abstract: 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. / Dissertation/Thesis / Ph.D. Geological Sciences 2014

<p> Science and decision making in commercial fisheries management take place in the context of uncertainty. This research demonstrates ways that local knowledge held by fishermen can be used to mitigate that uncertainty. This dissertation documents local knowledge of fishermen in Poland and Alaska, and contributes to the development of methods for utilizing that local knowledge in commercial fisheries management. Specific case study examples were developed through exploratory interviews with fishermen in the two study regions. Interviews were conducted with Baltic cod (<i>Gadus morhua</i>) fishermen in Poland and Pacific halibut (<i>Hippoglossus stenolepis</i>) fishermen in Alaska. Qualitative and quantitative methods were used to analyze local knowledge about ecosystems, as well as preferences held by fishermen about regulations. Cultural consensus analysis was used to quantify agreement among fishermen in Poland about the abundance and condition of cod, and generalized additive modeling was used to show how fishermen and scientists attributed different causes to similar observed phenomena. Multiple factor analysis and logistic regression were used to demonstrate how fishing characteristics influence encounters with incidental catch in the commercial fishery for halibut in Southeast Alaska. Finally, an analytic hierarchy process model was used to shed light on preferences halibut fishermen have about data collection methods on their vessels. All findings show how the inclusion of fishermen&rsquo;s local knowledge in fisheries management need not be limited to informal conversations or public testimony at meetings in order to be meaningfully interpretable by managers.</p><p>

Sustainability entails a system that has the capacity to sustain itself. Stormwater management is one part of the concept sustainable development but traditional practices entail adverse effects on social-ecological systems and there is a need for increasing the resilience of urban stormwater systems.  The growing pressure from climate change and intensified urbanization increase the need for stormwater management. If poorly managed the security and functioning of societies will be negatively affected. Regulations are essential in the achievement of sustainable urban environments. However, national regulations concerning stormwater management are spread through different legal frameworks from different times and it has been recognized that the spread could challenge implementation of the regulations and climate change adaptation. Administrative instruments are important to support the social, economic and ecological value of green and blue structures. The thesis target to analyze relevant regulations and investigate their effectiveness for a sustainable stormwater management through combined interpretation methods based on the intention behind the law and their function in society. The thesis claims that consequences of poorly regulated sustainable stormwater management results in an inefficient use of resources and pose a risk for the environment. Sustainable development is not visible in any article in the Law on General Water Services and it therefore risk to be overlooked in practice. The issues of urban stormwater need to be more integrated in the municipal work and planning processes. The analysis reveals that there is support for resilient stormwater management when there is a combination of up-to date research and an objective teleological interpretation. As the shift towards sustainable urban environments entails several aspects, the use of administrative instruments is one important strategy in ensuring urban resilience.

<p> Conventional cereal crop residues, namely, rice (<i> Oryza sativa</i> L.), corn (<i>Zea mays</i> L.), and wheat (<i>Triticum aestivum</i> L.) is very abundant and readily available widely. It has been a nuisance to agronomic producers to manage these immense &ldquo;so-called wastes&rdquo;. The Energy Independence and Security Act (EISA) promulgated by the United States and The EU&rsquo;s renewable energy directive mandated the substantial incorporation of renewable energy in their final energy consumption. These led to the increase in R&amp;D&rsquo;s on biomass and bioenergy products in the United States as well. </p><p> Hammer mill grinds of different cereal crop residues, rice, wheat, and corn, sieved through 5"/64 , 1"/8 , and 5"/32 hammer mill screen sizes (details in chapter 3) are mixed with different binders namely gelatin, wheat gluten, and dry milk at 1:10, 1:15, and 1:20 proportions (Chapter 4). Applying Taguchi-Grey relational analysis for four factors with three levels each, optimal operating level for the control factors based on multi-response characteristics was determined. The multi-responses used for the study are bulk density, durability, compressive strength, and gross heating values. Binder ratio was most influential in determining pellet quality. Binder type was next influential factor. The combination of factor levels A₁B₁C₃D₁ was found to be optimal conditions for pelletization as final results were confirmed with tests. </p><p> The pelletization parameters for making better quality composite pellets were also investigated (in Chapter V). The same Taguchi &ndash;Grey relational analysis method was used for optimization. The process (material variables) parameters those are material type, particle size or grind size, binder type, and proportion of binder were closely studied using L9 Taguchi orthogonal array. Binder ratio (blending ratio) has most significant impact, and particle size (Hammer mill grind) has second greatest impact on pelleting composite wastes. Tests conducted employing optimal conditions (A3B3C2D1) has confirmed that better pellets were produced compared with the hypothesized conditions. </p><p> The cost analysis using Invest for excel was carried out in order to study the feasibility of solid biofuel project. The biomass assessment using Biopower Atlas and associated GIS tools from NREL demonstrated that the State of Arkansas has agricultural residues sufficient to support 50 kilotons and 66 kilotons biomass pellet plant. Economy of scale effect can be observed when comparing 50 kilotons and 66 kilotons pellet mill. Gelatin-wheat pellet mill at 50 kiloton and even 66 kilotons were predicted to be unprofitable at the current stage. However, analysis results showed pellet produced from pine shavings &ndash; wheat residue blends is profitable. Crop residues are promising resources due to its wide distribution and availability. It can be termed as a &ldquo;Backstop resource&rdquo; because it is renewable and will be economically viable option as the price of oil and gas become expensive. </p><p>

<p>Polybrominated diphenyl ether (PBDE) flame retardants are ubiquitous contaminants in the environment due to their heavy usage in plastics, foam, and textiles to comply with flammability standards from the 1970s through the late 2000s. Due to their toxicity and persistence in the environment, two of the three PBDE commercial mixtures (PentaBDE and OctaBDE) were banned by the Stockholm Convention on Persistent Organic Pollutants in 2009. The DecaBDE commercial mixture, which consists primarily of the fully brominated congener BDE-209, has been banned or phased out in the United States and Europe but is still in use in other parts of the world. Human exposure to PBDEs persists via environmental reservoirs of PBDEs and products produced before the bans/phase-outs. PBDEs disrupt thyroid hormone levels and neurodevelopment in fish and rodents and are associated with altered thyroid hormone levels and neurodevelopmental impairments in humans. However, the mechanism by which PBDEs alter neurodevelopment remains unclear. Knowledge of the mechanisms and molecular targets of PBDEs is necessary for a causal link to be established between PBDEs and neurodevelopmental impairments. The hypothesis of this thesis research is that PBDEs alter thyroid hormone levels in the brain by interfering with the activity of PBDE-metabolizing deiodinase enzymes in brain cells, which may result in decreased levels of thyroid hormones in the brain and impaired neurodevelopment. </p><p>In the first aim of this thesis research, the biotransformation of PBDEs was examined to determine whether hydroxylated PBDEs (OH-BDEs) are formed in the human brain. In biotransformation assays performed with human astrocytes, which are cells located at the blood brain barrier, no debrominated or OH-BDE metabolites were identified. The results indicate that the enzyme responsible for PBDE hydroxylation (CYP2B6) was not expressed in sufficient quantities to metabolize PBDEs in the astrocyte cells used in this study, but future studies should analyze the potential for PBDE hydroxylation in other brain cells. </p><p>In the second aim of this thesis research, the effects of PBDEs on the thyroid-activating enzyme Type 2 deiodinase (DIO2) were determined in human astrocyte cells. DIO2 converts thyroxine (T4) into triiodothyronine (T3), which is the primary ligand that binds to the thyroid nuclear receptors, and is a very important signaling molecule during neurodevelopment. Cultured primary astrocytes and a human glioma cell line (H4 cells) were exposed to PBDEs and OH-BDEs, and changes in DIO2 activity were measured using liquid chromatography with tandem mass spectrometry (LC/MS/MS). Exposure to BDE-99, -153, and -209, 3-OH-BDE-47, and 5'-OH-BDE-99 all resulted in significant decreases in DIO2 activity in the H4 cells by up to 80% at doses of 500-1,000 nM. Further experiments deduced that the primary mechanism responsible for this decrease in activity was attributed to decreased DIO2 mRNA expression, increased post-translational degradation of DIO2, and competitive inhibition of DIO2. The reduction in DIO2 activity by PBDE and OH-BDE exposures could potentially reduce the concentration of T3 in the brain, which may be responsible for the neurodevelopmental impairments produced by exposure to this class of compounds and needs to be further explored. </p><p>In the third aim of this thesis research, the effects of PBDEs and OH-BDEs were examined in the H4 cells and in a mixed culture containing a human neuroblastoma cell line (SK-N-AS cells). The SK-N-AS cells express the thyroid hormone-inactivating enzyme Type 3 deiodinase (DIO3), which works in concert with DIO2 to buffer the concentration of T3 in the brain. Exposure to BDE-99 decreased the concentration of T3 and the inactive thyroid hormone rT3 in the cell culture medium of co-cultured cells by 59-76%. 3-OH-BDE-47 competitively inhibited DIO3 with an IC50 of 19 uM. 5'-OH-BDE-99 increased the rT3 concentrations in cell culture medium by 400%, increased DIO3 activity in exposed cells by 50%, and increased DIO3 catalytic activity in cellular homogenates by over 500%. Further effects on the mRNA expression of several thyroid-regulated genes (DIO3, TR-a, TR-b, MCT8, and ENPP2) and oxidative respiration were also assessed in the SK-N-AS cells. DIO3 mRNA expression increased by 9 fold in cells exposed to 400 nM BDE-99, and ENPP2 mRNA expression increased by 2 fold in cells exposed to 500 nM BDE-99 and a mixture of the three congeners, but no other significant effects on mRNA expression were observed. The basal respiration rates and other parameters of oxidative respiration were also not significantly altered by exposure to PBDEs or OH-BDEs, but proton leak was increased by over 400% in cells exposed to 2 uM 5'-OH-BDE-99. </p><p>This was the first study to examine the effects of an environmental contaminant on human DIO2 and DIO3 in cultured cells. The results indicated that BDE-99 and OH-BDEs decreased the activity of DIO2 and 5'-OH-BDE-99 increased the activity of DIO3, which combined would lead to decreased levels of T3 exported from the cells into the extracellular environment. These results provide more evidence that disruption of DIO2 and DIO3 by PBDEs during development may mediate the neurodevelopment effects associated with PBDEs.</p> / Dissertation

Hybrid artificial proteins, in which artificial repetitive polypeptides are fused with natural proteins or subunits, are proposed as a new approach to combining materials properties with the biological functions of natural proteins. As a model system, we have produced hybrid artificial proteins as "sticky enzymes" where the artificial domain serves to bind to surfaces while the natural domain performs catalytic activities. The artificial domains are repetitive polypeptides designed to provide multiple acidic functional groups and/or adopt regular secondary structures. A family of artificial proteins with sequence motifs-(-(AlaGly)$\sb{\rm x}$ZGly-) -$\sb{\rm n}$ (Z = Glu or ProGlu) is used to gain control over the materials properties of the hybrid. The natural domain is a bacterial phosphotriesterase which catalyzes rapid hydrolysis of organophosphorus pesticides and nerve agents. Hybrid artificial proteins are produced by fusion of genes encoding the artificial and enzyme domains through recombinant DNA technology. The target proteins, with molecular weights varied from 55 to 65 kDa, were expressed in Escherichia coli. All the hybrids, even in crude cell lysates, exhibit catalytic activity for hydrolysis of paraoxon (diethyl p-nitrophenyl phosphate). The hybrid that contains the artificial domain ((AlaGly)$\sb3$ProGluGly) $\sb{16}$ (designated HAP3PEG16) exhibits Michaelis-Menten kinetics, with K$\sb{\rm m}$ = 120 $\mu$M and k$\sb{\rm cat}$ = 2500 s$\sp{-1}$. The hybrid artificial proteins are selectively adsorbed on basic surfaces (e.g., DEAE Sephadex) through the anionic charges of the artificial domain, and elute only at NaCl $\geq$ 100 mM. Immobilized HAP3PEG16 exhibits k$\sb{\rm cat}$ of 1800 s$\sp{-1}$ when using Protein-Pak DEAE microspheres as the insoluble support, yielding 72% relative activity compared with the free soluble form judging from the k$\sb{\rm cat}$ value. In a related investigation, a recombinant phosphotriesterase with six consecutive histidine residues at the N-terminus was constructed and expressed in Escherichia coli under control of a T7 phage promoter. The hexahistidine sequence allows purification of the recombinant enzyme by metal chelate affinity chromatography. The recombinant enzyme catalyzes hydrolysis of paraoxon with a k$\sb{\rm cat}$ of 3880 s$\sp{-1}$ and K$\sb{\rm m}$ of 150 $\mu$M. The recombinant phosphotriesterase was immobilized on non-porous silica microspheres by physical adsorption at 34 units of enzyme activity per mg of support. The immobilized phosphotriesterase exhibits a catalytic rate constant of 3490 s$\sp{-1}$. A new method using a continuous-flow biosensor arrangement is proposed for direct spectrophotometric determination of organophosphate pesticides. The method has been demonstrated by immobilization of the recombinant phosphotriesterase on glass beads by physical adsorption and catalytic hydrolysis of paraoxon to product p-nitrophenolate, which can be quantitatively analyzed by electronic absorption spectroscopy. A low detection limit (5 ng/ml), wide linear range (25 to 2500 ng/ml), good precision (R.S.D.= 0.7-5.8%) and sample frequency of 24 samples per hour were achieved by the proposed method. (Abstract shortened by UMI.)

Under what conditions can one expect to see a sustained system of community management of forests in operation? Considerable theoretical scepticism has been expressed by economists and others about the viability of any such institution. In this view, such institutions will inevitably result in a "tragedy of the commons." However, evidence from around the world has accumulated in recent years which suggests that common property institutions do exist, and in some cases, have existed for a long time. Using archival sources in India and the U.K., this thesis explores the fate of community management of forests in a region of the central Himalayas known as Kumaun. Kumaun was under British administration over the period 1815-1949. The forests of the region were not under formal state management till the 1860s. In fact, there is evidence of customary cooperative arrangements--informal local institutions--before the arbitrary takeover of forests by the new administrators. The new property regime had a disruptive effect on local institutions and precipitated much deforestation, especially since the state did not have the logistical wherewithal to enforce the new forest rules at a time when local arrangements had lost credibility. Two schools of thought emerged within the state bureaucracy to address the emerging crisis of rapidly diminishing forests. The "centralizers" argued for more effective supervision and an increase in state power in order to protect the forests. The "devolutionists," by contrast, canvassed for decentralized management by user communities. Several decades of experimentation with centralized methods failed to protect forests effectively and caused much political protest. The government ultimately had to resurrect local institutions in the 1920s. In the beginning this was a failure, since community management had lost all credibility in the eyes of local users. However, persistent efforts by government officers finally paid off and the new system of van panchayats (village forest councils) finally solved a problem which the state, on its own, could not.

Global climate change has emerged a new environmental issue affecting developing countries particularly after the signing of the United Nations Framework Convention on Climate Change in June 1992. This dissertation focuses on the factors which motivate Indian responses to global climate change at the international level. The study evaluates the relative impacts of two policy frames in the formulation of India's national climate change policy stance. The concept of "policy frames" refers to the idea that the definition of, and responses to a particular problem are constructed in terms of another more pressing and salient policy concern. A "policy frame" is an analytically constructed policy filter comprised of key, identifiable, policy features and existing resource constraints in a sector. The study traces the evolution of national energy (coal power and renewable energy) and environment sector policies under centralized planning based on a survey of a series of Five Year Plans (1970-1997). Characteristic sectoral policies are identified as constituting an "energy-related development policy frame" and an "environment-related development policy frame" under two distinct phases of national economic development--a managed economy and a liberalized economy. The study demonstrates that the 1991 shift towards phased economic liberalization resulted not only in a new set of energy (coal, power and renewable energy) policies and consequently an altered energy policy frame, but also in a largely unchanged set of environmental sector policies and consequently only a marginally altered environmental policy frame. The study demonstrates that the post-1991 energy policy changes together with existing energy resource constraints, constitute the dominant policy frame driving both the formulation of Indian policy stances at international climate change negotiations and also Indian responsiveness to coal, power, renewable energy, and climate change projects funded by the World Bank and GEF. The study also demonstrates that key features of the energy policy frame functions as a shared cognitive reference for a select group of national policy actors (comprising both policy makers and policy experts), responsible for formulating climate change policy responses. The study highlights the influential role played by very small set of national policy experts who construct national climate change options on the basis of features of the energy policy frame.

This exploratory study, conducted in an integrated watershed management project in rural Nepal, was intended to explore elements that empower women as a group. The study also explores the contributions of functional literacy to the empowerment process. Experiences of five different mothers' groups from both Brahman and Gurung backgrounds informed the understandings presented in this study. The women's experiences are different, partly due to cultural differences. Open-ended interviews, document reviews and observations are the main sources used to identify empowering factors. Major factors which contribute to empowering women as a collective group found in this study include both programmatic and non-programmatic interventions. This implies that looking at empowerment of women in developing countries through one lens and drawing conclusions on that basis is premature. Women's lives are influenced by political, social, cultural, economic, and educational situations. Therefore, to consider one component in isolation is inappropriate if the objective is to achieve a multi-faceted goal like empowerment. The study implies that empowerment, which occurs at different levels at different points in one's life, is a fluid process. Finally, several issues deserve further attention. Functional literacy, assumed to be thought-controlling and mechanical, can contribute to the empowerment process. Functional literacy, which promotes knowledge and skills needed for the learners' daily lives, raises motivation and participation in actions. Engaged in action which makes their daily lives easier and given opportunities, women find it useful to explore other possibilities to improve their situations. This trend keeps women engaged in action, reflection, and dialogue, enhancing their confidence, self-esteem, and ability to take charge of their situations. Areas where the study showed investigation is needed include: how can positive socio-cultural traditions be built up to strengthen community-based women's groups? What roles and attitudes do men hold regarding women's participation in individual and community development processes? How can raising men's awareness about and participation in family health and sanitation issues be incorporated into the programs? How can a multi-caste group function as a cohesive unit? And how much do issues of caste, as opposed to economic conditions, affect the process?

The proposition of this research is that the use of geographic information systems (GIS) is capable of generating significant social benefits and that benefit-cost analysis methods including measures of willingness-to-pay can be an effective approach to the valuation of those benefits. It is based on the assertion that measurement of benefits from the use of GIS, especially those that are non-market based, is not only important and difficult, but highly useful and informative as well. The issues considered include the defining of the economic characteristics of spatial data, an examination of economic methods that have proven to be useful in similar circumstances, the selection of cases that will allow for the results of this study to apply to other cases, and an analysis of the characteristics of environmental applications. This research studies a subset of the full range of GIS applications, those that have to do with the environment. The focus on this sub-set of GIS applications is for two reasons; the nature of complex environmental problems and the range of the benefits that are likely to arise from the use of GIS for environmental planning and management problems. This research has involved the use of both quantitative and qualitative research methods. In each effort at measuring the benefits of GIS detailed information is needed to understand the manner in which the information products are used and to construct a valid approach to measurement. The case study approach offers some desirable features. Its more informal nature offers the potential to gather information that may be useful when seeking to measure non-market benefits. It offers the potential for a series of sequential steps base on information gathered during an initial round of interviews and the ability look at each case in greater detail than might otherwise be possible. The particular approach used in this research involved three levels of interviews. Four key conclusions from this research follow: (1) Methods that rely on measures of willingness-to-pay are useful tools. (2) Efficiency benefits in some cases are not as significant as effectiveness benefits. (3) Measuring only some of the benefits of using GIS is sufficient in many cases. (4) Benefits may occur several organizations or years removed from the original GIS use. In summary this research has resulted in improving methods with which we can study the benefits of using GIS to help resolve complex environmental problems. The case study approach produced results that should be replicable in other studies. It also succeeded to the extent that it was possible to look through this approach and make some observations about broader issues and to generate a number of interesting propositions that could form the basis of other research efforts.