Developing critical loads for nitrogen (N) in the Athabasca Oil Sands Region (AOSR) requires an understanding of the hydrological connectivity and potential for N transport among uplands, fens and bogs typical in the wetland-rich Boreal region of northern Alberta. The Cumulative Environmental Management Association’s (CEMA) overarching mandate is to determine a nitrogen critical load specific to the Boreal region of northern Alberta. To this end, nitrogen amendment experiments were initiated at two Boreal wetland sites: an upland – rich fen gradient at Jack Pine High (JPH) and an upland – fen – bog mosaic at Mariana Lakes (ML), 45 km north and 100 km south of Fort McMurray respectively. The objectives of this study are to use geochemical and isotopic tracers to describe baseline hydrogeochemical variability and connectivity between bog, fens and upland areas in the AOSR. Sites were instrumented with piezometer nests and water table wells along transects that cover the targeted landscape units (n = 108 sampling locations). Fieldwork related to this thesis was conducted during the open-water season: in June and August 2011, and in May, July, and September 2012. Field campaigns also included a snow survey (March 2012), and spring melt/freshet sampling (April 2012). The analysis of spatiotemporal variability of water isotopes and geochemistry in the years 2011-2012 yielded: i) a characterization of baseline conditions from which perturbations can be assessed, and ii) evidence of connectivity among landscape units. No evidence for elevated concentrations of nitrogen related to the amendment experiments was found in 2011 or 2012. The baseline characterization and annual monitoring did show increasing concentrations of inorganic ammonium with increasing depth associated with increasing solute concentrations: average concentrations of inorganic ammonium were 23 mg/L at deepest sampling locations (7 m) at ML bog and ML fen landscape units. These ammonium concentrations in porewaters, given a porosity of 0.90 for peatlands, constitute a store of ammonium that may be a significant source of nitrogen if the hydrology is altered due to co-occurring changes in vegetation (due to, for example, elevated nitrogen inputs), climate and/or landuse. Hydrologic connectivity at JPH is likely driven by topography. Hydraulic head in 2011 and 2012 field seasons showed that flow persisted from the upland to the fen. The consistent and distinct geochemical signatures and isotopic labelling of mid-depth and deep groundwater samples of fen and upland landscape units is consistent with such a stable groundwater continuum. Near-surface water samples at JPH fen however varied hydrogeochemically in response to seasonal changes in precipitation inputs, water levels, and biogeochemical productivity. At ML, hydrological connectivity is a function of antecedent moisture conditions (which determines run-off) and low and variable (10-6 to 10-9 m/s) hydrological conductivity of the peatland substrate (which may result in lateral flow where hydraulic head shows potential for vertical re- or discharge). Near-surface samples showed greater temporal than spatial variability as snowmelt inputs, variations in antecedent moisture conditions and seasonal changes in biogeochemical process rates affected nutrient and solute concentrations. In contrast, shallow, mid-depth and deep samples showed greater spatial than temporal variability. The spatial distributions of parameters could be associated to some degree with vegetation, distance along a surficial flowpath, or depth to mineral substrate or distance from the upland/edge transition. / Graduate / 0996 / 0388 / 0425 / cbkusel@yahoo.ca

Despite the importance of tropical rivers to the global carbon cycle, the nature of carbon cycling within these watersheds has been dealt with by only a handful of studies. The current work attempts to address this lack of information, using stable isotope and concentration measurements to constrain sources and sinks of carbon in two Peninsular Malaysian watersheds. The basins are located on the central-western and northeastern coasts of the Malaysian Peninsula, and are drained by the Langat and Kelantan Rivers, respectively. Water samples were collected from three points along the two rivers twice a month, in addition to the sampling of groundwater in adjacent aquifers. Principal component analyses (PCA) on water chemistry parameters in the Langat and Kelantan Rivers show the dominance of geogenic and anthropogenic influences, grouped in 4 to 6 components that comprise over 50 % of the total dataset variances. The geogenic input is reflected by components showing strong loadings by Ca, Mg, Mn, Si, and Sr, while anthropogenic influences via pollution are indicated via strong loadings by NO3, SO4, K, Zn and Cl. The carbon isotope and concentration data appear unrelated to these groups, suggesting that the riverine carbon cycle in both locations is dominated by other factors. These may include alternative sources of organic pollution, or inputs from the local vegetation and soils. The mean riverine 13CDOC of -27.8 ± 2.9 ‰ and -26.6 ± 2.2 ‰ in the Langat and Kelantan Basins, respectively, are consistent with the dominance of C3-type vegetation in both watersheds. Riverine 13CDIC signatures approach C3-like values at high DIC concentrations, with measurements as low as -19 ‰ in the Kelantan Basin and -20 ‰ observed in the Langat Basin, consistent with a biological origin for riverine DIC. However, the average 13CDIC in river water is 13C-enriched by about 10 ‰ relative to the expected C3 source in both rivers, and this 13C- enrichment appears to be largest with smaller DIC concentrations. Because of the overpressures of CO2 in the rivers, entrainment of isotopically-heavy atmospheric CO2 is not a likely explanation for the observed 13C-enrichment. Theoretically, dissolution of carbonates could be an alternative source of 13C-enriched carbon, but this lithology is scarce, particularly in the Langat watershed. The increase in DIC downstream and generally high pCO2 values in most river sections argues against aquatic photosynthesis as a primary causative factor for the observed isotopic enrichment. This elimination process leaves the speciation of riverine DIC and the evasion of CO2 as the most likely mechanisms for 13C-enrichment in DIC, via isotope fractionation during HCO3- hydration and CO2 diffusion. Potentially, methanogenic activity could also be, at least partially, responsible for the 13C-enrichment in DIC, particularly immediately downstream of the Langat Reservoir, but due to the absence of empirical data, this must remain only a theoretical proposition. The aquatic chemistry and dissolved carbon data suggests that pollution discharge into the Langat and Kelantan Rivers is the major factor that is responsible for the considerable CO2 overpressures and high DIC and DOC concentrations in the river waters, particularly in the downstream sections. This pollution is likely of biological origin, via sewage and palm oil mill effluent (POME) discharge, and therefore isotopically indistinguishable from natural C3 plant sources. Carbon budgets of the Langat and Kelantan River show CO2 degassing to be a significant mechanism of fluvial carbon loss, comprising roughly 50 %, or more, of the total riverine carbon export in both watersheds. The remainder of the river carbon is transported to the ocean in the form of DIC, DOC and POC in broadly comparable proportions. However, the combined riverine carbon export from the Kelantan and Langat Basins amount to 2 % or less of the total carbon sequestration of the watersheds. Thus, most of the sequestered carbon is returned to the atmosphere via respiration, with smaller amounts incorporated into ecosystem biomass . These results highlight the complexity of carbon cycling in tropical rivers, and agree with previous studies in showing riverine systems to be more than simple conduits of carbon from the land to the ocean.

Developing critical loads for nitrogen (N) in the Athabasca Oil Sands Region (AOSR) requires an understanding of the hydrological connectivity and potential for N transport among uplands, fens and bogs typical in the wetland-rich Boreal region of northern Alberta. The Cumulative Environmental Management Association’s (CEMA) overarching mandate is to determine a nitrogen critical load specific to the Boreal region of northern Alberta. To this end, nitrogen amendment experiments were initiated at two Boreal wetland sites: an upland – rich fen gradient at Jack Pine High (JPH) and an upland – fen – bog mosaic at Mariana Lakes (ML), 45 km north and 100 km south of Fort McMurray respectively. The objectives of this study are to use geochemical and isotopic tracers to describe baseline hydrogeochemical variability and connectivity between bog, fens and upland areas in the AOSR. Sites were instrumented with piezometer nests and water table wells along transects that cover the targeted landscape units (n = 108 sampling locations). Fieldwork related to this thesis was conducted during the open-water season: in June and August 2011, and in May, July, and September 2012. Field campaigns also included a snow survey (March 2012), and spring melt/freshet sampling (April 2012). The analysis of spatiotemporal variability of water isotopes and geochemistry in the years 2011-2012 yielded: i) a characterization of baseline conditions from which perturbations can be assessed, and ii) evidence of connectivity among landscape units. No evidence for elevated concentrations of nitrogen related to the amendment experiments was found in 2011 or 2012. The baseline characterization and annual monitoring did show increasing concentrations of inorganic ammonium with increasing depth associated with increasing solute concentrations: average concentrations of inorganic ammonium were 23 mg/L at deepest sampling locations (7 m) at ML bog and ML fen landscape units. These ammonium concentrations in porewaters, given a porosity of 0.90 for peatlands, constitute a store of ammonium that may be a significant source of nitrogen if the hydrology is altered due to co-occurring changes in vegetation (due to, for example, elevated nitrogen inputs), climate and/or landuse. Hydrologic connectivity at JPH is likely driven by topography. Hydraulic head in 2011 and 2012 field seasons showed that flow persisted from the upland to the fen. The consistent and distinct geochemical signatures and isotopic labelling of mid-depth and deep groundwater samples of fen and upland landscape units is consistent with such a stable groundwater continuum. Near-surface water samples at JPH fen however varied hydrogeochemically in response to seasonal changes in precipitation inputs, water levels, and biogeochemical productivity. At ML, hydrological connectivity is a function of antecedent moisture conditions (which determines run-off) and low and variable (10-6 to 10-9 m/s) hydrological conductivity of the peatland substrate (which may result in lateral flow where hydraulic head shows potential for vertical re- or discharge). Near-surface samples showed greater temporal than spatial variability as snowmelt inputs, variations in antecedent moisture conditions and seasonal changes in biogeochemical process rates affected nutrient and solute concentrations. In contrast, shallow, mid-depth and deep samples showed greater spatial than temporal variability. The spatial distributions of parameters could be associated to some degree with vegetation, distance along a surficial flowpath, or depth to mineral substrate or distance from the upland/edge transition. / Graduate / 0996 / 0388 / 0425 / cbkusel@yahoo.ca

The stable isotopes of oxygen and hydrogen have been employed worldwide as natural hydrological tracers, and most successfully in areas where extremes of climatic seasonality or relief exist. This project aims to assess the viability of the stable isotope technique for studies in the U.K. Systematic sampling was undertaken over two years in the Malham (Carboniferous limestone) and Lambourn (Chalk) areas. The monthly isotopic input signal in precipitation was found to be clearly definable, but less strongly seasonal than found elsewhere. Larger isotopic variations were revealed in weekly and within-storm samples. Snowmelt appeared to provide the most reliable 'spike' for tracing purposes. An attempt to relate weekly precipitation δ¹⁸0 values to air mass characteristics was encouraging for further investigations. Variations of isotope signal with altitude were erratic and not in accordance with normally accepted relationships. Isotopic variations in groundwaters of both areas, and in surface waters of the Lambourn area, rarely exceeded measurement error, and were close to mean annual values in precipitation. This indicated complete mixing of the input waters over one year or more. The isotopic range in precipitation was reduced by ~60% in surface waters of the Malham area. Early mixing and storage of water in the soil and/or upper karstic zone were indicated by comparison of the isotope data with conventional hydrological measurements at resurgences, and supported by strong signal attenuation measured in soil moisture. At certain sites, isotopic evidence revealed a persistence of winter recharge into summer baseflow. A smooth and strongly seasonal isotope signal, discovered in the waters of Malham Tarn, was attributed to evaporation processes and suggests important practical uses. It is concluded that the general application of the stable isotope technique may be more restricted in the U.K. than elsewhere, but that its provision of a new dimension to conventional data should contribute significantly in the future to selected hydrological studies.

Diverse fish species consume fruits and seeds in the Neotropics, in particular in the lowland reaches of large rivers, such as the Amazon, Orinoco, and Parana in South America. Floodplains of the Amazon River and its lowland tributaries are characterized by marked hydrological seasonality and diverse assemblages of frugivorous fishes, including closely related and morphologically similar species of several characiform families. Here, I investigated whether or not these fishes are capable of detecting fluctuations in food availability and if they are, how they adjust their feeding strategies. I tested predictions of optimal foraging, limiting similarity and resource partitioning theories with regard to expansion or compression of niche breadth and reduction in trophic niche overlap among species in relation with fluctuations in the availability of alternative food resources. I monitored fruiting phenology patterns to assess food availability and conducted intensive fishing during the high-, falling-, and low-water seasons in an oligotrophic river and an adjacent oxbow lake in the Colombian Amazon. I combined analysis of stomach contents and stable isotope ratios to evaluate dietary patterns, niche breadth, and niche overlap. Diets of six characiform fish species (Brycon falcatus, B. melanopterus, Myloplus asterias, M. rubripinnis, and M. torquatus) changed in a manner that indicated responses to fluctuations in food availability. Feeding strategies during the peak of the flood pulse were consistent with predictions of optimal foraging theory. During times of high fruit abundance, fish preferentially consumed items to which their phenotype is best adapted, maximizing net energy gain and enhancing fitness. As the flood pulse subsided and the availability of forest food resources was reduced in aquatic habitats, there was not a consistent pattern of diet breadth expansion or compression, even though diet shifts occurred, suggesting interspecific differences in foraging efficiencies. Analyses of diets and isotopic ratios revealed a general pattern of increased dietary segregation as the water level receded. Although there never was complete niche segregation among these fishes, these dietary changes effectively reduced interspecific niche overlap. Implications of these results and contribution of allochthonous food resources to diversity maintenance of floodplain fishes are discussed.

Thesis (Ph.D.) - University of Queensland, 2003. / Includes bibliography.

Thesis (Ph. D.)--Drexel University, 2006. / Includes abstract and vita. Includes bibliographical references.

The Summitville high-sulfidation gold deposit is hosted by a volcanic dome consisting of the South Mountain Quartz Latite that was erupted 23 Ma ago during formation of the Platoro Caldera complex in the San Juan volcanic field of south central Colorado. Alteration and mineralization developed during or shortly after dome emplacement as a result of metal-rich magmatic fluids and vapor emanating from a crystallizing intrusion at depth. Copper, arsenic, silver and gold are enriched in the deposit with two of the last paragenetic stages, the barite-base metal sulfide and goethite stages, containing the highest gold grades. Barite contains magmatic sulfur with a range of δ34S values (19.3 – 31.8 ‰) that reflects SO42– – H2S isotopic equilibration over a temperature range of 115 to 180 °C, which is consistent a calculated temperature of 147 °C based on the sulfur isotopic fractionation between intergrown barite and galena. Barite δ18O values (19.3 – 31.8 ‰) indicate the barite fluids contained a minor component of meteoric water. Barite growth zones with acicular crystals (wires) of emplectite (CuBiS2), a mineral not previously reported from Summitville, contained primary fluid inclusions that yielded a wide range of vapor to liquid homogenization temperatures as a result of stretching but consistent freezing point depressions that infer an average salinity of 5.1 wt. % NaCl equivalent. These data indicate that the barite fluids were modestly enriched in magmatic sulfur and metals (Cu, As, Bi, Pb, Zn, Au, Ag) and that barite precipitation was likely triggered by cooling during mixing with meteoric waters. The goethite stage developed during weathering of the deposit that likely occurred during uplift and exposure around 9 to 7.7 Ma ago based on 40Ar/39Ar dates on jarosite. The assemblage goethite + hematite ± jarosite ± scorodite ± gold filled open spaces and coated barite of the barite-base metal sulfide stage. Inclusions of barite and bladed alunite in the iron oxide/hydroxide (FeOx) matrix have the texture, composition and isotopic values of their earlier formed counterparts in the deposit and therefore represent residual material that survived the weathering event. Three 40Ar/39Ar dates on the bladed alunite ranged from 23.15 to 22.88 Ma, confirming their origin as magmatic hydrothermal alteration alunite. Layers of compositionally zoned, small rhombohedral crystals of alunite were also discovered in the FeOx matrix. Although these could not be successfully dated, they had a distinct texture, chemistry and isotopic composition (δ34S = 0.8 ‰ δ18O = 4.7 ‰) that indicated they formed during the weathering event. The acidic, oxidizing supergene fluids remobilized and broadly enriched the top of the deposit in Cu and Ag and locally in native gold (5 wt. % Ag).

The marked decline in tree island cover across the Everglades over the last century, has been attributed to landscape-scale hydrologic degradation. To preserve and restore Everglades tree islands, a clear understanding of tree island groundwater-surface water interactions is needed, as these interactions strongly influence the chemistry of shallow groundwater and the location and patterns of vegetation in many wetlands. The goal of this work was to define the relationship between groundwater-surface water interactions, plant-water uptake, and the groundwater geochemical condition of tree islands. Groundwater and surface water levels, temperature, and chemistry were monitored on eight constructed and one natural tree island in the Everglades from 2007-2010. Sap flow, diurnal water table fluctuations and stable oxygen isotopes of stem, ground and soil water were used to determine the effect of plant-water uptake on groundwater-surface water interactions. Hydrologic and geochemical modeling was used to further explore the effect of plant-groundwater-surface water interactions on ion concentrations and potential mineral formation. A comparison of groundwater and surface water levels, along with calculated groundwater evapotranspiration rates, revealed that the presence of a water table depression under the islands was concurrent with elevated groundwater uptake by the overlying trees. Groundwater chemistry indicated that the water table depression resulted in the advective movement of regional groundwater into the islands. A chloride budget and oxygen isotopes indicated that the elevated ionic strength of tree island groundwater was a result of transpiration. Geochemical modeling indicated that the elevated ionic strength of the groundwater created conditions conducive to the precipitation of aragonite and calcite, and suggests that trees may alter underlying geologic and hydrologic properties. The interaction of tree island and regional groundwater was mediated by the underlying soil type and aboveground biomass, with greater inputs of regional groundwater found on islands underlain by limestone with high amounts of aboveground biomass. Variations in climate, geologic material and aboveground biomass created complex groundwater-surface water interactions that affected the hydrogeochemical condition of tree islands.

The decline of freshwater ecosystems, generally result from land use activities in the river catchment and is of great concern worldwide. This study was conducted along Umtata River in the Eastern Cape province of South Africa between May 2010 and April 2011. The study was aimed at identifying macrophytes families (to species level) and determining the stable isotope signatures (C:N ratios, δ13C and δ15N) and to relate their isotopic signatures to the land use activities along the river catchment. Analysis of variance was performed to test the effect of sites and sampling period on the C:N ratios, δ13C and δ15N signatures. There were 16 macrophyte families represented by 26 species recorded along the river. There was only a significant difference in sites and sampling period in δ15N (p< 0.05). The highest C:N ratios value (30.75±9.65‰) was recorded in the upper reaches while the lowest value (6.10±2.35‰) occurred in the lower reaches. The δ13C values varied throughout the length of the river with highest values (-19.63±5.44‰) obtained in the middle reaches. Spatial variation was evident in δ15N throughout the length of the river and showed increase from the upper reaches to middle reaches and decreased towards lower reaches. The δ15N ranged from 3.92±2.43‰ in the upper reaches to 10.02±4.56‰ in the middle reaches. Temporal variation in δ15N was also evident throughout the sampling period with highest peak in May (9.77± 4.49‰) and lowest in February (0.50±2.49‰) respectively. The highest values of isotope signatures at spatial level demonstrated the true reflection of urban development, sewage discharge and agricultural activities taking place along the river system. Continued monitoring is recommended that may ultimately come up with a better management options for the communities living within the study area, and also to better enhanced land utilization.