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- All Subjects: Environmental engineering
- Creators: Abbaszadegan, Morteza
- Creators: Halden, Rolf U.
Analysis of photocatalysis for precursor removal and formation inhibition of disinfection byproducts
Description
Disinfection byproducts are the result of reactions between natural organic matter (NOM) and a disinfectant. The formation and speciation of DBP formation is largely dependent on the disinfectant used and the natural organic matter (NOM) concentration and composition. This study examined the use of photocatalysis with titanium dioxide for the oxidation and removal of DBP precursors (NOM) and the inhibition of DBP formation. Water sources were collected from various points in the treatment process, treated with photocatalysis, and chlorinated to analyze the implications on total trihalomethane (TTHM) and the five haloacetic acids (HAA5) formations. The three sub-objectives for this study included: the comparison of enhanced and standard coagulation to photocatalysis for the removal of DBP precursors; the analysis of photocatalysis and characterization of organic matter using size exclusion chromatography and fluorescence spectroscopy and excitation-emission matrices; and the analysis of photocatalysis before GAC filtration. There were consistencies in the trends for each objective including reduced DBP precursors, measured as dissolved organic carbon DOC concentration and UV absorbance at 254 nm. Both of these parameters decreased with increased photocatalytic treatment and could be due in part to the adsorption to as well as the oxidation of NOM on the TiO2 surface. This resulted in lower THM and HAA concentrations at Medium and High photocatalytic treatment levels. However, at No UV exposure and Low photocatalytic treatment levels where oxidation reactions were inherently incomplete, there was an increase in THM and HAA formation potential, in most cases being significantly greater than those found in the raw water or Control samples. The size exclusion chromatography (SEC) results suggest that photocatalysis preferentially degrades the higher molecular mass fraction of NOM releasing lower molecular mass (LMM) compounds that have not been completely oxidized. The molecular weight distributions could explain the THM and HAA formation potentials that decreased at the No UV exposure samples but increased at Low photocatalytic treatment levels. The use of photocatalysis before GAC adsorption appears to increase bed life of the contactors; however, higher photocatalytic treatment levels have been shown to completely mineralize NOM and would therefore not require additional GAC adsorption after photocatalysis.
ContributorsDaugherty, Erin (Author) / Abbaszadegan, Morteza (Thesis advisor) / Fox, Peter (Committee member) / Mayer, Brooke (Committee member) / Arizona State University (Publisher)
Created2011
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
Many manmade chemicals used in consumer products are ultimately washed down the drain and are collected in municipal sewers. Efficient chemical monitoring at wastewater treatment (WWT) plants thus may provide up-to-date information on chemical usage rates for epidemiological assessments. The objective of the present study was to extrapolate this concept, termed 'sewage epidemiology', to include municipal sewage sludge (MSS) in identifying and prioritizing contaminants of emerging concern (CECs). To test this the following specific aims were defined: i) to screen and identify CECs in nationally representative samples of MSS and to provide nationwide inventories of CECs in U.S. MSS; ii) to investigate the fate and persistence in MSS-amended soils, of sludge-borne hydrophobic CECs; and iii) to develop an analytical tool relying on contaminant levels in MSS as an indicator for identifying and prioritizing hydrophobic CECs. Chemicals that are primarily discharged to the sewage systems (alkylphenol surfactants) and widespread persistent organohalogen pollutants (perfluorochemicals and brominated flame retardants) were analyzed in nationally representative MSS samples. A meta-analysis showed that CECs contribute about 0.04-0.15% to the total dry mass of MSS, a mass equivalent of 2,700-7,900 metric tonnes of chemicals annually. An analysis of archived mesocoms from a sludge weathering study showed that 64 CECs persisted in MSS/soil mixtures over the course of the experiment, with half-lives ranging between 224 and >990 days; these results suggest an inherent persistence of CECs that accumulate in MSS. A comparison of the spectrum of chemicals (n=52) analyzed in nationally representative biological specimens from humans and MSS revealed 70% overlap. This observed co-occurrence of contaminants in both matrices suggests that MSS may serve as an indicator for ongoing human exposures and body burdens of pollutants in humans. In conclusion, I posit that this novel approach in sewage epidemiology may serve to pre-screen and prioritize the several thousands of known or suspected CECs to identify those that are most prone to pose a risk to human health and the environment.
ContributorsVenkatesan, Arjunkrishna (Author) / Halden, Rolf U. (Thesis advisor) / Westerhoff, Paul (Committee member) / Fox, Peter (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
In situ remediation of contaminated aquifers, specifically in situ bioremediation (ISB), has gained popularity over pump-and-treat operations. It represents a more sustainable approach that can also achieve complete mineralization of contaminants in the subsurface. However, the subsurface reality is very complex, characterized by hydrodynamic groundwater movement, geological heterogeneity, and mass-transfer phenomena governing contaminant transport and bioavailability. These phenomena cannot be properly studied using commonly conducted laboratory batch microcosms lacking realistic representation of the processes named above. Instead, relevant processes are better understood by using flow-through systems (sediment columns). However, flow-through column studies are typically conducted without replicates. Due to additional sources of variability (e.g., flow rate variation between columns and over time), column studies are expected to be less reproducible than simple batch microcosms. This was assessed through a comprehensive statistical analysis of results from multiple batch and column studies. Anaerobic microbial biotransformations of trichloroethene and of perchlorate were chosen as case studies. Results revealed that no statistically significant differences were found between reproducibility of batch and column studies. It has further been recognized that laboratory studies cannot accurately reproduce many phenomena encountered in the field. To overcome this limitation, a down-hole diagnostic device (in situ microcosm array - ISMA) was developed, that enables the autonomous operation of replicate flow-through sediment columns in a realistic aquifer setting. Computer-aided design (CAD), rapid prototyping, and computer numerical control (CNC) machining were used to create a tubular device enabling practitioners to conduct conventional sediment column studies in situ. A case study where two remediation strategies, monitored natural attenuation and bioaugmentation with concomitant biostimulation, were evaluated in the laboratory and in situ at a perchlorate-contaminated site. Findings demonstrate the feasibility of evaluating anaerobic bioremediation in a moderately aerobic aquifer. They further highlight the possibility of mimicking in situ remediation strategies on the small-scale in situ. The ISMA is the first device offering autonomous in situ operation of conventional flow-through sediment microcosms and producing statistically significant data through the use of multiple replicates. With its sustainable approach to treatability testing and data gathering, the ISMA represents a versatile addition to the toolbox of scientists and engineers.
ContributorsMcClellan, Kristin (Author) / Halden, Rolf U. (Thesis advisor) / Johnson, Paul C (Committee member) / Krajmalnik-Brown, Rosa (Committee member) / Arizona State University (Publisher)
Created2013
Description
Bacteroides have been suggested as alternative indicators of fecal pollution since they are highly abundant in feces and are thought to have limited potential to grow in environment. However, recent literature suggests that Bacteroides can potentially survive within water distribution systems. The first objective of this study was therefore to investigate the validity of Bacteroides as a fecal indicator for drinking water through laboratory experiments and field studies. Experiments were performed using a laboratory scale PVC model water distribution system that was spiked with 109 Bacteroides. Samples were collected over the following four and analyzed by culture and molecular-based techniques. Second, field studies were performed by collecting water meters from two large chlorinated water distribution systems in central Arizona. Upon removal for repair by city personnel, meters were collected and biofilms samples were gathered within two hours. The biofilms were then analyzed using culture and molecular-based assays. The results from these studies support the hypothesis that Bacteroides DNA may be found in water distribution systems despite the difficulty of cultivating these bacterial cells. These experiments present the importance of considering biofilm interactions with fecal indicator bacteria when performing molecular assays on environmental samples, as biofilms may provide protection from high oxygen concentrations and grazing protozoa in bulk water that limit the persistence Bacteroides in the environment. Although the significance of biofilm interactions with surface or recreational waters may be small, they are likely important when considering drinking water delivered through distribution systems. The second objective of this study was to investigate alternative detection methodologies for the fecal indicator Bacteroides. In particular, this study focused on using a simplified protocol of Nucleic Acid Sequence Based Amplification (NASBA) and Thermophilic Helicase-Dependent Amplification (tHDA) to amplify the highly conserved 16s rRNA gene in the genomic DNA of fecal indicator Bacteroides. The results of this study show that the simplified NASBA procedure was not able to amplify the target, while continuous problems with tHDA exposed the methods lack of reliability. These results suggest higher reliability in the isothermal amplification methods needs to be achieved before application to environmental samples.
ContributorsDunkin, Nate (Author) / Abbaszadegan, Morteza (Thesis advisor) / Alum, Absar (Committee member) / Fox, Peter (Committee member) / Arizona State University (Publisher)
Created2012
Analysis and modeling of residual compounds in process streams from U.S. wastewater treatment plants
Description
The presence of compounds such as pharmaceuticals and personal care products (PPCPs) in the environment is a cause for concern as they exhibit secondary effects on non-target organisms and are also indicative of incomplete removal by wastewater treatment plants (WWTPs) during water reclamation. Analytical methods and predictive models can help inform on the rates at which these contaminants enter the environment via biosolids use or wastewater effluent release to estimate the risk of adverse effects. The goals of this research project were to integrate the results obtained from the two different methods of risk assessment, (a) in silico modeling and (b) experimental analysis. Using a previously published empirical model, influent and effluent concentration ranges were predicted for 10 sterols and validated with peer-reviewed literature. The in silico risk assessment analysis performed for sterols and hormones in biosolids concluded that hormones possess high leaching potentials and that particularly 17-α-ethinyl estradiol (EE2) can pose significant threat to fathead minnows (P. promelas) via leaching from terrestrial depositions of biosolids. Six mega-composite biosolids samples representative of 94 WWTPs were analyzed for a suite of 120 PPCPs using the extended U.S. EPA Method 1694 protocol. Results indicated the presence of 26 previously unmonitored PPCPs in the samples with estimated annual release rates of 5-15 tons yr-1 via land application of biosolids. A mesocosm sampling analysis that was included in the study concluded that four compounds amitriptyline, paroxetine, propranolol and sertraline warrant further monitoring due to their high release rates from land applied biosolids and their calculated extended half-lives in soils. There is a growing interest in the scientific community towards the development of new analytical protocols for analyzing solid matrices such as biosolids for the presence of PPCPs and other established and emerging contaminants of concern. The two studies presented here are timely and an important addition to the increasing base of scientific articles regarding environmental release of PPCPs and exposure risks associated with biosolids land application. This research study emphasizes the need for coupling experimental results with predictive analytical modeling output in order to more fully assess the risks posed by compounds detected in biosolids.
ContributorsPrakash Chari, Bipin (Author) / Halden, Rolf U. (Thesis advisor) / Westerhoff, Paul (Committee member) / Fox, Peter (Committee member) / Arizona State University (Publisher)
Created2012
Description
Contamination by chlorinated ethenes is widespread in groundwater aquifers, sediment, and soils worldwide. The overarching objectives of my research were to understand how the bacterial genus Dehalococcoides function optimally to carry out reductive dechlorination of chlorinated ethenes in a mixed microbial community and then apply this knowledge to manage dechlorinating communities in the hydrogen-based membrane biofilm reactor (MBfR). The MBfR is used for the biological reduction of oxidized contaminants in water using hydrogen supplied as the electron donor by diffusion through gas-transfer fibers. First, I characterized a new anaerobic dechlorinating community developed in our laboratory, named DehaloR^2, in terms of chlorinated ethene turnover rates and assessed its microbial community composition. I then carried out an experiment to correlate performance and community structure for trichloroethene (TCE)-fed microbial consortia. Fill-and-draw reactors inoculated with DehaloR^2 demonstrated a direct correlation between microbial community function and structure as the TCE-pulsing rate was increased. An electron-balance analysis predicted the community structure based on measured concentrations of products and constant net yields for each microorganism. The predictions corresponded to trends in the community structure based on pyrosequencing and quantitative PCR up to the highest TCE pulsing rate, where deviations to the trend resulted from stress by the chlorinated ethenes. Next, I optimized a method for simultaneous detection of chlorinated ethenes and ethene at or below the Environmental Protection Agency maximum contaminant levels for groundwater using solid phase microextraction in a gas chromatograph with a flame ionization detector. This method is ideal for monitoring biological reductive dechlorination in groundwater, where ethene is the ultimate end product. The major advantage of this method is that it uses a small sample volume of 1 mL, making it ideally suited for bench-scale feasibility studies, such as the MBfR. Last, I developed a reliable start-up and operation strategy for TCE reduction in the MBfR. Successful operation relied on controlling the pH-increase effects of methanogenesis and homoacetogenesis, along with creating hydrogen limitation during start-up to allow dechlorinators to compete against other microorgansims. Methanogens were additionally minimized during continuous flow operation by a limitation in bicarbonate resulting from strong homoacetogenic activity.
ContributorsZiv-El, Michal (Author) / Rittmann, Bruce E. (Thesis advisor) / Krajmalnik-Brown, Rosa (Thesis advisor) / Halden, Rolf U. (Committee member) / Arizona State University (Publisher)
Created2012
Description
Water quality in surface water is frequently degraded by fecal contamination from human and animal sources, imposing negative implications for recreational water use and public safety. For this reason it is critical to identify the source of fecal contamination in bodies of water in order to take proper corrective actions for controlling fecal pollution. Bacteroides genetic markers have been widely used to differentiate human from other sources of fecal bacteria in water. The results of this study indicate that many assays currently used to detect human-specific Bacteroides produce false positive results in the presence of freshwater fish. To further characterize Bacteroides from fish and human, the fecal samples were cultured, speciated, and identified. As a result, forty six new Bacteroides 16S rRNA gene sequences have been deposited to the NCBI database. These sequences, along with selected animal fecal sample Bacteroides, were aligned against human B. volgatus, B. fragilis, and B. dorei to identify multi-segmented variable regions within the 16S rRNA gene sequence. The collected sequences were truncated and used to construct a cladogram, showing a clear separation between human B. dorei and Bacteroides from other sources. A proposed strategy for source tracking was field tested by collecting water samples from central AZ source water and three different recreational ponds. PCR using HF134 and HF183 primer sets were performed and sequences for positive reactions were then aligned against human Bacteroides to identify the source of contamination. For the samples testing positive using the HF183 primer set (8/13), fecal contamination was determined to be from human sources. To confirm the results, PCR products were sequenced and aligned against the four variable regions and incorporated within the truncated cladogram. As expected, the sequences from water samples with human fecal contamination grouped within the human clade. As an outcome of this study, a tool box strategy for Bacteroides source identification relying on PCR amplification, variable region analysis, human-specific Bacteroides PCR assays, and subsequent truncated cladogram grouping analysis has been developed. The proposed strategy offers a new method for microbial source tracking and provides step-wise methodology essential for identifying sources of fecal pollution.
ContributorsKabiri-Badr, Leila (Author) / Abbaszadegan, Morteza (Thesis advisor) / Bingham, Scott (Committee member) / Rock, Channah (Committee member) / Fox, Peter (Committee member) / Mclain, Jean (Committee member) / Arizona State University (Publisher)
Created2012
Description
Nanotechnology is a scientific field that has recently expanded due to its applications in pharmaceutical and personal care products, industry and agriculture. As result of this unprecedented growth, nanoparticles (NPs) have become a significant environmental contaminant, with potential to impact various forms of life in environment. Metal nanoparticles (mNPs) exhibit unique properties such as increased chemical reactivity due to high specific surface area to volume ratios. Bacteria play a major role in many natural and engineered biogeochemical reactions in wastewater treatment plants and other environmental compartments. I have evaluated the laboratory isolates of E. coli, Bacillus, Alcaligenes, Pseudomonas; wastewater isolates of E. coli and Bacillus; and pathogenic isolate of E. coli for their response to 50 & 100 nm sized Cu nanoparticles (CuNPs). Bactericidal tests, scanning electron microscopy (SEM) analyses, and probable toxicity pathways assays were performed. The results indicate that under continuous mixing conditions, CuNPs are effective in inactivation of the selected bacterial isolates. In general, exposure to CuNPs resulted in 4 to >6 log reduction in bacterial population within 2 hours. Based on the GR, LDH and MTT assays, bacterial cells showed different toxicity elicitation pathways after exposure to CuNPs. Therefore, it can be concluded that the laboratory isolates are good candidates for predicting the behavior of environmental isolates exposed to CuNPs. Also, high inactivation values recorded in this study suggest that the presence of CuNPs in different environmental compartments may have an impact on pollutants attenuation and wastewater biological treatment processes. These results point towards the need for an in depth investigation of the impact of NPs on the biological processes; and long-term effect of high load of NPs on the stability of aquatic and terrestrial ecologies.
ContributorsAlboloushi, Ali (Author) / Abbaszadegan, Morteza (Thesis advisor) / Alum, Absar (Committee member) / Fox, Peter (Committee member) / Olson, Larry (Committee member) / Arizona State University (Publisher)
Created2012