Matching Items (66)
Description
Hydrology and biogeochemistry are coupled in all systems. However, human decision-making regarding hydrology and biogeochemistry are often separate, even though decisions about hydrologic systems may have substantial impacts on biogeochemical patterns and processes. The overarching question of this dissertation was: How does hydrologic engineering interact with the effects of nutrient loading and climate to drive watershed nutrient yields? I conducted research in two study systems with contrasting spatial and temporal scales. Using a combination of data-mining and modeling approaches, I reconstructed nitrogen and phosphorus budgets for the northeastern US over the 20th century, including anthropogenic nutrient inputs and riverine fluxes, for ~200 watersheds at 5 year time intervals. Infrastructure systems, such as sewers, wastewater treatment plants, and reservoirs, strongly affected the spatial and temporal patterns of nutrient fluxes from northeastern watersheds. At a smaller scale, I investigated the effects of urban stormwater drainage infrastructure on water and nutrient delivery from urban watersheds in Phoenix, AZ. Using a combination of field monitoring and statistical modeling, I tested hypotheses about the importance of hydrologic and biogeochemical control of nutrient delivery. My research suggests that hydrology is the major driver of differences in nutrient fluxes from urban watersheds at the event scale, and that consideration of altered hydrologic networks is critical for understanding anthropogenic impacts on biogeochemical cycles. Overall, I found that human activities affect nutrient transport via multiple pathways. Anthropogenic nutrient additions increase the supply of nutrients available for transport, whereas hydrologic infrastructure controls the delivery of nutrients from watersheds. Incorporating the effects of hydrologic infrastructure is critical for understanding anthropogenic effects on biogeochemical fluxes across spatial and temporal scales.
ContributorsHale, Rebecca Leslie (Author) / Grimm, Nancy (Thesis advisor) / Childers, Daniel (Committee member) / Vivoni, Enrique (Committee member) / York, Abigail (Committee member) / Wu, Jianguo (Committee member) / Arizona State University (Publisher)
Created2013
Description
This dissertation is presented in two sections. First, I explore two methods of using stable isotope analysis to trace environmental and biogeochemical processes. Second, I present two related studies investigating student understanding of the biogeochemical concepts that underlie part one. Fe and Hg are each biogeochemically important elements in their own way. Fe is a critical nutrient for phytoplankton, while Hg is detrimental to nearly all forms of life. Fe is often a limiting factor in marine phytoplankton growth. The largest source, by mass, of Fe to the open ocean is windblown mineral dust, but other more soluble sources are more bioavailable. To look for evidence of these non-soil dust sources of Fe to the open ocean, I measured the isotopic composition of aerosol samples collected on Bermuda. I found clear evidence in the fine size fraction of a non-soil dust Fe source, which I conclude is most likely from biomass burning. Widespread adoption of compact fluorescent lamps (CFL) has increased their importance as a source of environmental Hg. Isotope analysis would be a useful tool in quantifying this impact if the isotopic composition of Hg from CFL were known. My measurements show that CFL-Hg is isotopically fractionated, in a unique pattern, during normal operation. This fractionation is large and has a distinctive, mass-independent signature, such that CFL Hg can be uniquely identified from other sources. Misconceptions research in geology has been a very active area of research, but student thinking regarding the related field of biogeochemistry has not yet been studied in detail. From interviews with 40 undergraduates, I identified over 150 specific misconceptions. I also designed a multiple-choice survey (concept inventory) to measure understanding of these same biogeochemistry concepts. I present statistical evidence, based on the Rasch model, for the reliability and validity of this instrument. This instrument will allow teachers and researchers to easily quantify learning outcomes in biogeochemistry and will complement existing concept inventories in geology, chemistry, and biology.
ContributorsMead, Chris (Author) / Anbar, Ariel (Thesis advisor) / Semken, Steven (Committee member) / Shock, Everett (Committee member) / Herckes, Pierre (Committee member) / Hartnett, Hilairy (Committee member) / Arizona State University (Publisher)
Created2014
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
Description
Black carbon (BC) is the product of incomplete combustion of biomass and fossil fuels. It is found ubiquitously in nature and is relevant to studies in atmospheric science, soil science, oceanography, and anthropology. Black carbon is best described using a combustion continuum that sub-classifies BC into slightly charred biomass, char, charcoal and soot. These sub-classifications range in particle size, formation temperature, and relative reactivity. Interest in BC has increased because of its role in the long-term storage of organic matter and the biogeochemistry of urban areas. The global BC budget is unbalanced. Production of BC greatly outweighs decomposition of BC. This suggests that there are unknown or underestimated BC removal processes, and it is likely that some of these processes are occurring in soils. However, little is known about BC reactivity in soil and especially in desert soil. This work focuses on soot BC, which is formed at higher temperatures and has a lower relative reactivity than other forms of BC. Here, I assess the contribution of soot BC to central AZ soils and use the isotopic composition of soot BC to identify sources of soot BC. Soot BC is a significant (31%) fraction of the soil organic matter in central AZ and this work suggests that desert and urban soils may be a storage reservoir for soot BC. I further identify previously unknown removal processes of soot BC found naturally in soil and demonstrate that soil soot BC undergoes abiotic (photo-oxidation) and biotic reactions. Not only is soot BC degraded by these processes, but its chemical composition is altered, suggesting that soot BC contains some chemical moieties that are more reactive than others. Because soot BC demonstrates both refractory and reactive character, it is likely that the structure of soot BC; therefore, its interactions in the environment are complex and it is not simply a recalcitrant material.
ContributorsHamilton, George (Author) / Hartnett, Hilairy E (Thesis advisor) / Herckes, Pierre (Committee member) / Hall, Sharon (Committee member) / Arizona State University (Publisher)
Created2013
Description
Research shows that many water governance regimes are failing to guide social-ecological systems away from points, beyond which, damage to social and environmental well-being will be difficult to correct. This problem is apparent in regions that face water conflicts and climate threats. There remains a need to clarify what is it about governance that people need to change in water conflict prone regions, how to collectively go about doing that, and how research can actively support this. To address these needs, here I present a collaborative research project from the dry tropics of Guanacaste Province, Costa Rica. The project addressed the overarching questions: How can water be governed sustainably in water-contested and climate-threatened regions? And, how can people transition current water governance regimes toward more sustainable ones? In pursuit of these questions, a series of individual studies were performed with many partners and collaborators. These studies included: a participatory analysis and sustainability assessment of current water governance regimes; a case analysis and comparison of water conflicts; constructing alternative governance scenarios; and, developing governance transition strategies. Results highlight the need for water governance that addresses asymmetrical knowledge gaps especially concerning groundwater resources, reconciles disenfranchised groups, and supports local leaders. Yet, actions taken based on these initial results, despite some success influencing policy, found substantial challenges confronting them. In-depth conflict investigations, for example, found that deeply rooted issues such friction between opposing local-based and national institutions were key conflict drivers in the region. To begin addressing these issues, researchers and stakeholders then constructed a set of governing alternatives and devised governance transition strategies that could actively support people to achieve more sustainable alternatives and avoid less sustainable ones. These efforts yielded insight into the collective actions needed to implement more sustainable water governance regimes, including ways to overcoming barriers that drive harmful water conflicts. Actions based on these initial strategies yielded further opportunities, challenges, and lessons. Overall, the project addresses the research and policy gap between identifying what is sustainable water governance and understanding the strategies needed to implement it successfully in regions that experience water conflict and climate impacts.
ContributorsKuzdas, Christopher Paul (Author) / Wiek, Arnim (Thesis advisor) / Childers, Daniel (Thesis advisor) / Vignola, Raffaele (Committee member) / Eakin, Hallie (Committee member) / Basile, George (Committee member) / Arizona State University (Publisher)
Created2014
Description
This is a study of the plight of smallholder agriculture in Northwest Costa Rica. More specifically, this is the story of 689 rice farms, of an average size of 7.2 hectares and totaling just less than 5,300 hectares within the largest agricultural irrigation system in Central America. I was able to define the physical bounds of this study quite clearly, but one would be mistaken to think that this simplicity transfers to a search for rural development solutions in this case. Those solutions lie in the national and international politics that appear to have allowed a select few to pick winners and losers in Costa Rican agriculture in the face of global changes. In this research, I found that water scarcity among smallholder farms between 2006 and 2013 was the product of the adaptations of other, more powerful actors in 2002 to threats of Costa Rica's ratification of the Central American Free Trade Agreement. I demonstrate how the adaptations of these more powerful actors produced new risks for others, and how this ultimately prevented the rural development program from meeting its development goals. I reflect on my case study to draw conclusions about the different ways risks may emerge in rural development programs of this type. Then, I focus on the household level and show that determinants of successful adaptation to one type of global change risk may make farmers more vulnerable to other types, creating a "catch-22" among vulnerable farmers adapting to multiple global change risks. Finally, I define adaptation limits in smallholder rice farming in Northwest Costa Rica. I show that the abandonment of livelihood security and well-being, and of the unique "parcelaro" identities of rice farmers in this region define adaptation limits in this context.
ContributorsWarner, Benjamin (Author) / Childers, Daniel (Thesis advisor) / Eakin, Hallie (Committee member) / Abbott, Joshua (Committee member) / Wiek, Arnim (Committee member) / Arizona State University (Publisher)
Created2014
Description
Americans spend upwards of 90% of their time indoors, hence indoor air quality (IAQ) and the impact of IAQ on human health is a major public health concern. IAQ can be negatively impacted by outdoor pollution infiltrating indoors, the emission of indoor pollutants, indoor atmospheric chemistry and poor ventilation. Energy saving measures like retrofits to seal the building envelope to prevent the leakage of heated or cooled air will impact IAQ. However, existing studies have been inconclusive as to whether increased energy efficiency is leading to detrimental IAQ. In this work, field campaigns were conducted in apartment homes in Phoenix, Arizona to evaluate IAQ as it relates to particulate matter (PM), carbonyls, and tobacco specific nitrosamines (TSNA).
To investigate the impacts of an energy efficiency retrofit on IAQ, indoor and outdoor air quality sampling was carried out at Sunnyslope Manor, a city-subsidized senior living apartment complex. Measured indoor formaldehyde levels before the building retrofit exceeded reference exposure limits, but in the long term follow-up sampling, indoor formaldehyde decreased for the entire study population by a statistically significant margin. Indoor PM levels were dominated by fine particles and showed a statistically significant decrease in the long term follow-up sampling within certain resident subpopulations (i.e. residents who reported smoking and residents who had lived longer at the apartment complex). Additionally, indoor glyoxal and methylglyoxal exceeded outdoor concentrations, with methylglyoxal being more prevalent pre-retrofit than glyoxal, suggesting different chemical pathways are involved. Indoor concentrations reported are larger than previous studies. TSNAs, specifically N'-nitrosonornicotine (NNN), 4-(methyl-nitrosamino)-4-(3-pyridyl)-butanal (NNA) and 4-(methylnitrosoamino)-1-(3-pyridyl)-1-butanone (NNK) were evaluated post-retrofit at Sunnyslope Manor. Of the units tested, 86% of the smoking units and 46% of the non-smoking units had traces of at least one of the nitrosamines.
To investigate the impacts of an energy efficiency retrofit on IAQ, indoor and outdoor air quality sampling was carried out at Sunnyslope Manor, a city-subsidized senior living apartment complex. Measured indoor formaldehyde levels before the building retrofit exceeded reference exposure limits, but in the long term follow-up sampling, indoor formaldehyde decreased for the entire study population by a statistically significant margin. Indoor PM levels were dominated by fine particles and showed a statistically significant decrease in the long term follow-up sampling within certain resident subpopulations (i.e. residents who reported smoking and residents who had lived longer at the apartment complex). Additionally, indoor glyoxal and methylglyoxal exceeded outdoor concentrations, with methylglyoxal being more prevalent pre-retrofit than glyoxal, suggesting different chemical pathways are involved. Indoor concentrations reported are larger than previous studies. TSNAs, specifically N'-nitrosonornicotine (NNN), 4-(methyl-nitrosamino)-4-(3-pyridyl)-butanal (NNA) and 4-(methylnitrosoamino)-1-(3-pyridyl)-1-butanone (NNK) were evaluated post-retrofit at Sunnyslope Manor. Of the units tested, 86% of the smoking units and 46% of the non-smoking units had traces of at least one of the nitrosamines.
ContributorsFrey, Sarah E (Author) / Herckes, Pierre (Thesis advisor) / Fraser, Matthew P (Thesis advisor) / Destaillats, Hugo (Committee member) / Chizmeshya, Andrew (Committee member) / Arizona State University (Publisher)
Created2014
Description
Geopolymers, a class of X-ray amorphous, ceramic-like aluminosilicate materials are produced at ambient temperatures through a process called geopolymerization. Due to both low energy requirement during synthesis and interesting mechanical and chemical properties, geopolymers are grabbing enormous attention. Although geopolymers have a broad range of applications including thermal/acoustic insulation and waste immobilization, they are always prepared in monolithic form. The primary aim of this study is to produce new nanostructured materials from the geopolymerization process, including porous monoliths and powders.
In view of the current interest in porous geopolymers for non-traditional applications, it is becoming increasingly important to develop synthetic techniques to introduce interconnected pores into the geopolymers. This study presents a simple synthetic route to produce hierarchically porous geopolymers via a reactive emulsion templating process utilizing triglyceride oil. In this new method, highly alkaline geopolymer resin is mixed with canola oil to form a homogeneous viscous emulsion which, when cured at 60 °C, gives a hard monolithic material. During the process, the oil in the alkaline emulsion undergoes a saponification reaction to decompose into water-soluble soap and glycerol molecules which are extracted to yield porous geopolymers. Nitrogen sorption studies indicates the presence of mesopores, whereas the SEM studies reveals that the mesoporous geopolymer matrix is dotted with spherical macropores. The method exhibits flexibility in that the pore structure of the final porous geopolymers products can be adjusted by varying the precursor composition.
In a second method, the geopolymerization process is modified to produce highly dispersible geopolymer particles, by activating metakaolin with sodium silicate solutions containing excess alkali, and curing for short duration under moist conditions. The produced geopolymer particles exhibit morphology similar to carbon blacks and structured silicas, while also being stable over a wide pH range.
Finally, highly crystalline hierarchical faujasite zeolites are prepared by yet another modification of the geopolymerization process. In this technique, the second method is combined with a saponification reaction of triglyceride oil. The resulting hierarchical zeolites exhibit superior CO2-sorption properties compared to equivalent commercially available and currently reported materials. Additionally, the simplicity of all three of these techniques means they are readily scalable.
In view of the current interest in porous geopolymers for non-traditional applications, it is becoming increasingly important to develop synthetic techniques to introduce interconnected pores into the geopolymers. This study presents a simple synthetic route to produce hierarchically porous geopolymers via a reactive emulsion templating process utilizing triglyceride oil. In this new method, highly alkaline geopolymer resin is mixed with canola oil to form a homogeneous viscous emulsion which, when cured at 60 °C, gives a hard monolithic material. During the process, the oil in the alkaline emulsion undergoes a saponification reaction to decompose into water-soluble soap and glycerol molecules which are extracted to yield porous geopolymers. Nitrogen sorption studies indicates the presence of mesopores, whereas the SEM studies reveals that the mesoporous geopolymer matrix is dotted with spherical macropores. The method exhibits flexibility in that the pore structure of the final porous geopolymers products can be adjusted by varying the precursor composition.
In a second method, the geopolymerization process is modified to produce highly dispersible geopolymer particles, by activating metakaolin with sodium silicate solutions containing excess alkali, and curing for short duration under moist conditions. The produced geopolymer particles exhibit morphology similar to carbon blacks and structured silicas, while also being stable over a wide pH range.
Finally, highly crystalline hierarchical faujasite zeolites are prepared by yet another modification of the geopolymerization process. In this technique, the second method is combined with a saponification reaction of triglyceride oil. The resulting hierarchical zeolites exhibit superior CO2-sorption properties compared to equivalent commercially available and currently reported materials. Additionally, the simplicity of all three of these techniques means they are readily scalable.
ContributorsMedpelli, Dinesh (Author) / Seo, Dong-Kyun (Thesis advisor) / Herckes, Pierre (Committee member) / Petuskey, William (Committee member) / Arizona State University (Publisher)
Created2015
Description
The focus of this thesis is to study dissolved organic carbon composition and reactivity along the Colorado and Green Rivers. Dissolved organic carbon (DOC) in large-scale, managed rivers is relatively poorly studied as most literature has focused on pristine unmanaged rivers. The Colorado River System is the 7th largest in the North America; there are seventeen large dams along the Colorado and Green River. DOC in rivers and in the lakes formed by dams (reservoirs) undergo photo-chemical and bio-degradation. DOC concentration and composition in these systems were investigated using bulk concentration, optical properties, and fluorescence spectroscopy. The riverine DOC concentration decreased from upstream to downstream but there was no change in the specific ultraviolet absorbance at 254 nm (SUVA254). Total fluorescence also decreased along the river. In general, the fluorescence index (FI) increased slightly, the humification index (HIX) decreased, and the freshness index (β/α) increased from upstream to downstream. Photo-oxidation and biodegradation experiments were used to determine if the observed changes in DOC composition along the river could be driven by these biogeochemical alteration processes.
In two-week natural sunlight photo-oxidation experiments the DOC concentration did not change, while the SUVA254 and TF decreased. In addition, the FI and ‘freshness’ increased and HIX decreased during photo-oxidation. Photo-oxidation can explain the upstream to downstream trends for TF, FI, HIX, and freshness observed in river water. Serial photo-oxidation and biodegradation experiments were performed on water collected from three sites along the Colorado River. Bulk DOC concentration in all samples decreased during the biodegradation portion of the study, but DOC bioavailability was lower in samples that were photo-oxidized prior to the bioavailability study.
The upstream to downstream trends in DOC concentration and composition along the river can be explained by a combination of photo-chemical and microbial degradation. The bulk DOC concentration change is primarily driven by microbial degradation, while the changes in the composition of the fluorescent DOC are driven by photo-oxidation.
In two-week natural sunlight photo-oxidation experiments the DOC concentration did not change, while the SUVA254 and TF decreased. In addition, the FI and ‘freshness’ increased and HIX decreased during photo-oxidation. Photo-oxidation can explain the upstream to downstream trends for TF, FI, HIX, and freshness observed in river water. Serial photo-oxidation and biodegradation experiments were performed on water collected from three sites along the Colorado River. Bulk DOC concentration in all samples decreased during the biodegradation portion of the study, but DOC bioavailability was lower in samples that were photo-oxidized prior to the bioavailability study.
The upstream to downstream trends in DOC concentration and composition along the river can be explained by a combination of photo-chemical and microbial degradation. The bulk DOC concentration change is primarily driven by microbial degradation, while the changes in the composition of the fluorescent DOC are driven by photo-oxidation.
ContributorsBowman, Margaret (Author) / Hartnett, Hilairy E (Thesis advisor) / Hayes, Mark A. (Committee member) / Herckes, Pierre (Committee member) / Arizona State University (Publisher)
Created2015
Description
Climate change will result not only in changes in the mean state of climate but also on changes in variability. However, most studies of the impact of climate change on ecosystems have focused on the effect of changes in the central tendency. The broadest objective of this thesis was to assess the effects of increased interannual precipitation variation on ecosystem functioning in grasslands. In order to address this objective, I used a combination of field experimentation and data synthesis. Precipitation manipulations on the field experiments were carried out using an automated rainfall manipulation system developed as part of this dissertation. Aboveground net primary production responses were monitored during five years. Increased precipitation coefficient of variation decreased primary production regardless of the effect of precipitation amount. Perennial-grass productivity significantly decreased while shrub productivity increased as a result of enhanced precipitation variance. Most interesting is that the effect of precipitation variability increased through time highlighting the existence of temporal lags in ecosystem response.
Further, I investigated the effect of precipitation variation on functional diversity on the same experiment and found a positive response of diversity to increased interannual precipitation variance. Functional evenness showed a similar response resulting from large changes in plant-functional type relative abundance including decreased grass and increased shrub cover while functional richness showed non-significant response. Increased functional diversity ameliorated the direct negative effects of precipitation variation on ecosystem ANPP but did not control ecosystem stability where indirect effects through the dominant plant-functional type determined ecosystem stability.
Analyses of 80 long-term data sets, where I aggregated annual productivity and precipitation data into five-year temporal windows, showed that precipitation variance had a significant effect on aboveground net primary production that is modulated by mean precipitation. Productivity increased with precipitation variation at sites where mean annual precipitation is less than 339 mm but decreased at sites where precipitation is higher than 339 mm. Mechanisms proposed to explain patterns include: differential ANPP response to precipitation among sites, contrasting legacy effects and soil water distribution.
Finally, increased precipitation variance may impact global grasslands affecting plant-functional types in different ways that may lead to state changes, increased erosion and decreased stability that can in turn limit the services provided by these valuable ecosystems.
Further, I investigated the effect of precipitation variation on functional diversity on the same experiment and found a positive response of diversity to increased interannual precipitation variance. Functional evenness showed a similar response resulting from large changes in plant-functional type relative abundance including decreased grass and increased shrub cover while functional richness showed non-significant response. Increased functional diversity ameliorated the direct negative effects of precipitation variation on ecosystem ANPP but did not control ecosystem stability where indirect effects through the dominant plant-functional type determined ecosystem stability.
Analyses of 80 long-term data sets, where I aggregated annual productivity and precipitation data into five-year temporal windows, showed that precipitation variance had a significant effect on aboveground net primary production that is modulated by mean precipitation. Productivity increased with precipitation variation at sites where mean annual precipitation is less than 339 mm but decreased at sites where precipitation is higher than 339 mm. Mechanisms proposed to explain patterns include: differential ANPP response to precipitation among sites, contrasting legacy effects and soil water distribution.
Finally, increased precipitation variance may impact global grasslands affecting plant-functional types in different ways that may lead to state changes, increased erosion and decreased stability that can in turn limit the services provided by these valuable ecosystems.
ContributorsGherardi Arbizu, Laureano (Author) / Sala, Osvaldo E. (Thesis advisor) / Childers, Daniel (Committee member) / Grimm, Nancy (Committee member) / Hall, Sharon (Committee member) / Wu, Jingle (Committee member) / Arizona State University (Publisher)
Created2014