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Description
This work focuses on a generalized assessment of source zone natural attenuation (SZNA) at chlorinated aliphatic hydrocarbon (CAH) impacted sites. Given the numbers of sites and technical challenges for cleanup there is a need for a SZNA method at CAH impacted sites. The method anticipates that decision makers will be

This work focuses on a generalized assessment of source zone natural attenuation (SZNA) at chlorinated aliphatic hydrocarbon (CAH) impacted sites. Given the numbers of sites and technical challenges for cleanup there is a need for a SZNA method at CAH impacted sites. The method anticipates that decision makers will be interested in the following questions: 1-Is SZNA occurring and what processes contribute? 2-What are the current SZNA rates? 3-What are the longer-term implications? The approach is macroscopic and uses multiple lines-of-evidence. An in-depth application of the generalized non-site specific method over multiple site events, with sampling refinement approaches applied for improving SZNA estimates, at three CAH impacted sites is presented with a focus on discharge rates for four events over approximately three years (Site 1:2.9, 8.4, 4.9, 2.8kg/yr as PCE, Site 2:1.6, 2.2, 1.7, 1.1kg/y as PCE, Site 3:570, 590, 250, 240kg/y as TCE). When applying the generalized CAH-SZNA method, it is likely that different practitioners will not sample a site similarly, especially regarding sampling density on a groundwater transect. Calculation of SZNA rates is affected by contaminant spatial variability with reference to transect sampling intervals and density with variations in either resulting in different mass discharge estimates. The effects on discharge estimates from varied sampling densities and spacings were examined to develop heuristic sampling guidelines with practical site sampling densities; the guidelines aim to reduce the variability in discharge estimates due to different sampling approaches and to improve confidence in SZNA rates allowing decision-makers to place the rates in perspective and determine a course of action based on remedial goals. Finally bench scale testing was used to address longer term questions; specifically the nature and extent of source architecture. A rapid in-situ disturbance method was developed using a bench-scale apparatus. The approach allows for rapid identification of the presence of DNAPL using several common pilot scale technologies (ISCO, air-sparging, water-injection) and can identify relevant source architectural features (ganglia, pools, dissolved source). Understanding of source architecture and identification of DNAPL containing regions greatly enhances site conceptualization models, improving estimated time frames for SZNA, and possibly improving design of remedial systems.
ContributorsEkre, Ryan (Author) / Johnson, Paul Carr (Thesis advisor) / Rittmann, Bruce (Committee member) / Krajmalnik-Brown, Rosa (Committee member) / Arizona State University (Publisher)
Created2013
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Description
Biofuel from microbial biomass is a viable alternative to current energy production practices that could mitigate greenhouse gas levels and reduce dependency on fossil fuels. Sustainable production of microbial biomass requires efficient utilization of nutrients like phosphorus (P). P is a limited resource which is vital for global food security.

Biofuel from microbial biomass is a viable alternative to current energy production practices that could mitigate greenhouse gas levels and reduce dependency on fossil fuels. Sustainable production of microbial biomass requires efficient utilization of nutrients like phosphorus (P). P is a limited resource which is vital for global food security. This paper seeks to understand the fate of P through biofuel production and proposes a proof-of-concept process to recover P from microbial biomass. The photosynthetic cyanobacterium Synechocystis sp. PCC 6803 is found to contain 1.4% P by dry weight. After the crude lipids are extracted for biofuel processing, 92% of the intercellular P is found within the residual biomass. Most intercellular P is associated with nucleic acids which remain within the cell after lipids are extracted. Phospholipids comprise a small percentage of cellular P. A wet chemical advanced oxidation process of adding 30% hydrogen peroxide followed by 10 min of microwave heating converts 92% of the total cellular P from organic-P and polyphosphate into orthophosphate. P was then isolated and concentrated from the complex digested matrix by use of resins. An anion exchange resin impregnated with iron nanoparticles demonstrates high affinity for P by sorbing 98% of the influent P through 20 bed volumes, but only was able to release 23% of it when regenerated. A strong base anion exchange resin sorbed 87% of the influent P through 20 bed volumes then released 50% of it upon regeneration. The overall P recovery process was able to recover 48% of the starting intercellular P into a pure and concentrated nutrient solution available for reuse. Further optimization of elution could improve P recovery, but this provides a proof-of-concept for converting residual biomass after lipid extraction to a beneficial P source.
ContributorsGifford, James McKay (Author) / Westerhoff, Paul (Thesis advisor) / Rittmann, Bruce (Committee member) / Vannela, Ravindhar (Committee member) / Arizona State University (Publisher)
Created2012
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Description
Nitrate, a widespread contaminant in surface water, can cause eutrophication and toxicity to aquatic organisms. To augment the nitrate-removal capacity of constructed wetlands, I applied the H2-based Membrane Biofilm Reactor (MBfR) in a novel configuration called the in situ MBfR (isMBfR). The goal of my thesis is to

Nitrate, a widespread contaminant in surface water, can cause eutrophication and toxicity to aquatic organisms. To augment the nitrate-removal capacity of constructed wetlands, I applied the H2-based Membrane Biofilm Reactor (MBfR) in a novel configuration called the in situ MBfR (isMBfR). The goal of my thesis is to evaluate and model the nitrate removal performance for a bench-scale isMBfR system.

I operated the bench-scale isMBfR system in 7 different conditions to evaluate its nitrate-removal performance. When I supplied H2 with the isMBfR (stages 1 - 6), I observed at least 70% nitrate removal, and almost all of the denitrification occurred in the "MBfR zone." When I stopped the H2 supply in stage 7, the nitrate-removal percentage immediately dropped from 92% (stage 6) to 11% (stage 7). Denitrification raised the pH of the bulk liquid to ~ 9.0 for the first 6 stages, but the high pH did not impair the performance of the denitrifiers. Microbial community analyses indicated that DB were the dominant bacteria in the "MBfR zone," while photosynthetic Cyanobacteria were dominant in the "photo-zone".

I derived stoichiometric relationships among COD, alkalinity, H2, Dissolved Oxygen (DO), and nitrate to model the nitrate removal capacity of the "MBfR zone." The stoichiometric relationships corresponded well to the nitrate-removal capacity for all stages expect stage 3, which was limited by the abundance of Denitrifying Bacteria (DB) so that the H2 supply capacity could not be completely used.

Finally, I analyzed two case studies for the real-world application of the isMBfR to constructed wetlands. Based on the characteristics for the wetlands and the stoichiometric relationships, I designed a feasible operation condition (membrane area and H2 pressure) for each wetland. In both cases, the amount of isMBfR surface area was modest, from 0.022 to 1.2 m2/m3 of wetland volume.
ContributorsLi, Yizhou (Author) / Rittmann, Bruce (Thesis advisor) / Vivoni, Enrique (Committee member) / Krajmalnik-Brown, Rosa (Committee member) / Arizona State University (Publisher)
Created2014
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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

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
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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

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
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Description
The production and applications of engineered nanomaterials (ENM) has increased rapidly in the last decade, with release of ENM to the environment through the sewer system and municipal wastewater treatment plants (WWTPs) being of concern. Currently, the literature on ENM release from WWTPs and removal of ENM by WWTPs is

The production and applications of engineered nanomaterials (ENM) has increased rapidly in the last decade, with release of ENM to the environment through the sewer system and municipal wastewater treatment plants (WWTPs) being of concern. Currently, the literature on ENM release from WWTPs and removal of ENM by WWTPs is insufficient and disorganized. There is little quantitative data on the removal of multi-walled carbon nanotubes (MWCNTs), graphene oxide (GO), or few-layer graphene (FLG), from wastewater onto biomass. The removal of pristine and oxidized MWCNTs (O-MWCNTs), graphene oxide (GO), few-layer graphene (FLG) and Tween™ 20-coated Ag ENM by the interaction with biomass were determined by programmable thermal analysis (PTA) and UV-Vis spectrophotometry. The removal of pristine and O-MWCNTs was 96% from the water phase via aggregation and 30-min settling in presence or absence of biomass with an initial MWCNT concentration of 25 mg/L. The removal of 25 mg/L GO was 65% with biomass concentration at or above 1,000 mg TSS/L. The removal of 1 mg/L FLG was 16% with 50 mg TSS/L. The removal of Tween™ 20 Ag ENM with concentration from 0.97 mg/L to 2.6 mg/L was from 11% to 92% with biomass concentration of 500 mg TSS/L to 3,000 mg TSS/L, respectively.

A database of ENM removal by biomass was established by analyzing data from published papers, and non-linear solid-liquid distribution functions were built into the database. A conventional activated sludge (CAS) model was built based on a membrane bioreactor (MBR) model from a previous paper. An iterative numeric approach was adapted to the CAS model to calculate the result of non-linear adsorption of ENM by biomass in the CAS process. Kinetic studies of the CAS model showed the model performance changed mostly in the first 10 days after changing influent chemical oxygen demand (COD) concentration, and reached a steady state after 11 days. Over 60% of ENMs which have distribution coefficients in the database reached higher than 50% removal by the CAS model under general operational conditions. This result suggests that traditional WWTP which include the CAS process can remove many known types of ENMs in certain degree.
ContributorsYu, Zhicheng (Author) / Westerhoff, Paul (Thesis advisor) / Rittmann, Bruce (Committee member) / Herckes, Pierre (Committee member) / Arizona State University (Publisher)
Created2015
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Description
To date, the production of algal biofuels is not economically sustainable due to the cost of production and the low cost of conventional fuels. As a result, interest has been shifting to high value products in the algae community to make up for the low economic potential of algal biofuels.

To date, the production of algal biofuels is not economically sustainable due to the cost of production and the low cost of conventional fuels. As a result, interest has been shifting to high value products in the algae community to make up for the low economic potential of algal biofuels. The economic potential of high-value products does not however, eliminate the need to consider the environmental impacts. The majority of the environmental impacts associated with algal biofuels overlap with algal bioproducts in general (high-energy dewatering) due to the similarities in their production pathways. Selecting appropriate product sets is a critical step in the commercialization of algal biorefineries.

This thesis evaluates the potential of algae multiproduct biorefineries for the production of fuel and high-value products to be economically self-sufficient and still contribute to climate change mandates laid out by the government via the Energy Independence and Security Act (EISA) of 2007. This research demonstrates:

1) The environmental impacts of algal omega-3 fatty acid production can be lower than conventional omega-3 fatty acid production, depending on the dewatering strategy.

2) The production of high-value products can support biofuels with both products being sold at prices comparable to 2016 prices.

3) There is a tradeoff between revenue and fuel production

4) There is a tradeoff between the net energy ratio of the algal biorefinery and the economic viability due to the lower fuel production in a multi-product model that produces high-value products and diesel vs. the lower economic potential from a multi-product model that just produces diesel.

This work represents the first efforts to use life cycle assessment and techno-economic analysis to assess the economic and environmental sustainability of an existing pilot-scale biorefinery tasked with the production of high-value products and biofuels. This thesis also identifies improvements for multiproduct algal biorefineries that will achieve environmentally sustainable biofuel and products while maintaining economic viability.
ContributorsBarr, William James (Author) / Landis, Amy E. (Thesis advisor) / Westerhoff, Paul (Thesis advisor) / Rittmann, Bruce (Committee member) / Khanna, Vikas (Committee member) / Arizona State University (Publisher)
Created2016
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Description
The dissimilatory reduction of nitrate, or denitrification, offers the potential of a sustainable, cost effective method for the non-disruptive mitigation of earthquake-induced soil liquefaction. Worldwide, trillions of dollars of infrastructure are at risk for liquefaction damage in earthquake prone regions. However, most techniques for remediating liquefiable soils are

The dissimilatory reduction of nitrate, or denitrification, offers the potential of a sustainable, cost effective method for the non-disruptive mitigation of earthquake-induced soil liquefaction. Worldwide, trillions of dollars of infrastructure are at risk for liquefaction damage in earthquake prone regions. However, most techniques for remediating liquefiable soils are either not applicable to sites near existing infrastructure, or are prohibitively expensive. Recently, laboratory studies have shown the potential for biogeotechnical soil improvement techniques such as microbially induced carbonate precipitation (MICP) to mitigate liquefaction potential in a non-disruptive manner. Multiple microbial processes have been identified for MICP, but only two have been extensively studied. Ureolysis, the most commonly studied process for MICP, has been shown to quickly and efficiently induce carbonate precipitation on particle surfaces and at particle contacts to improve the stiffness, strength, and dilatant behavior of liquefiable soils. However, ureolysis also produces copious amounts of ammonium, a potentially toxic byproduct. The second process studied for MICP, denitrification, has been shown to precipitate carbonate, and hence improve soil properties, much more slowly than ureolysis. However, the byproducts of denitrification, nitrogen and carbon dioxide gas, are non-toxic, and present the added benefit of rapidly desaturating the treated soil. Small amounts of desaturation have been shown to increase the cyclic resistance, and hence the liquefaction resistance, of liquefiable soils. So, denitrification offers the potential to mitigate liquefaction as a two-stage process, with desaturation providing short term mitigation, and MICP providing long term liquefaction resistance. This study presents the results of soil testing, stoichiometric modeling, and microbial ecology characterization to better characterize the potential use of denitrification as a two-stage process for liquefaction mitigation.
ContributorsO'Donnell, Sean (Author) / Kavazanjian, Edward (Thesis advisor) / Rittmann, Bruce (Committee member) / Houston, Sandra (Committee member) / Arizona State University (Publisher)
Created2016
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Description
The waterways in the United States are polluted by agricultural, mining, and industrial activities. Recovery of valuable materials, such as energy and nutrients, from these waste streams can improve the economic and environmental sustainability of wastewater treatment. A number of state-of-the-art anaerobic bioreactors have promise for intensified anaerobic biological treatment

The waterways in the United States are polluted by agricultural, mining, and industrial activities. Recovery of valuable materials, such as energy and nutrients, from these waste streams can improve the economic and environmental sustainability of wastewater treatment. A number of state-of-the-art anaerobic bioreactors have promise for intensified anaerobic biological treatment and energy recovery, but they have drawbacks. The drawbacks should be overcome with a novel anaerobic biological wastewater treatment process: the anaerobic biofilm membrane bioreactor (AnBfMBR). This research works aims to advance key components of the AnBfMBR. The AnBfMBR is a hybrid suspended growth and biofilm reactor. The two main components of an AnBfMBR are plastic biofilm carriers and membranes. The plastic biofilm carriers provide the surface onto which the biofilms grow. Membranes provide liquid-solid separation, retention of suspended biomass, and a solids-free effluent. Introducing sufficient surface area promotes the biofilm accumulation of slow-growing methanogens that convert volatile fatty acids into methane gas. Biofilms growing on these surfaces will have a mixed culture that primarily consists of methanogens and inert particulate solids, but also includes some acetogens. Biomass that detaches from biofilms become a component of the suspended growth. A bench-scale AnBfMBR was designed by the AnBfMBR project team and constructed by SafBon Water Technology (SWT). The primary objective of this thesis project was to evaluate the ability of plastic biofilm carriers to minimize ceramic-membrane fouling in the AnBfMBR setting. A systematic analysis of mixing for the bench-scale AnBfMBR was also conducted with the plastic biofilm carriers. Experiments were conducted following a ‘run to failure’ method, in which the ceramic membranes provide filtration, and the time it takes to reach a ‘failure transmembrane pressure (TMP)’ was recorded. The experiments revealed two distinct trends. First, the time to failure TMP decreased as mixed liquor suspended solids concentration (MLSS) concentration increased. Second, increasing the carrier fill extend the time to failure, particularly for higher MLSS concentrations. Taken together, the experiments identified an optimized “sweet spot” for the AnBfMBR: an operating flux of 0.25-m/d, a failure TMP of 0.3-atm pressure, MLSS of 5,000 – 7,500 mg/L, and 40% carrier fill.
ContributorsRoman, Brian Aaron (Author) / Rittmann, Bruce (Thesis advisor) / Boltz, Joshua (Committee member) / Perreault, Francois (Committee member) / Fox, Peter (Committee member) / Arizona State University (Publisher)
Created2021
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Description
While most household surfactants are biodegradable in aerobic conditions, their presence in a microbiological treatment process can lead to the proliferation of antimicrobial-resistance genes (ARG) in bacteria, such as Pseudomonas aeruginosa. Surfactants can be cationic, anionic, or zwitterionic, and these different classes may have different effects on the proliferation

While most household surfactants are biodegradable in aerobic conditions, their presence in a microbiological treatment process can lead to the proliferation of antimicrobial-resistance genes (ARG) in bacteria, such as Pseudomonas aeruginosa. Surfactants can be cationic, anionic, or zwitterionic, and these different classes may have different effects on the proliferation of ARG. This study evaluated how the three classes of surfactants affected the microbial community’s structure and ARG in O2-based membrane biofilm reactors (O2-MBfRs) that provided at least 98% surfactant removal. Cationic cetrimonium bromide (CTAB) had by far the strongest impact with highest ARG abundance in the biofilm. In particular, Pseudomonas and Stenotrophomonas, the two main genera in the biofilm treating CTAB, were highly correlated to the abundance of ARG for efflux pumps and antibiotic inactivation. CTAB also promoted potential of horizontal gene transfer (HGT) of ARG. Combining results from the metabolome and metagenome identified four possible pathways for CTAB biodegradation. Of special important is a new pathway: β-carbon oxidation of CTAB to produce betaine. An insufficient nitrogen source could lead to irreversible ARB and ARG enrichment in the MBfR biofilm. Finally, a two-stage O2-MBfR successfully removed a high concentration (730 mg/L) of CTAB: Partial CTAB removal in the Lead reactor relieved inhibition in the Lag reactor. Metagenomic analysis also revealed that the Lag reactor was enriched in genes for CTAB and metabolite oxygenation.
ContributorsZheng, Chenwei (Author) / Rittmann, Bruce (Thesis advisor) / Delgado, Anca (Committee member) / Krajmalnik-Brown, Rosa (Committee member) / Lai, Yen-Jung (Committee member) / Arizona State University (Publisher)
Created2023