Little is known about the enzyme-substrate interactions occurring during the dechlorination of chloroform (CF) and 1,1,1-trichloroethane (1,1,1-TCA) by the enrichment culture containing Dehalobacters, hereafter called DHB-CF/MEL. Compound specific isotope analysis (CSIA) is used to investigate the factors which may affect the isotope fractionation observed for CF and 1,1,1-TCA dechlorination. This thesis reports the first isotope enrichment factors observed for CF biodegradation at -27.5‰ ± 0.9‰, thus providing fundamental information for comparing isotope enrichment factors observed during trichlorinated alkane degradation by DHB-CF/MEL. The thesis also reports how the presence of CF and 1,1,1-TCA influences isotope fractionation and explores the possible influence of substrate inhibition on isotope fractionation during 1,1,1-TCA dechlorination. The data suggests that substrate inhibition during 1,1,1-TCA dechlorination by DHB-CF/MEL may not affect carbon isotope fractionation. The results suggest that CSIA is a promising monitoring tool even for the simultaneous biodegradation of CF and 1,1,1-TCA at different 1,1,1-TCA starting concentration.

Current estimates of terrestrial carbon (C) fluxes overlook explicit hydrological controls. In this research project, a spatially explicit hydro-ecological model, BEPS-TerrainLab V2.0 was further developed to improve our understanding of the non-linearities associated with various hydro-ecological processes. A modeling study was conducted in a humid boreal ecosystem in north central Quebec, Canada. The sizes and nature of various ecosystem-C-pools were comprehensively reconstructed under a climate change and disturbance scenario prior to simulation in order to ensure realistic biogeochemical modeling. Further, several ecosystem processes were simulated and validated using field measurements for two years. A sensitivity analysis was also performed. After gaining confidence in the model’s ability to simulate various hydrologically controlled ecophysiological and biogeochemical processes and having understood that topographically driven sub-surface baseflow is the main process determining the soil moisture regime in humid boreal ecosystem, its influence on ecophysiological and biogeochemical processes were investigated. Three modeling scenarios were designed that represent strategies that are currently used in ecological models to represent hydrological controls. These scenarios were: 1) Explicit, where realistic lateral water routing was considered 2) Implicit, where calculations were based on a bucket-modeling approach 3) NoFlow, where the lateral sub-surface flow was turned off in the model. In general, the Implicit scenario overestimated GPP, ET and NEP, as opposed to the Explicit scenario. The NoFlow scenario underestimated GPP and ET but overestimated NEP. The key processes controlling the differences were due to the combined effects of variations in plant physiology, photosynthesis, heterotrophic respiration, autotrophic respiration and nitrogen mineralization; all of which occurred simultaneously in different directions, at different rates, affecting the spatio-temporal distribution of terrestrial C-sources or sinks (NEP). From these results it was clear that lateral water flow does play a significant role in the net terrestrial C distribution and it was discovered that non-explicit forms of hydrological representations underestimate the sizes of terrestrial C-sources rather than C-sinks. The scientific implication of this work demonstrates that regional or global scale terrestrial C estimates could have significant errors if proper hydrological constraints are not considered for modeling ecological processes due to large topographic variations of the Earth’s surface.

I studied how geology, land use and rainfall, correlated with peak flow responses in 110 headwater stream sites during a drought year. Highest discharges were observed in the most developed catchments and in the most poorly drained soils, but specific responses were variable depending on both geology and land disturbance. Redundancy analysis indicated that both surficial geology and land disturbance were important predictors of discharge and that rainfall was in general a poor predictor of discharge. I conclude that responses of headwater streams to individual storms are unpredictable from data generated using GIS, but increased peak flows occur associated with human development, mitigated by surficial geology. The headwater streams that are most vulnerable to flow alterations occur on poorly drained soils, and where urbanization tends to concentrate. Much greater attention to managing water is required if further degradation of stream ecosystems is to be prevented from our future land use.

Upland environments are important sources of mercury (Hg) to downstream wetlands and water bodies. Hydrology is instrumental in facilitating Hg transport within, and export from watersheds. Two complementary studies were conducted to assess the role hydrological processes play in controlling Hg mobility and transport in forested uplands. A field study compared runoff and Hg fluxes from three, replicate hillslope plots during two contrasting spring snowmelt periods, in terms of snowpack depth and timing. Hillslope Hg fluxes were predominately flow-driven. The melting of soil frost significantly delayed a large portion of the Hg flux later into the spring following a winter with minimal snow accumulation. A microcosm laboratory study using a stable Hg isotope tracer applied to intact soil cores investigated the relative controls of soil moisture and precipitation on Hg mobility. Both hydrologic factors control the mobility of contemporary Hg; with greatest Hg flushing from dry soils under high-flow conditions.

Master of Science / Department of Biological & Agricultural Engineering / Kyle R. Douglas-Mankin / The Great Plains once encompassed 160 million hectares of grassland in the central United States. In the last several decades, conversion of grassland to urban and agricultural production areas has caused significant increases in runoff and erosion. Past attempts to slow this hydrologic system degradation have shown success, but climate change could once again significantly alter the hydrology. The Intergovernmental Panel on Climate Change (IPCC) studies the state of knowledge pertaining to climate change. The IPCC has developed four possible future scenarios (A1, A2, B1 and B2). The output temperature and precipitation data for Northeast Kansas from fifteen A2 General Circulation Models (GCMs) were analyzed in this study. This analysis showed that future temperature increases are consistent among the GCMs. On the other hand, precipitation projections varied greatly among GCMs both on annual and monthly scales. It is clear that the results of a hydrologic study will vary depending on which GCM is used to generate future climate data. To overcome this difficulty, a way to take all GCMs into account in a hydrologic analysis is needed. Separate methods were used to develop three groups of scenarios from the output of fifteen A2 GCMs. Using a stochastic weather generator, WINDS, monthly adjustments for future temperature and precipitation were applied to actual statistics from the 1961 – 1990 to generate 105 years of data for each climate scenario. The SWAT model was used to simulate watershed processes for each scenario. The streamflow output was analyzed with the Indicators of Hydrologic Alteration program, which calculated multiple hydrologic indices that were then compared back to a baseline scenario. This analysis showed that large changes in projected annual precipitation caused significant hydrologic alteration. Similar alterations were obtained using scenarios with minimal annual precipitation change. This was accomplished with seasonal shifts in precipitation, or by significantly increasing annual temperature. One scenario showing an increase in spring precipitation accompanied by a decrease in summer precipitation caused an increase in both flood and drought events for the study area. The results of this study show that climate change has the potential to alter hydrologic regimes in Northeast Kansas.

Master of Science / Department of Geology / Saugata Datta / With the ever-rising atmospheric concentrations of CO₂ there arises a need to either reduce emissions or develop technology to store or utilize the gas. Geologic carbon storage is a potential solution to this global problem. This work is a part of the U.S. Department of Energy small-scale pilot studies investigating different areas for carbon storage within North America, with Kansas being one of them. This project is investigating the feasibility for CO₂ storage within the hyper-saline Arbuckle aquifer in Kansas. The study incorporates the investigation of three wells that have been drilled to basement; one well used as a western calibration study (Cutter), and the other two as injection and monitoring wells (Wellington 1-28 and 1-32). Future injection will occur at the Wellington field within the Arbuckle aquifer at a depth of 4,900-5,050 ft. This current research transects the need to understand the lateral connectivity of the aquifers, with Cutter being the focus of this study. Three zones are of interest: the Mississippian pay zone, a potential baffle zone, and the Arbuckle injection zone. Cored rock analyses and analyzed formation water chemistry determined that at Wellington there exists a zone that separated the vertical hydrologic flow units within the Arbuckle. This potential low porosity baffle zone within the Arbuckle could help impede the vertical migration of the buoyant CO₂ gas after injection. Geochemical analysis from formation water within Cutter indicates no vertical separation of the hydrologic units and instead shows a well-mixed zone. The lateral distance between Cutter and Wellington is approximately 217 miles. A well-mixed zone would allow the CO₂ plume to migrate vertically and potentially into potable water sources. Formation brine from Cutter was co-injected with supercritical CO₂ into a cored rock from within the Arbuckle (7,098 ft.). Results show that the injected CO₂ preferentially preferred a flow pathway between the chert nodules and dolomite. Post reaction formation chemistry of the brine showed the greatest reactivity occurring with redox sensitive species. Reactivity of these species could indicate that they will only be reactive on the CO₂ plumes front, and show little to no reactivity within the plume.

Master of Science / Department of Geology / Saugata Datta / Mass poisoning of arsenic (As) has affected roughly 60 million people in the Bengal Basin (Bangladesh and West Bengal, India) and 43 million people alone in West Bengal. Elevated levels of Manganese (Mn) is another alarming issue in the groundwaters of this region (MCLs: As<10µg/L and Mn< 0.4mg/L). Four locations in Murshidabad district (south-central part of Bengal Basin) were chosen for this current study. Among the 4 locations, two of them showed high concentration of As (>50 - 4622µg/L; 2009 survey) and they are Beldanga: 23° 56'N& 88°15'E and Hariharpara: 24°3.68'N & 88° 21.63'E. On the other hand: Nabagram (24°12.08'N & 88°13.29'E) and Kandi (23°58.6'N & 88°6.68'E) demonstrated less dissolved As (<10µg/L) in groundwaters. Study areas were located to the west (Nabagram, Kandi) and east (Beldanga, Hariharpara) of the river Bhagirathi, a tributary of the river Ganges, flowing N-S through the district of Murshidabad. Eastern side of the river is occupied by grey colored Holocene sediments and western side has more oxidized orangish-brown Pleistocene sediments. Comparative study of major water quality parameters between these sites revealed high As (10-1263µg/L) and low Mn (0.1-1.3mg/L) in the areas like Beldanga, Hariharpara while low As (0-15µg/L) and higher Mn (0.2-4.2mg/L) in Nabagram and Kandi. The pH range for high and low As areas were 4.5-7.8 and 5.1-8.2 respectively. Phosphates showed values <0.04-2.21mg/L in high As areas and <0.08-2.52mg/L in low areas whereas Cl- values were higher within low As areas (29-200mg/L) and lower within high As areas (3.9-78.4mg/L). Fe(t) and Fe2+ values at high and low As areas were 0-13.5mg/L, 0.01-0.11mg/L and 0-1.4mg/L, 0.04-0.06mg/L respectively. δ18O and δD results revealed that monsoonal precipitation is the major recharge source in this area with some input from the surficial waterbodies as ponds in shallower depths within high As areas. The total As extracted from core sediments in these areas do not show much difference: total As in high and low As areas ranges from 6.4-18 mg/kg. Sequential extraction results revealed that majority of the sediment bound As is present in residual phases (>40%). DOC in groundwaters in high and low As areas were 1.5-3.2 and 0.5-1.3mg/L respectively and they had positive correlation with As within the depth profiles. Dissolved organic matter (DOM) characterization studies indicated that microbial proteins (Tyrosine and Tryptophan) are the major components in the groundwaters in the low As region, whereas high As area groundwaters tend to have higher content of humic DOM (A and C). Cl/Br molar ratio of high As wells were low compared to the low As wells. Current study revealed the importance of organic matters (and not the mineralogy of the sediments) both in sediments and groundwaters in controlling the release of As from sediment, at least in the shallow parts of Bengal delta aquifer and microbial mediated reductive dissolution of FeOOH in the presence of organic matter is the major mechanisms by which sediment bound As (<50m depth) is released into the groundwater. The darker organic matter rich sediments (OM both sediment bound and anthropogenically derived) existing at the depth range 20m-50m with reducing environment persisting in both high and low As areas are possible reasons for elevated levels of As in this region.

Master of Landscape Architecture / Department of Landscape Architecture/Regional and Community Planning / Eric A. Bernard / This study is an integration of GIS, the Arc Hydro data model and tools, and hydrologic models to solve land use planning issues in the Little Kitten Creek watershed, Riley County, Kansas. Every day designers plan and design in watersheds. These designs alter the land use cover and change the hydrologic regime. Generally the design and development process does not consider upstream/downstream impacts on water quality and quantity. As a result development often increases flooding and water pollution. With the advent of the geodatabase, and the Arc Hydro geodatabase data model, designers have a flexible new tool for rapid simulation of a watershed. Arc Hydro allows the incorporation of traditional hydrologic data into linked modeling software together enabling users a “one-stop” approach for assimilating and modeling water resource systems. Once hydrologic data is in the Arc Hydro format it can be incorporated into assessment models, such as the Map to Map model. This case study assessed the floodplain analysis capabilities of the Map to Map model in the Little Kitten Creek (HUC 14) watershed. Steps to accomplish this goal were: data collection (digital and field surveys) and processing, geodatabase construction, linking the geodatabase with hydrologic modeling programs and, analysis of land uses within the watershed using the Map to Map model with the intent to produce flood maps based on land use changes.

Doctor of Philosophy / Department of Agronomy / P.V. Vara Prasad / Agriculture is the largest (90%) consumer of all fresh water in the world. The consumptive use of water by vegetation represented by the process evapotranspiration (ET) has a vital role in the dynamics of water, carbon and energy fluxes of the biosphere. Consequently, mapping ET is essential for making water a sustainable resource and also for monitoring ecosystem response to water stress and changing climate. Over the past three decades, numerous thermal remote sensing based ET mapping algorithms were developed and these have brought a significant theoretical and technical advancement in the spatial modeling of ET. Though these algorithms provided a robust, economical, and efficient tool for ET estimations at field and regional scales, yet the uncertainties in flux estimations were large, making evaluation a difficult task. The main objective of this study was to evaluate and improve the performance of widely used remote sensing based energy balance models, namely: the Surface Energy Balance Algorithm for Land (SEBAL), Mapping Evapotranspiration at high Resolution and with Internalized Calibration (METRIC), and Surface Energy Balance System (SEBS). Data used in this study was collected as part of a multi-disciplinary and multi-institutional field campaign BEAREX (Bushland Evapotranspiration and Agricultural Remote Sensing Experiment) that was conducted during 2007 and 2008 summer cropping seasons at the USDA-ARS Conservation and Production Research Laboratory (CPRL) in Bushland, Texas. Seventeen high resolution remote sensing images taken from multispectral sensors onboard aircraft and field measurements of the agro-meteorological variables from the campaign were used for model evaluation and improvement. Overall relative error measured in terms of mean absolute percent difference (MAPD) for instantaneous ET (mm h[superscript]-[superscript]1) were 22.7%, 23.2%, and 12.6% for SEBAL, METRIC, and SEBS, respectively. SEBAL and METRIC performances for irrigated fields representing higher ET with limited or no water stress and complete ground cover surfaces were markedly better than that for dryland fields representing lesser ET and greater soil water deficits with sparser vegetation cover. SEBS algorithm performed equally well for both irrigated and dryland conditions but required accurate air temperature data. Overall, this study provides new insights into the performance of three widely used thermal remote sensing based algorithms for estimating ET and proposed modifications to improve the accuracy of estimated ET for efficient management of water resources.

Ce mémoire a pour objectif d’approfondir les connaissances scientifiques sur les comportements hydrologiques des bassins versants arctiques et subarctiques. Les rivières drainant ces bassins versants sont parmi les systèmes fluviaux les moins étudiés et compris, étant donné leur vaste étendue et leur localisation éloignée. L’approche utilisée, issue de la discipline de l’hydrologie paysagère, présente une technique de classifications non-supervisées jumelées à des données de télédétection afin de caractériser le comportement hydrologique et les changements à l’échelle du paysage qui se sont produits sur les 35 dernières années dans un bassin versant subarctique de 42 000 km2. Plus précisément, plusieurs analyses géographiques d’image orientées-objet (AGIOO), employant des variables hydrogéomorphométriques et combinées à l’algorithme de classification Fuzzy C-Means, ont été produites, puis comparées afin de classifier et identifier les changements dans le paysage du vaste bassin versant de la Rivière George (BVRG), situé au Nunavik (Canada). Nos résultats indiquent que le BVRG contient deux types distincts de sous-bassins versants typologiquement similaires, distribués selon un gradient latitudinal, mettant en lumière une hétérogénéité spatiale dans les structures des sous-bassins constituant le BVRG. De plus, une expansion du type de bassins versants du sud dans le nord du BVRG est observée depuis les 35 dernières années. Cette expansion est principalement due à une augmentation de la production végétale et de l’humidité contenue dans les sols et la végétation, elle-même induite par une augmentation des températures moyennes annuelles et des précipitations totales annuelles associée aux changements climatiques. Ces changements observés dans la couverture terrestre ont des impacts importants et à long terme sur les processus hydrologiques du BVRG en augmentant les taux d’évapotranspiration. Ce phénomène pourrait expliquer la diminution d’environ 1% des débits annuels observée dans le BVRG entre les années 1970 et 2017. / The objective of this study is to develop scientific knowledge on the hydrological behaviors of Arctic and Subarctic watersheds. Rivers draining high-latitude watersheds are among the least studied and understood fluvial systems, given their large extent and their remote locations. Here we develop a landscape hydrology approach which pairs unsupervised classifications with remote sensing data to characterize the hydrological behavior and landscape scale changes that have occurred over a 42 000 km2 sub-arctic watershed over the last 35 years. More precisely, multiple Geographic Object-Based Image Analysis (GeOBIA), employing hydrogeomorphometric variables and combined to the Fuzzy C-Means clustering algorithm, were produced and then compared to classify and identify landscape change across the vast George River Watershed (GRW), situated in Nunavik (Canada). Our results indicate that the GRW contains two distinct subwatershed types which are distinct in their typology and distributed along a latitudinal gradient, which highlights spatial heterogeneity in the structures of the subwatersheds constituting the GRW. Moreover, an expansion of the southern type subwatersheds in the north of the GRW has been observed since the last 35 years. This expansion is principally due to increases in vegetation production and moisture content in soils and vegetation, themselves induced by increases in mean annual temperature (MAT) and total annual precipitation (TAP) associated with the changing climate in this northern watershed. These land cover changes are likely to have important and long-term impacts on the hydrological processes within the GRW by increasing rates of evapotranspiration. This phenomenon may explain the decrease of about 1% in the George River’s annual discharge observed between the mid-1970s and 2017.