Matching Items (10)
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- All Subjects: Environmental sciences
- Creators: Fox, Peter
- Creators: Westerhoff, Paul
Description
Filtration for microfluidic sample-collection devices is desirable for sample selection, concentration, preprocessing, and downstream manipulation, but microfabricating the required sub-micrometer filtration structure is an elaborate process. This thesis presents a simple method to fabricate polydimethylsiloxane (PDMS) devices with an integrated membrane filter that will sample, lyse, and extract the DNA from microorganisms in aqueous environments. An off-the-shelf membrane filter disc was embedded in a PDMS layer and sequentially bound with other PDMS channel layers. No leakage was observed during filtration. This device was validated by concentrating a large amount of cyanobacterium Synechocystis in simulated sample water with consistent performance across devices. After accumulating sufficient biomass on the filter, a sequential electrochemical lysing process was performed by applying 5VDC across the filter. This device was further evaluated by delivering several samples of differing concentrations of cyanobacterium Synechocystis then quantifying the DNA using real-time PCR. Lastly, an environmental sample was run through the device and the amount of photosynthetic microorganisms present in the water was determined. The major breakthroughs in this design are low energy demand, cheap materials, simple design, straightforward fabrication, and robust performance, together enabling wide-utility of similar chip-based devices for field-deployable operations in environmental micro-biotechnology.
ContributorsLecluse, Aurelie (Author) / Meldrum, Deirdre (Thesis advisor) / Chao, Joseph (Thesis advisor) / Westerhoff, Paul (Committee member) / Arizona State University (Publisher)
Created2011
Description
The North American Monsoon System (NAMS) contributes ~55% of the annual rainfall in the Chihuahuan Desert during the summer months. Relatively frequent, intense storms during the NAMS increase soil moisture, reduce surface temperature and lead to runoff in ephemeral channels. Quantifying these processes, however, is difficult due to the sparse nature of coordinated observations. In this study, I present results from a field network of rain gauges (n = 5), soil probes (n = 48), channel flumes (n = 4), and meteorological equipment in a small desert shrubland watershed (~0.05 km2) in the Jornada Experimental. Using this high-resolution network, I characterize the temporal and spatial variability of rainfall, soil conditions and channel runoff within the watershed from June 2010 to September 2011, covering two NAMS periods. In addition, CO2, water and energy measurements at an eddy covariance tower quantify seasonal, monthly and event-scale changes in land-atmosphere states and fluxes. Results from this study indicate a strong seasonality in water and energy fluxes, with a reduction in Bowen ratio (B, the ratio of sensible to latent heat fluxes) from winter (B = 14) to summer (B = 3.3). This reduction is tied to shallow soil moisture availability during the summer (s = 0.040 m3/m3) as compared to the winter (s = 0.004 m3/m3). During the NAMS, I analyzed four consecutive rainfall-runoff events to quantify the soil moisture and channel flow responses and how water availability impacted the land-atmosphere fluxes. Spatial hydrologic variations during events occur over distances as short as ~15 m. The field network also allowed comparisons of several approaches to estimate evapotranspiration (ET). I found a more accurate ET estimate (a reduction of mean absolute error by 38%) when using distributed soil moisture data, as compared to a standard water balance approach based on the tower site. In addition, use of spatially-varied soil moisture data yielded a more reasonable relationship between ET and soil moisture, an important parameterization in many hydrologic models. The analyses illustrates the value of high-resolution sampling for quantifying seasonal fluxes in desert shrublands and their improvements in closing the water balance in small watersheds.
ContributorsTempleton, Ryan (Author) / Vivoni, Enrique R (Thesis advisor) / Mays, Larry (Committee member) / Fox, Peter (Committee member) / Arizona State University (Publisher)
Created2011
Description
The overall goal of this dissertation is to advance understanding of biofilm reduction of oxidized contaminants in water and wastewater. Chapter 1 introduces the fundamentals of biological reduction of three oxidized contaminants (nitrate, perchlorate, and trichloriethene (TCE)) using two biofilm processes (hydrogen-based membrane biofilm reactors (MBfR) and packed-bed heterotrophic reactors (PBHR)), and it identifies the research objectives. Chapters 2 through 6 focus on nitrate removal using the MBfR and PBHR, while chapters 7 through 10 investigate simultaneous reduction of nitrate and another oxidized compound (perchlorate, sulfate, or TCE) in the MBfR. Chapter 11 summarizes the major findings of this research. Chapters 2 and 3 demonstrate nitrate removal in a groundwater and identify the maximum nitrate loadings using a pilot-scale MBfR and a pilot-scale PBHR, respectively. Chapter 4 compares the MBfR and the PBHR for denitrification of the same nitrate-contaminated groundwater. The comparison includes the maximum nitrate loading, the effluent water quality of the denitrification reactors, and the impact of post-treatment on water quality. Chapter 5 theoretically and experimentally demonstrates that the nitrate biomass-carrier surface loading, rather than the traditionally used empty bed contact time or nitrate volumetric loading, is the primary design parameter for heterotrophic denitrification. Chapter 6 constructs a pH-control model to predict pH, alkalinity, and precipitation potential in heterotrophic or hydrogen-based autotrophic denitrification reactors. Chapter 7 develops and uses steady-state permeation tests and a mathematical model to determine the hydrogen-permeation coefficients of three fibers commonly used in the MBfR. The coefficients are then used as inputs for the three models in Chapters 8-10. Chapter 8 develops a multispecies biofilm model for simultaneous reduction of nitrate and perchlorate in the MBfR. The model quantitatively and systematically explains how operating conditions affect nitrate and perchlorate reduction and biomass distribution via four mechanisms. Chapter 9 modifies the nitrate and perchlorate model into a nitrate and sulfate model and uses it to identify operating conditions corresponding to onset of sulfate reduction. Chapter 10 modifies the nitrate and perchlorate model into a nitrate and TCE model and uses it to investigate how operating conditions affect TCE reduction and accumulation of TCE reduction intermediates.
ContributorsTang, Youneng (Author) / Rittmann, Bruce E. (Thesis advisor) / Westerhoff, Paul (Committee member) / Krajmalnik-Brown, Rosa (Committee member) / Halden, Rolf (Committee member) / Arizona State University (Publisher)
Created2012
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
Safe, readily available, and reliable sources of water are an essential component of any municipality’s infrastructure. Phoenix, Arizona, a southwestern city, has among the highest per capita water use in the United States, making it essential to carefully manage its reservoirs. Generally, municipal water bodies are monitored through field sampling. However, this approach is limited spatially and temporally in addition to being costly. In this study, the application of remotely sensed reflectance data from Landsat 7’s Enhanced Thematic Mapper Plus (ETM+) and Landsat 8’s Operational Land Imager (OLI) along with data generated through field-sampling is used to gain a better understanding of the seasonal development of algal communities and levels of suspended particulates in the three main terminal reservoirs supplying water to the Phoenix metro area: Bartlett Lake, Lake Pleasant, and Saguaro Lake. Algal abundances, particularly the abundance of filamentous cyanobacteria, increased with warmer temperatures in all three reservoirs and reached the highest comparative abundance in Bartlett Lake. Prymnesiophytes (the class of algae to which the toxin-producing golden algae belong) tended to peak between June and August, with one notable peak occurring in Saguaro Lake in August 2017 during which time a fish-kill was observed. In the cooler months algal abundance was comparatively lower in all three lakes, with a more even distribution of abundance across algae classes. In-situ data from March 2017 to March 2018 were compared with algal communities sampled approximately ten years ago in each reservoir to understand any possible long-term changes. The findings show that the algal communities in the reservoirs are relatively stable, particularly those of the filamentous cyanobacteria, chlorophytes, and prymnesiophytes with some notable exceptions, such as the abundance of diatoms, which increased in Bartlett Lake and Lake Pleasant. When in-situ data were compared with Landsat-derived reflectance data, two-band combinations were found to be the best-estimators of chlorophyll-a concentration (as a proxy for algal biomass) and total suspended sediment concentration. The ratio of the reflectance value of the red band and the blue band produced reasonable estimates for the in-situ parameters in Bartlett Lake. The ratio of the reflectance value of the green band and the blue band produced reasonable estimates for the in-situ parameters in Saguaro Lake. However, even the best performing two-band algorithm did not produce any significant correlation between reflectance and in-situ data in Lake Pleasant. Overall, remotely-sensed observations can significantly improve our understanding of the water quality as measured by algae abundance and particulate loading in Arizona Reservoirs, especially when applied over long timescales.
ContributorsRussell, Jazmine Barkley (Author) / Neuer, Susanne (Thesis advisor) / Fox, Peter (Committee member) / Myint, Soe (Committee member) / Arizona State University (Publisher)
Created2018
Description
Six high-production-volume neonicotinoids were traced through a municipal wastewater treatment plant (WWTP) and engineered wetland located downstream, in a study motivated by reports on these insecticides posing threats to non-target invertebrate species and potentially playing a role in the global honeybee colony collapse disorder. An array of automated samplers was deployed in a five-day monitoring campaign and resultant flow-weighted samples were analyzed by liquid chromatography tandem mass spectrometry (LC-MS/MS) using the isotope dilution method. Concentrations in WWTP influent and effluent were 54.7 ± 2.9 and 48.6 ± 2.7 ng/L for imidacloprid, respectively, and 3.7 ± 0.3 and 1.8 ± 0.1 ng/L for acetamiprid, respectively. A mass balance over the WWTP showed no (p=0.09, CI = 95%) removal of imidacloprid, and 56 ± 6% aqueous removal of acetamiprid. In the constructed wetland downstream, a lack of removal was noted for both imidacloprid (from 54.4 ± 3.4 ng/L to 49.9 ± 14.6 ng/L) and acetamiprid (from 2.00 ± 0.03 ng/L to 2.30 ± 0.21 ng/L). Clothianidin was detected only inconsistently in the WWTP and wetland (>2 to 288 ng/L; 60% detection frequency), whereas thiamethoxam (<10 ng/L), thiacloprid (<2 ng/L), and dinotefuran (<180 ng/L) were not detected at all. Thus, imidacloprid and acetamiprid were identified as recalcitrant sewage constituents (estimated U.S. WWTP discharge of 1920- 4780 kg/y) that persist during conventional wastewater treatment to enter U.S. surface waters at potentially harmful concentrations.
ContributorsSadaria, Akash Mahendra (Author) / Halden, Rolf (Thesis advisor) / Fox, Peter (Committee member) / Popat, Sudeep (Committee member) / Arizona State University (Publisher)
Created2015
Description
N-Nitrosodimethylamine (NDMA), a probable human carcinogen, has been found in clouds and fogs at concentration up to 500 ng/L and in drinking water as disinfection by-product. NDMA exposure to the general public is not well understood because of knowledge gaps in terms of occurrence, formation and fate both in air and water. The goal of this dissertation was to contribute to closing these knowledge gaps on potential human NDMA exposure through contributions to atmospheric measurements and fate as well as aqueous formation processes.
Novel, sensitive methods of measuring NDMA in air were developed based on Solid Phase Extraction (SPE) and Solid Phase Microextraction (SPME) coupled to Gas Chromatography-Mass Spectrometry (GC-MS). The two measuring techniques were evaluated in laboratory experiments. SPE-GC-MS was applicable in ambient air sampling and NDMA in ambient air was found in the 0.1-13.0 ng/m3 range.
NDMA photolysis, the main degradation atmospheric pathway, was studied in the atmospheric aqueous phase. Water soluble organic carbon (WSOC) was found to have more impact than inorganic species on NDMA photolysis by competing with NDMA for photons and therefore could substantially increase the NDMA lifetime in the atmosphere. The optical properties of atmospheric WSOC were investigated in aerosol, fog and cloud samples and showed WSOC from atmospheric aerosols has a higher mass absorption efficiency (MAE) than organic matter in fog and cloud water, resulting from a different composition, especially in regards of volatile species, that are not very absorbing but abundant in fogs and clouds.
NDMA formation kinetics during chloramination were studied in aqueous samples including wastewater, surface water and ground water, at two monochloramine concentrations. A simple second order NDMA formation model was developed using measured NDMA and monochloramine concentrations at select reaction times. The model fitted the NDMA formation well (R2 >0.88) in all water matrices. The proposed model was then optimized and applied to fit the data of NDMA formation from natural organic matter (NOM) and model precursors in previously studies. By determining the rate constants, the model was able to describe the effect of water conditions such as DOC and pH on NDMA formation.
Novel, sensitive methods of measuring NDMA in air were developed based on Solid Phase Extraction (SPE) and Solid Phase Microextraction (SPME) coupled to Gas Chromatography-Mass Spectrometry (GC-MS). The two measuring techniques were evaluated in laboratory experiments. SPE-GC-MS was applicable in ambient air sampling and NDMA in ambient air was found in the 0.1-13.0 ng/m3 range.
NDMA photolysis, the main degradation atmospheric pathway, was studied in the atmospheric aqueous phase. Water soluble organic carbon (WSOC) was found to have more impact than inorganic species on NDMA photolysis by competing with NDMA for photons and therefore could substantially increase the NDMA lifetime in the atmosphere. The optical properties of atmospheric WSOC were investigated in aerosol, fog and cloud samples and showed WSOC from atmospheric aerosols has a higher mass absorption efficiency (MAE) than organic matter in fog and cloud water, resulting from a different composition, especially in regards of volatile species, that are not very absorbing but abundant in fogs and clouds.
NDMA formation kinetics during chloramination were studied in aqueous samples including wastewater, surface water and ground water, at two monochloramine concentrations. A simple second order NDMA formation model was developed using measured NDMA and monochloramine concentrations at select reaction times. The model fitted the NDMA formation well (R2 >0.88) in all water matrices. The proposed model was then optimized and applied to fit the data of NDMA formation from natural organic matter (NOM) and model precursors in previously studies. By determining the rate constants, the model was able to describe the effect of water conditions such as DOC and pH on NDMA formation.
ContributorsZhang, Jinwei (Author) / Herckes, Pierre (Thesis advisor) / Westerhoff, Paul (Thesis advisor) / Fraser, Matthew (Committee member) / Shock, Everett (Committee member) / Arizona State University (Publisher)
Created2016
Description
Although the Caribbean has been continuously inhabited for the last 7,000 years, European contact in the last 500 years dramatically reshaped the cultural and genetic makeup of island populations. Several recent studies have explored the genetic diversity of Caribbean Latinos and have characterized Native American variation present within their genomes. However, the difficulty of obtaining ancient DNA from pre-contact populations and the underrepresentation of non-Latino Caribbean islanders in current research have prevented a complete understanding of genetic variation over time and space in the Caribbean basin. This dissertation uses two approaches to characterize the role of migration and admixture in the demographic history of Caribbean islanders. First, autosomal variants were genotyped in a sample of 55 Afro-Caribbeans from five islands in the Lesser Antilles: Grenada, St. Kitts, St. Lucia, Trinidad, and St. Vincent. These data were used to characterize genetic structure, ancestry and signatures of selection in these populations. The results demonstrate a complex pattern of admixture since European contact, including a strong signature of sex-biased mating and inputs from at least five continental populations to the autosomal ancestry of Afro-Caribbean peoples. Second, ancient mitochondrial and nuclear DNA were obtained from 60 skeletal remains, dated between A.D. 500–1300, from three archaeological sites in Puerto Rico: Paso del Indio, Punta Candelero and Tibes. The ancient data were used to reassesses existing models for the peopling of Puerto Rico and the Caribbean and to examine the extent of genetic continuity between ancient and modern populations. Project findings support a largely South American origin for Ceramic Age Caribbean populations and identify some genetic continuity between pre and post contact islanders. The above study was aided by development and testing of extraction methods optimized for recovery of ancient DNA from tropical contexts. Overall, project findings characterize how ancient indigenous groups, European colonial regimes, the African Slave Trade and modern labor movements have shaped the genomic diversity of Caribbean islanders. In addition to its anthropological and historical importance, such knowledge is also essential for informing the identification of medically relevant genetic variation in these populations.
ContributorsNieves Colón, Maria (Author) / Stone, Anne C (Thesis advisor) / Pestle, William J. (Committee member) / Benn-Torres, Jada (Committee member) / Stojanowski, Christopher (Committee member) / Arizona State University (Publisher)
Created2017
Description
The objective of this research was to predict the persistence of potential future contaminants in indirect potable reuse systems. In order to accurately estimate the fates of future contaminants in indirect potable reuse systems, results describing persistence from EPI Suite were modified to include sorption and oxidation. The target future contaminants studied were the approximately 2000 pharmaceuticals currently undergoing testing by United States Food and Drug Administration (US FDA). Specific organic substances such as analgesics, antibiotics, and pesticides were used to verify the predicted half-lives by comparing with reported values in the literature. During sub-surface transport, an important component of indirect potable reuse systems, the effects of sorption and oxidation are important mechanisms. These mechanisms are not considered by the quantitative structure activity relationship (QSAR) model predictions for half-lives from EPI Suite. Modifying the predictions from EPI Suite to include the effects of sorption and oxidation greatly improved the accuracy of predictions in the sub-surface environment. During validation, the error was reduced by over 50% when the predictions were modified to include sorption and oxidation. Molecular weight (MW) is an important criteria for estimating the persistence of chemicals in the sub-surface environment. EPI Suite predicts that high MW compounds are persistent since the QSAR model assumes steric hindrances will prevent transformations. Therefore, results from EPI Suite can be very misleading for high MW compounds. Persistence was affected by the total number of halogen atoms in chemicals more than the sum of N-heterocyclic aromatics in chemicals. Most contaminants (over 90%) were non-persistent in the sub-surface environment suggesting that the target future drugs do not pose a significant risk to potable reuse systems. Another important finding is that the percentage of compounds produced from the biotechnology industry is increasing rapidly and should dominate the future production of pharmaceuticals. In turn, pharmaceuticals should become less persistent in the future. An evaluation of indirect potable reuse systems that use reverse osmosis (RO) for potential rejection of the target contaminants was performed by statistical analysis. Most target compounds (over 95%) can be removed by RO based on size rejection and other removal mechanisms.
ContributorsLim, Seung (Author) / Fox, Peter (Thesis advisor) / Abbaszadegan, Morteza (Committee member) / Halden, Rolf (Committee member) / Arizona State University (Publisher)
Created2011
Description
This dissertation focused on the development and application of state-of-the-art monitoring tools and analysis methods for tracking the fate of trace level contaminants in the natural and built water environments, using fipronil as a model; fipronil and its primary degradates (known collectively as fiproles) are among a group of trace level emerging environmental contaminants that are extremely potent arthropodic neurotoxins. The work further aimed to fill in data gaps regarding the presence and fate of fipronil in engineered water systems, specifically in a wastewater treatment plant (WWTP), and in an engineered wetland. A review of manual and automated “active” water sampling technologies motivated the development of two new automated samplers capable of in situ biphasic extraction of water samples across the bulk water/sediment interface of surface water systems. Combined with an optimized method for the quantification of fiproles, the newly developed In Situ Sampler for Biphasic water monitoring (IS2B) was deployed along with conventional automated water samplers, to study the fate and occurrence of fiproles in engineered water environments; continuous sampling over two days and subsequent analysis yielded average total fiprole concentrations in wetland surface water (9.9 ± 4.6 to 18.1 ± 4.6 ng/L) and wetland sediment pore water (9.1 ± 3.0 to 12.6 ± 2.1 ng/L). A mass balance of the WWTP located immediately upstream demonstrated unattenuated breakthrough of total fiproles through the WWTP with 25 ± 3 % of fipronil conversion to degradates, and only limited removal of total fiproles in the wetland (47 ± 13%). Extrapolation of local emissions (5–7 g/d) suggests nationwide annual fiprole loadings from WWTPs to U.S. surface waters on the order of about one half to three quarters of a metric tonne. The qualitative and quantitative data collected in this work have regulatory implications, and the sampling tools and analysis strategies described in this thesis have broad applicability in the assessment of risks posed by trace level environmental contaminants.
ContributorsSupowit, Samuel (Author) / Halden, Rolf U. (Thesis advisor) / Westerhoff, Paul (Committee member) / Johnson, Paul C (Committee member) / Arizona State University (Publisher)
Created2015