMs) become used in industry and commerce their loading to sewage will increase. However, the fate of widely used NMs in wastewater treatment plants (WWTPs) remains poorly understood. In this research, sequencing batch reactors (SBRs) were operated with hydraulic (HRT) and sludge (SRT) retention times representative of full-scale biological WWTPs for several weeks. NM loadings at the higher range of expected environmental concentrations were selected. To achieve the pseudo-equilibrium state concentration of NMs in biomass, SBR experiments needed to operate for more than three times the SRT value, approximately 18 days. Under the conditions tested, NMs had negligible effects on ability of the wastewater bacteria to biodegrade organic material, as measured by chemical oxygen demand (COD). NM mass balance closure was achieved by measuring NMs in liquid effluent and waste biosolids. All NMs were well removed at the typical biomass concentration (1~2 gSS/L). However, carboxy-terminated polymer coated silver nanoparticles (fn-Ag) were removed less effectively (88% removal) than hydroxylated fullerenes (fullerols; >90% removal), nano TiO2 (>95% removal) or aqueous fullerenes (nC60; >95% removal). Although most NMs did not settle out of the feed solution without bacteria present, approximately 65% of the titanium dioxide was removed even in the absence of biomass simply due to self-aggregation and settling. Experiments conducted over 4 months with daily loadings of nC60 showed that nC60 removal from solution depends on the biomass concentration. Under conditions representative of most suspended growth biological WWTPs (e.g., activated sludge), most of the NMs will accumulate in biosolids rather than in liquid effluent discharged to surface waters. Significant fractions of fn-Ag were associated with colloidal material which suggests that efficient particle separation processes (sedimentation or filtration) could further improve removal of NM from effluent. As most NMs appear to accumulate in biosolids, future research should examine the fate of NMs during disposal of WWTP biosolids, which may occur through composting or anaerobic digestion and/or land application, incineration, or landfill disposal.
ContributorsWang, Yifei (Author) / Westerhoff, Paul (Thesis advisor) / Krajmalnik-Brown, Rosa (Committee member) / Rittmann, Bruce (Committee member) / Hristovski, Kiril (Committee member) / Arizona State University (Publisher)
Created2012
Description
Population growth and fresh water depletion challenge drinking water utilities. Surface water quality is impacted significantly by climate variability, human activities, and extreme events like natural disasters. Dissolved organic carbon (DOC) is an important water quality index and the precursor of disinfection by-products (DBPs) that varies with both hydrologic and anthropogenic factors. Granular activated carbon (GAC) is a best available technology for utilities to meet Stage 2 D/DBP rule compliance and to remove contaminants of emerging concern (CECs) (e.g., pharmaceutical, personal care products (PCPs), etc.). Utilities can operate GAC with more efficient and flexible strategies with the understanding of organic occurrence in source water and a model capable predicting DOC occurrence. In this dissertation, it was found that DOC loading significantly correlated with spring runoff and was intensified by dry-duration antecedent to first flush. Dynamic modeling based on reservoir management (e.g., pump-back operation) was established to simulate the DOC transport in the reservoir system. Additionally, summer water recreational activities were found to raise the level of PCPs, especially skin-applied products, in raw waters. GAC was examined in this dissertation for both carbonaceous and emerging nitrogenous DBP (N-DBP) precursors (i.e., dissolved organic nitrogen (DON)) removal. Based on the experimental findings, GAC preferentially removes UV254-absorbing material, and DOC is preferentially removed over DON which may be composed primarily of hydrophilic organic and results in the low affinity for adsorption by GAC. The presence of organic nitrogen can elevate the toxicity of DBPs by forming N-DBPs, and this could be a major drawback for facilities considering installation of a GAC adsorber owing to the poor removal efficiency of DON by GAC. A modeling approach was established for predicting DOC and DON breakthrough during GAC operation. However, installation of GAC adsorber is a burden for utilities with respect to operational and maintenance cost. It is common for utilities to regenerate saturated GAC in order to save the cost of purchasing fresh GAC. The traditional thermal regeneration technology for saturated GAC is an energy intensive process requiring high temperature of incineration. Additionally, small water treatment sites usually ship saturated GAC to specialized facilities for regeneration increasing the already significant carbon footprint of thermal regeneration. An innovative GAC regeneration technique was investigated in this dissertation for the feasibility as on-site water treatment process. Virgin GAC was first saturated by organic contaminant then regenerated in-situ by iron oxide nanocatalysts mixed with hydrogen peroxide. At least 70 % of adsorption capacity of GAC can be regenerated repeatedly for experiments using modeling compound (phenol) or natural organic matter (Suwannee River humic acid). The regeneration efficiency increases with increasing adsorbate concentration. Used-iron nanocatalysts can be recovered repeatedly without significant loss of catalytic ability. This in-situ regeneration technique provides cost and energy efficient solution for water utilities considering GAC installation. Overall, patterns were found for DOC and CEC variations in drinking water sources. Increasing concentrations of bulk (DOC and DON) and/or trace organics challenge GAC operation in utilities that have limited numbers of bed-volume treated before regeneration is required. In-situ regeneration using iron nanocatalysts and hydrogen peroxide provides utilities an alternative energy-efficient operation mode when considering installation of GAC adsorber.
ContributorsChiu, Chao-An (Author) / Westerhoff, Paul (Thesis advisor) / Rittmann, Bruce (Committee member) / Hristovski, Kiril (Committee member) / Arizona State University (Publisher)
Created2012
Description
Electroactive bacteria connect biology to electricity, acting as livingelectrochemical catalysts. In nature, these bacteria can respire insoluble compounds like
iron oxides, and in the laboratory, they are able to respire an electrode and produce an
electrical current. This document investigates two of these electroactive bacteria:
Geobacter sulfurreducens and Thermincola ferriacetica. G. sulfurreducens is a Gramnegative iron-reducing soil bacterium, and T. ferriacetica is a thermophilic, Grampositive bacterium that can reduce iron minerals and several other electron acceptors.
Respiring insoluble electron acceptors like metal oxides presents challenges to a
bacterium. The organism must extend its electron transport chain from the inner
membrane outside the cell and across a significant distance to the surface of the electron
acceptor. G. sulfurreducens is one of the most-studied electroactive bacteria, and despite
this there are many gaps in knowledge about its mechanisms for transporting electrons
extracellularly. Research in this area is complicated by the presence of multiple pathways
that may be concurrently expressed. I used cyclic voltammetry to determine which
pathways are present in electroactive biofilms of G. sulfurreducens grown under different
conditions and correlated this information with gene expression data from the same
conditions. This correlation presented several genes that may be components of specific
pathways not just at the inner membrane but along the entire respiratory pathway, and I
propose an updated model of the pathways in this organism. I also characterized the
composition of G. sulfurreducens and found that it has high iron and lipid content
independent of growth condition, and the high iron content is explained by the large
abundance of multiheme cytochrome expression that I observed. I used multiple
microscopy techniques to examine extracellular respiration in G. sulfurreducens, and in
the process discovered a novel organelle: the intracytoplasmic membrane. I show 3D
reconstructions of the organelle in G. sulfurreducens and discuss its implications for the
cell’s metabolism. Finally, I discuss gene expression in T. ferriacetica in RNA samples
collected from an anode-respiring culture and highlight the most abundantly expressed
genes related to anode-respiring metabolism.
ContributorsHowley, Ethan Thomas (Author) / Torres, César I (Thesis advisor) / Krajmalnik-Brown, Rosa (Thesis advisor) / Nannenga, Brent (Committee member) / Arizona State University (Publisher)
Created2022
Description
Trichloroethene (TCE) and hexavalent chromium (Cr (VI)) are ubiquitous subsurface contaminants affecting the water quality and threatening human health. Microorganisms capable of TCE and Cr (VI) reductions can be explored for bioremediation at contaminated sites. The goal of my dissertation research was to address challenges that decrease the efficiency of bioremediation in the subsurface. Specifically, I investigated strategies to (i) promote improve microbial reductive dechlorination extent through the addition of Fe0 and (ii) Cr (VI) bio-reduction through enrichment of specialized microbial consortia. Fe0 can enhance microbial TCE reduction by inducing anoxic conditions and generating H2 (electron donor). I first evaluated the effect of Fe0 on microbial reduction of TCE (with ClO4– as co-contaminant) using semi-batch soil microcosms. Results showed that high concentration of Fe0 expected during in situ remediation inhibited microbial TCE and ClO4– reduction when added together with Dehalococcoides mccartyi-containing cultures. A low concentration of aged Fe0 enhanced microbial TCE dechlorination to ethene and supported complete microbial ClO4– reduction. I then evaluated a decoupled Fe0 and biostimulation/bioaugmentation treatment approach using soil packed columns with continuous flow of groundwater. I demonstrated that microbial TCE reductive dechlorination to ethene can be benefitted by Fe0 abiotic reactions, when biostimulation and bioaugmentation are performed downstream of Fe0 addition. Furthermore, I showed that ethene production can be sustained in the presence of aerobic groundwater (after Fe0 exhaustion) by the addition of organic substrates. I hypothesized that some lessons learned from TCE Bioremediation can be applied also for other pollutants that can benefit from anaerobic reductions, like Cr (VI). Bioremediation of Cr (VI) has historically relied on biostimulation of native microbial communities, partially due to the lack of knowledge of the benefits of adding enriched consortia of specialized microorganisms (bioaugmentation). To determine the merits of a specialized consortium on bio-reduction of Cr (VI), I first enriched a culture on lactate and Cr (VI). The culture had high abundance of putative Morganella species and showed rapid and sustained Cr (VI) bio-reduction compared to a subculture grown with lactate only (without Morganella). Overall, this dissertation work documents possible strategies for synergistic abiotic and biotic chlorinated ethenes reduction, and highlights that specialized consortia may benefit Cr (VI) bio-reduction.
ContributorsMohana Rangan, Srivatsan (Author) / Krajmalnik-Brown, Rosa (Thesis advisor) / Delgado, Anca G (Thesis advisor) / Torres, César I (Committee member) / van Paassen, Leon (Committee member) / Arizona State University (Publisher)
Created2022