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- Creators: Barrett, The Honors College
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
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
There is growing concern over the future availability of water for electricity generation. Because of a rapidly growing population coupled with an arid climate, the Western United States faces a particularly acute water/energy challenge, as installation of new electricity capacity is expected to be required in the areas with the most limited water availability. Electricity trading is anticipated to be an important strategy for avoiding further local water stress, especially during drought and in the areas with the most rapidly growing populations. Transfers of electricity imply transfers of "virtual water" - water required for the production of a product. Yet, as a result of sizable demand growth, there may not be excess capacity in the system to support trade as an adaptive response to long lasting drought. As the grid inevitably expands capacity due to higher demand, or adapts to anticipated climate change, capacity additions should be selected and sited to increase system resilience to drought. This paper explores the tradeoff between virtual water and local water/energy infrastructure development for the purpose of enhancing the Western US power grid's resilience to drought. A simple linear model is developed that estimates the economically optimal configuration of the Western US power grid given water constraints. The model indicates that natural gas combined cycle power plants combined with increased interstate trade in power and virtual water provide the greatest opportunity for cost effective and water efficient grid expansion. Such expansion, as well as drought conditions, may shift and increase virtual water trade patterns, as states with ample water resources and a competitive advantage in developing power sources become net exporters, and states with limited water or higher costs become importers.
ContributorsHerron, Seth (Author) / Ruddell, Benjamin L (Thesis advisor) / Ariaratnam, Samuel (Thesis advisor) / Allenby, Braden (Committee member) / Williams, Eric (Committee member) / Arizona State University (Publisher)
Created2013
Description
The United Nation's Framework Convention on Climate Change (UNFCCC) recognizes development as a priority for carbon dioxide (CO2) allocation, under its principle of "common but differentiated responsibilities". This was codified in the Kyoto Protocol, which exempt developing nations from binding emission reduction targets. Additionally, they could be the recipients of financed sustainable development projects in exchange for emission reduction credits that the developed nations could use to comply with emission targets. Due to ineffective results, post-Kyoto policy discussions indicate a transition towards mitigation commitments from major developed and developing emitters, likely supplemented by market-based mechanisms to reduce mitigation costs. Although the likelihood of achieving substantial emission reductions is increased by the new plan, there is a paucity of consideration to how an ethic of development might be advanced. Therefore, this research empirically investigates the role that CO2 plays in advancing human development (in terms of the Human Development Index or HDI) over the 1990 to 2010 time period. Based on empirical evidence, a theoretical CO2-development framework is established, which provides a basis for designing a novel policy proposal that integrates mitigation efforts with human development objectives. Empirical evidence confirms that CO2 and HDI are highly correlated, but that there are diminishing returns to HDI as per capita CO2 emissions increase. An examination of development pathways reveals that as nations develop, their trajectories generally become less coupled with CO2. Moreover, the developing countries with the greatest gains in HDI are also nations that have, or are in the process of moving toward, outward-oriented trade policies that involve increased domestic capabilities for product manufacture and export. With these findings in mind, future emission targets should reduce current emissions in developed nations and allow room for HDI growth in developing countries as well as in the least developed nations of the world. Emission trading should also be limited to nations with similar HDI levels to protect less-developed nations from unfair competition for capacity building resources. Lastly, developed countries should be incentivized to invest in joint production ventures within the LDCs to build capacity for self-reliant and sustainable development over the long-term.
ContributorsClark, Susan Spierre (Author) / Seager, Thomas P. (Thesis advisor) / Allenby, Braden (Committee member) / Klinsky, Sonja (Committee member) / Arizona State University (Publisher)
Created2013
Description
Urban water systems face sustainability challenges ranging from water quality, leaks, over-use, energy consumption, and long-term supply concerns. Resiliency challenges include the capacity to respond to drought, managing pipe deterioration, responding to natural disasters, and preventing terrorism. One strategy to enhance sustainability and resiliency is the development and adoption of smart water grids. A smart water grid incorporates networked monitoring and control devices into its structure, which provides diverse, real-time information about the system, as well as enhanced control. Data provide input for modeling and analysis, which informs control decisions, allowing for improvement in sustainability and resiliency. While smart water grids hold much potential, there are also potential tradeoffs and adoption challenges. More publicly available cost-benefit analyses are needed, as well as system-level research and application, rather than the current focus on individual technologies. This thesis seeks to fill one of these gaps by analyzing the cost and environmental benefits of smart irrigation controllers. Smart irrigation controllers can save water by adapting watering schedules to climate and soil conditions. The potential benefit of smart irrigation controllers is particularly high in southwestern U.S. states, where the arid climate makes water scarcer and increases watering needs of landscapes. To inform the technology development process, a design for environment (DfE) method was developed, which overlays economic and environmental performance parameters under different operating conditions. This method is applied to characterize design goals for controller price and water savings that smart irrigation controllers must meet to yield life cycle carbon dioxide reductions and economic savings in southwestern U.S. states, accounting for regional variability in electricity and water prices and carbon overhead. Results from applying the model to smart irrigation controllers in the Southwest suggest that some areas are significantly easier to design for.
ContributorsMutchek, Michele (Author) / Allenby, Braden (Thesis advisor) / Williams, Eric (Committee member) / Westerhoff, Paul (Committee member) / Arizona State University (Publisher)
Created2012
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. 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
Description
A methodology is developed that integrates institutional analysis with Life Cycle Assessment (LCA) to identify and overcome barriers to sustainability transitions and to bridge the gap between environmental practitioners and decisionmakers. LCA results are rarely joined with analyses of the social systems that control or influence decisionmaking and policies. As a result, LCA conclusions generally lack information about who or what controls different parts of the system, where and when the processes' environmental decisionmaking happens, and what aspects of the system (i.e. a policy or regulatory requirement) would have to change to enable lower environmental impact futures. The value of the combined institutional analysis and LCA (the IA-LCA) is demonstrated using a case study of passenger transportation in the Phoenix, Arizona metropolitan area. A retrospective LCA is developed to estimate how roadway investment has enabled personal vehicle travel and its associated energy, environmental, and economic effects. Using regional travel forecasts, a prospective life cycle inventory is developed. Alternative trajectories are modeled to reveal future "savings" from reduced roadway construction and vehicle travel. An institutional analysis matches the LCA results with the specific institutions, players, and policies that should be targeted to enable transitions to these alternative futures. The results show that energy, economic, and environmental benefits from changes in passenger transportation systems are possible, but vary significantly depending on the timing of the interventions. Transition strategies aimed at the most optimistic benefits should include 1) significant land-use planning initiatives at the local and regional level to incentivize transit-oriented development infill and urban densification, 2) changes to state or federal gasoline taxes, 3) enacting a price on carbon, and 4) nearly doubling vehicle fuel efficiency together with greater market penetration of alternative fuel vehicles. This aggressive trajectory could decrease the 2050 energy consumption to 1995 levels, greenhouse gas emissions to 1995, particulate emissions to 2006, and smog-forming emissions to 1972. The potential benefits and costs are both private and public, and the results vary when transition strategies are applied in different spatial and temporal patterns.
ContributorsKimball, Mindy (Author) / Chester, Mikhail (Thesis advisor) / Allenby, Braden (Committee member) / Golub, Aaron (Committee member) / Arizona State University (Publisher)
Created2014
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
This thesis research focuses on developing a single-cell gene expression analysis method for marine diatom Thalassiosira pseudonana and constructing a chip level tool to realize the single cell RT-qPCR analysis. This chip will serve as a conceptual foundation for future deployable ocean monitoring systems. T. pseudonana, which is a common surface water microorganism, was detected in the deep ocean as confirmed by phylogenetic and microbial community functional studies. Six-fold copy number differences between 23S rRNA and 23S rDNA were observed by RT-qPCR, demonstrating the moderate functional activity of detected photosynthetic microbes in the deep ocean including T. pseudonana. Because of the ubiquity of T. pseudonana, it is a good candidate for an early warning system for ocean environmental perturbation monitoring. This early warning system will depend on identifying outlier gene expression at the single-cell level. An early warning system based on single-cell analysis is expected to detect environmental perturbations earlier than population level analysis which can only be observed after a whole community has reacted. Preliminary work using tube-based, two-step RT-qPCR revealed for the first time, gene expression heterogeneity of T. pseudonana under different nutrient conditions. Heterogeneity was revealed by different gene expression activity for individual cells under the same conditions. This single cell analysis showed a skewed, lognormal distribution and helped to find outlier cells. The results indicate that the geometric average becomes more important and representative of the whole population than the arithmetic average. This is in contrast with population level analysis which is limited to arithmetic averages only and highlights the value of single cell analysis. In order to develop a deployable sensor in the ocean, a chip level device was constructed. The chip contains surface-adhering droplets, defined by hydrophilic patterning, that serve as real-time PCR reaction chambers when they are immersed in oil. The chip had demonstrated sensitivities at the single cell level for both DNA and RNA. The successful rate of these chip-based reactions was around 85%. The sensitivity of the chip was equivalent to published microfluidic devices with complicated designs and protocols, but the production process of the chip was simple and the materials were all easily accessible in conventional environmental and/or biology laboratories. On-chip tests provided heterogeneity information about the whole population and were validated by comparing with conventional tube based methods and by p-values analysis. The power of chip-based single-cell analyses were mainly between 65-90% which were acceptable and can be further increased by higher throughput devices. With this chip and single-cell analysis approaches, a new paradigm for robust early warning systems of ocean environmental perturbation is possible.
ContributorsShi, Xu (Author) / Meldrum, Deirdre R. (Thesis advisor) / Zhang, Weiwen (Committee member) / Chao, Shih-hui (Committee member) / Westerhoff, Paul (Committee member) / Arizona State University (Publisher)
Created2013
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