Over the past century, woody plants and shrubs have increased in abundance at the expense of grasslands in many semiarid regions. The availability and concentrations of nutrients influence the relative success of plants, but the effects of fire frequency on soil nutrients is unknown for semiarid grasslands. On the gunnery ranges of Fort Huachuca in southeastern Arizona, study sites were established to examine the effects of fire frequency on soil biogeochemistry, plant biochemistry, and δ¹³C values in soil organic matter (SOM). The sites were on homogeneous granitic alluvium where wildfire frequency history is known from 1973 to present and no cattle grazing has occurred in recent decades. Subplots represent fire frequencies of no burns, 3 fires per decade, and 5 fires per decade. The "no burn" plot has abundant C3 Prosopis velentina (mesquite) trees, whereas the burned plots are open C4-dominated grasslands with scattered mesquite trees. Prosopis trees have altered SOM pools by the concentration of plant nutrients and the addition of isotopically light shrub litter. Frequent fires have altered the basic geochemistry and nutrient availabilities of the soil, and the changes appear to be significant enough to affect plant growth. Soil pH increases with burning frequency, and TOC, total nitrogen, and plant-available phosphorus show significant increases on the infrequently burned plot. Burning is advantageous for preservation or restoration of grasslands, as total living grass biomass is greater on the two burned plots. Root biomass 11 is significantly lower on the "frequently burned" plot. Concentrations of the key nutrients nitrogen and phosphorus are reduced in plants on the burned sites compared to plants on the unburned site. Fires help re-distribute nutrients but evidence of nutrient concentrations and δ¹³C values are retained in SOM for many decades. Estimates of bulk carbon turnover rates range from 112 to 504 years. Evidence for modern C3 shrub expansion is found in the shift of SOM δ¹³C values from values characteristic of C4 grasses to C3 shrubs in surface soil layers. δ¹³CSOM values indicate that the Holocene and Late Pleistocene were dominated by C4 grasslands, and the pre-Late Pleistocene vegetation was a C4-grass savanna with abundant C3 plants.

Understanding the extent of microbial transport, distribution and activity in the subsurface is paramount for effective in-situ bioremediation. In one study, we investigated the impact a substrate pulse has on the movement of inoculated or indigenous bacteria through saturated porous media. In another study, we developed a method to visualize the distribution of bacteria on soil surfaces. The elution of either inoculated or indigenous bacteria was monitored from model (homogenous) sand or natural (heterogenous) soil column systems. Sand columns receiving salicylate resulted in enhanced elution of inoculated P. putida. However, the salicylate pulse did not result in enhanced elution of P. putida from a natural system. For natural heterogenous systems, the salicylate pulse significantly affected the elution of certain indigenous bacteria. Specifically, more heterotrophs were eluted from soil columns receiving salicylate than from those that did not for both loamy sand soils tested. On the other hand, there were consistently fewer salicylate-degrading cells eluted in the presence of salicylate from one of the two soils tested. These data suggest that bacterial transport is a function of both the porous medium and the microbial population(s) under investigation. In the second study, an agar lift-DNA/DNA hybridization technique was developed to visualize the distribution of eubacteria on soil surfaces. Briefly, a single layer of soil was lifted from the surface of soil microcosms onto agar slabs and allowed to incubate. Bacterial colonies were lifted from the agar slabs onto membranes. The location of individual colonies was detected on the membranes by hybridization with a probe complementary to a conserved region of the eubacterial genome. This method was able to detect active microorganisms on different soil surfaces. The probe signal correlated well with the number of metabolically active microorganisms found in soils amended with a carbon source. This technique also allowed for visualization of localized microbial activity. A combined approach utilizing both soil column studies and the agar-lift technique should allow researchers to better elucidate microbial transport, distribution and activity in subsurface environments.

Lake Tanganyika, East Africa, is one of the world's unique freshwater ecosystems. This lake is approximately 10 million years old and contains an extremely diverse fauna with high levels of endemicity. Most of the biodiversity in the lake is concentrated along the rocky shoreline, and this dissertation focused on the land-water interactions that may affect the littoral ecosystem as human population densities increase. First, the potential of carbon and nitrogen stable isotopes as indicators of human impact was examined. Sedimentary organic matter from four river deltas with contrasting patterns of land use was used to develop a predictive relationship between terrestrial patterns and geochemical signals. Stable isotope analyses of cores taken at two disturbed and two undisturbed watersheds were consistent with patterns seen in surface sediments. These results suggest that nitrogen isotopes are a better indicator of land use while carbon isotopes are useful in determining changes in vegetation patterns. To evaluate the effect of deforestation on ecosystem dynamics, epilithic metabolism was measured at several sites over a period of one year. Epilithic net productivity did not differ significantly between the disturbed and undisturbed watersheds, but epilithic respiration and algal biomass were significantly higher at the disturbed site. Further evidence of disturbance was given by greater amounts of inorganic material on the rocks and lower ambient oxygen concentrations at the impacted site. Finally, in order to identify species more susceptible to changes in benthic productivity, the food web structure of the pelagic and littoral food webs was elucidated using stable isotopic analyses. Diet specificity is not apparent in the littoral food web, suggesting that broad dietary preferences may help stabilize this persistent food web during environmental perturbations. The isotopic structure of the pelagic food web suggests that upwelling of deeper waters is an important nutrient source for the food web, which is consistent with current nutrient and hydrodynamic models.

Forest disturbance is expanding in rate and extent and is affecting many montane catchments critical to water resources. Western North America is experiencing an epidemic of mountain pine beetle (MPB) that has affected 20 million hectares of forest in Canada and the United states. This epidemic may have long-lasting consequences for coupled cycles of water, energy, and biogeochemicals. While impacts of forest disturbance by fire and harvest have been studied for more than a half-century, insect-driven mortality differs from these events in the timing and accompanying biophysical impacts. In this work, we quantified catchment hydrologic and hydrochemical response to severe MPB infestation in a lodgepole pine ecosystem. Observations were organized laterally in a nested fashion from soil observations to nested headwater catchments. Vertical observations encompassed what is often termed the critical zone, from atmospheric interactions at the top of the forest through the ground surface and the rooting zone to the interface with groundwater. We quantified responses manifest in snowpack, the primary hydrologic input to this montane ecosystem, in water partitioning between vapor flux and streamflow, and in biogeochemical patterns across the landscape. Key findings of this study include 1) Loss of shelter from the atmosphere caused compensatory sublimation of snowpack to offset decreased interception losses after MPB-driven canopy loss; 2) Vaporization at multiple scales increased over time and in comparison to control forest, reducing water available for streamflow; 3) Nitrogen (N) concentrations were elevated in hillslope groundwater, but attenuation in the riparian zone protected streams from major N influx; and 4) headwater streams rapidly attenuated dissolved carbon (C) and N inputs. Collectively these results demonstrate compensatory negative feedbacks which help explain the lack of strong response to streamflow and stream chemistry observed in the recent MPB epidemic.

Forest disturbance is expanding in rate and extent and is affecting many montane catchments critical to water resources. Western North America is experiencing an epidemic of mountain pine beetle (MPB) that has affected 20 million hectares of forest in Canada and the United states. This epidemic may have long-lasting consequences for coupled cycles of water, energy, and biogeochemicals. While impacts of forest disturbance by fire and harvest have been studied for more than a half-century, insect-driven mortality differs from these events in the timing and accompanying biophysical impacts. In this work, we quantified catchment hydrologic and hydrochemical response to severe MPB infestation in a lodgepole pine ecosystem. Observations were organized laterally in a nested fashion from soil observations to nested headwater catchments. Vertical observations encompassed what is often termed the critical zone, from atmospheric interactions at the top of the forest through the ground surface and the rooting zone to the interface with groundwater. We quantified responses manifest in snowpack, the primary hydrologic input to this montane ecosystem, in water partitioning between vapor flux and streamflow, and in biogeochemical patterns across the landscape. Key findings of this study include 1) Loss of shelter from the atmosphere caused compensatory sublimation of snowpack to offset decreased interception losses after MPB-driven canopy loss; 2) Vaporization at multiple scales increased over time and in comparison to control forest, reducing water available for streamflow; 3) Nitrogen (N) concentrations were elevated in hillslope groundwater, but attenuation in the riparian zone protected streams from major N influx; and 4) headwater streams rapidly attenuated dissolved carbon (C) and N inputs. Collectively these results demonstrate compensatory negative feedbacks which help explain the lack of strong response to streamflow and stream chemistry observed in the recent MPB epidemic.

The general goal of this thesis was to examine and quantify the role of rooted submerged aquatic macrophytes in the cycling of metals in the littoral zone. An empirical study using data from an extensive literature survey showed that aquatic plants do not differ markedly in element composition from the sediments in which they grow, and that during uptake the plant's roots do not discriminate between elements essential and not essential for growth. The organic content, pH and redox potential of the sediments were shown to affect the bioavailability of metals to the plants. Biomass density was used to categorize species to assess broad patterns in plant-sediment metal relationships. It was found that the presence/absence of an understory contributed variation to the plant-sediment metal relationships. The role of rooted macrophytes as vectors for various elements between the sediments and attached epiphyte was quantified by growing Myriophyllum spicatum in radio-labelled sediments. This species was found to be a link between the sediments and attached epiphytes for the 4 elements studied (Co, Cs, Eu and Mn). Finally, the export of dissolved metals from weedbeds during plant senescence was quantified using a mass balance approach. It was found that approximately 15% to 30% (depending on the metal) of the metal inventory of the plants at maximum seasonal biomass was lost as dissolved compounds during senescence. During the growing season the macrophyte beds were net sources of metals to the lake, but were net sinks annually.

Discrepancies in ecotoxicity effects data derived from soils amended with dissolved metals in the laboratory and soils from historically aged metal-contaminated sites pose a challenge in deriving environmentally relevant soil quality criteria. In this thesis, the chemical artefacts produced by dissolved metal additions and the subsequent effects on metal bioavailability, toxicity and bioaccumulation are examined. The overall goal of this research is to advance the understanding of soil trace metal bioavailability mechanisms and improve current methods for ecotoxicity testing and bioavailability modeling. / The first objective was to develop a leaching method which would minimize the "salt-effect" commonly observed in freshly-spiked soil samples. This was achieved by adapting a column leaching procedure in order to spike and leach larger volumes of test soil as a preparatory step prior to ecotoxicity assays. An experiment was set up to observe changes to leachate chemistry resulting from the dissolved Cu additions and subsequent leaching with two weak electrolyte solutions. Results showed that leaching removed the excess dissolved Cu as well as the excess acidity and base cations that were solubilized during the Cu additions. Differences between control and spiked samples of some key soil solution parameters (e.g. pH, DOC and total dissolved Ca, Mg, Al, Fe) were reduced thereby resulting in a set of spiked samples more conducive to deriving causal dose-response relationships. / A second experiment compared soil and soil solution properties of samples which underwent the spike/leach procedure to those of freshly spiked samples. Lower soil pH (up to 0.81 pH units) and DOC concentrations were observed in non-leached samples as well as up to 35-fold and 55-fold increases of dissolved Ca and Mg concentrations, typical of the salt-effect. It was estimated that the non-leached samples contained up to 100-fold greater Cu2+ and 50-fold greater Al3+ activities which, I hypothesized, could result in greater phytotoxicity of non-leached samples. Bioassays were conducted wherein Hordeum vulgare (barley) seedlings were exposed to the leached and non-leached Cu-spiked soil samples for 14 days. The leached samples were less toxic to barley and showed significant increases (up to 1.7-fold) in median inhibitory concentrations (i.e. IC50) for root elongation in two of the three test soils. The Cu2+ fraction was able to explain much of the variability in toxicity between leached and non-leached samples, as well as among the different test soils. One exception was the most acidic test soil for which plants in the leached samples showed up to 10-fold greater toxicity than plants in the non-leached samples, when exposed to similar Cu2+ activities. Soil speciation and bioaccumulation data for Cu, Al and Ca were used to deduce that Ca deficiency and possibly Al toxicity contributed to the toxicity observed in this sample set. / In a modeling exercise, the concepts of the terrestrial biotic ligand model (TBLM), which take into account ion competition at the soil solution/root interface, to describe toxic response in our samples. Results showed that the additive effects of Cu and Al toxicity estimated from the Cu-root ligand complex (Cu-BL+) and Al-root ligand complex (Al-BL2+ ) accounted for more of the variability in toxic response data than did the Cu2+ fraction or the Cu-BL+ fraction alone. The model however, could not account for the effects of the Cu-induced Ca deficiency in the most acidic test soil, thus highlighting one of the limitations of the TBLM. This thesis has contributed to the understanding of metal bioavailability mechanisms affected by soil spiking procedures and highlights the benefits of soil leaching in preparing soil samples for ecotoxicity assays which should improve trace metal risk assessment in the future.

Ten dry cleaning sites were evaluated in the Houston area. At the dry cleaning sites studied, the contamination may be attributed to deficiencies in the separation equipment of the dry cleaning equipment, allowing free phase perchloroethene (PCE) to enter the sanitary sewer lines and escape by permeating through the pipe, or through defects in the pipe. Three sites with different geologic characteristics were chosen for intensive study to examine if there exists a pattern of transformation of PCE to the daughter product trichloroethene (TCE) in the sites. Transformation is compared by calculating the ratio of PCE to TCE for each well for a single sampling event, and by modeling at one of the sites. One site was modeled with the model RT3D, and the results from the model confirm the change in PCE to TCE ratio as being a result of a change in the reaction rate. A pattern was noticed in the site data which sites with sandier hydrologies, as measured by hydraulic conductivity, tended to have lower transformation rates than sites with tighter formations. It is suggested that this difference in apparent reaction rate may be due to enhanced reaction in the tighter formations due to lack of oxygen recharge, leading to an anaerobic region that is conducive to reductive dechlorination.

No description available.

Two catchments amended with snow fences were paired with unaltered controls to investigate the influences of increased snow accumulation on the hydrology, soil thermal regime, and nutrient fluxes from High Arctic headwater catchments, representative of polar desert and mid-moisture vegetative classes at the Cape Bounty Arctic Watershed Observatory (CBAWO). The impact of augmented snow accumulation on the winter soil thermal regime was highly variable during the period studied. Soil temperatures were 8-9°C warmer beneath a drift 54 cm deep compared to ambient snow (10 cm) in the winter of 2006-2007, whereas soil temperatures were not significantly warmer beneath drifts (88 and 50 cm) compared to ambient snow (18 and 35 cm) in the winter of 2007-2008. Departures between air and ground surface temperatures suggest that snow accumulation was insufficient to insulate soils before February 2007-2008 due to late snow accumulation, compared to earlier snow accumulation in September in the winter of 2006-2007. The augmented snow accumulation did not significantly impact the timing of soil thaw in spring or active layer thickness at this site. Greater snow accumulation in the amended catchments altered runoff characteristics, including an extended duration of runoff by 30-80%, a delay in peak flow of ~5 days, and increased runoff ratios. Augmented snow accumulation, resulted in greater fluxes of dissolved organic carbon (DOC), dissolved organic nitrogen (DON), dissolved inorganic carbon (DIC), nitrate (NO3-), ammonium (NH4+) and total inorganic solutes (TIS) in amended catchments relative to control sites. The seasonality of solute fluxes were also affected, with a greater proportion of inorganic solute fluxes occurring in the later portion of the runoff season compared to the controls. Snow accumulation was strong factor in determining total specific solute fluxes, with the magnitude of DOC and DON fluxes also strongly dependent on vegetative class. An active layer detachment that occurred in one of the amended catchments may have contributed to changes in nutrient fluxes, but the precise influence of the active layer detachment could not be differentiated from the combined impact of the disturbance and increased snow accumulation. / Thesis (Master, Geography) -- Queen's University, 2010-09-23 10:36:11.833