<p>This study focuses on the development of a Direct Aqueous Injection Gas Chromatographic method with Flame Ionization Detection (DAI-GC/FID) for the analysis of MTBE and TBA. The analytical method was then applied in a site specific study where MTBE contamination was evident. The method achieved detection limits of 1 ppm for MTBE and 0.1 ppm for TBA. The method showed good precision, accuracy and selectivity. The method was selected primarily for its ability to simultaneously analyze MTBE and TBA. The result of the site specific study showed the persistence of high concentrations of MTBE and TBA at the source of contamination, whilst concentrations at the adjacent primary school dropped to below detection limits as a result of rapid natural attenuation. It was found that an overall decrease in MTBE concentrations was met with an increase in TBA concentrations / which is a direct indication of MTBE degradation. Despite the fact that problematic MTBE concentrations persist at the source of contamination, limited evidence of the persistence of MTBE contamination was identified at the adjacent primary school. As such, MTBE health risks from existing pathways were found to be irrelevant for receptors at the adjacent school.</p>

Understanding the hydrology of the riparian zone in a catchment can be an important prerequisite for determining solute loads and concentrations in streams. The riparian zone is the transition zone between surrounding landscape and an open water stream. This study focuses on the spatial and temporal variations of shallow groundwater levels in a forested headwater catchment in the Bergslagen area of central Sweden. Three snapshot campaigns were conducted during dry, humid and wet conditions to map the spatial variability of the groundwater levels. Piezometers giving the total hydraulic head were placed in the riparian zone along a stream network consisting of three first order streams and one second order stream. To asses temporal variations five groundwater wells were installed with automatic loggers to record continuous data during the wet period. Historical streamflow records from a permanent field station were collected and related to the groundwater levels in order to assess the relationship between groundwater levels and streamflow. Additionally a landscape analysis using GIS methods was conducted in order to identify potential drivers of spatial variation of groundwater levels in the riparian zone. The results showed that the slope could partially explain the observed spatial variability of riparian groundwater levels. The results from the spatially distributed piezometers and the continuously monitored groundwater wells with loggers were contradicting. Where the piezometers showed increasing depth to the groundwater table with increasing slope the loggers indicated the opposite. However, because the piezometers outnumbered the loggers the piezometer results can be considered more representative of the spatial variation of groundwater levels. There could be no general result concluded on the catchment scale but when looking at specific subcatchments it could be found that the variations in the riparian groundwater levels could be better explained where the stream had a more distinct channel. This indicates the importance to evaluate not only slope but the profile curvature as well for groundwater predictions.

In the last few decades protection of the environment has moved to the forefront of earth science research. Sustainable development is becoming more important to rapidly growing communities throughout southern Ontario including the City of Waterloo which has adopted an ecosystem planning approach toward future urban expansion. The City of Waterloo is located in the Regional Municipality of Waterloo which relies mainly on local groundwater resources for its drinking water supply. The Waterloo West Side is a collective name for several new developments occurring at the western limit of the City of Waterloo. Development of the Waterloo West Side is encroaching on a potential regional groundwater recharge area. Recent studies have recommended that some of these developments will require artificial infiltration facilities to augment the reduction in infiltration rates at the post-development stage. For this study, the pre-development groundwater flow system was characterized using a three-dimensional finite element model (WATFLOW). The regional Waterloo Moraine Model (approximately 750 km2) was refined in the study area (approximately 25 km2) so as to include the regional-scale influence on the local-scale groundwater flow. In addition, to approximate the complex groundwater flow system, within the study area, modifications were made to the current conceptual model. Several existing techniques were utilized in the numerical approach including three-dimensional parameterization and automated calibration methods. Simulations were completed to steady-state therefore results are averaged on a yearly basis. The potential impact of urbanization on the groundwater flow system was investigated by modifying the surficial boundary condition to simulate post-development infiltration rates (increased runoff) in areas where development will occur. The impact to local surface water was investigated for each post-development scenario. In addition, the effect on the regional and local groundwater flow systems were compared for each scenario.

Near-surface sediments play an important role in governing the movement of water and contaminants from the land surface through the vadose zone to groundwater. Generally, low permeability surficial soils restrict water flow through the vadose zone and form a natural protective barrier to migration of surface applied contaminants. These types of fine-grained soils commonly contain macropores, such as fractures, animal burrows, and root holes, that have been identified as preferential flow pathways in the subsurface. Accordingly, macropores have the potential to influence groundwater recharge rates and compromise the protective capacity of surficial soils, particularly where the overburden is thin and aquifers are close to the surface. Partially saturated flow and transport in these environments is inherently complex and not well understood. The objective of this thesis was to examine preferential flow processes and the associated movement of contaminants in macroporous, low permeability soils. This was accomplished by conducting numerical and field experiments to investigate and describe the dynamics of macropore flow during episodic infiltration through the vadose zone and evaluate the corresponding influence of macropores on vertical water flow and contaminant transport. Numerical simulations were conducted to identify the important physical factors controlling flow and transport behaviour in partially saturated, fractured soils. A three-dimensional discrete fracture model, HydroGeoSphere, was used to simulate infiltration into homogeneous soil blocks containing a single vertical rough-walled fracture. Relatively large rainfall events with return periods ranging from 5 to 100 years were used, since they are more likely to generate significant preferential flow. Initial results showed that flow system dynamics were considerably more sensitive to matrix properties, namely permeability and antecedent moisture content, than fracture properties. Capillary forces, combined with the larger water storage capacity in the soil matrix, resulted in significant fracture-matrix interaction which effectively limited preferential flow down the fracture. It is also believed that fracture-matrix interaction reduced the influence of fracture roughness and other related small-scale fracture properties. The results imply that aperture variability within individual fractures may be neglected when modeling water flow through unsaturated soils. Nevertheless, fracture flow was still an important process since the fracture carried the majority of the water flow and virtually all of the mass of a surface applied tracer to depth in the soil profile. Model runs designed to assess transport variability under a variety of different physical settings, including a wider range of soil types, were also completed. Vertical contaminant fluxes were examined at several depths in the soil profile. The results showed that the presence of macropores (in the form of fractures) was more important than matrix permeability in controlling the rate of contaminant migration through soils. The depth of contaminant migration was strongly dependent on the antecedent moisture content and the presence of vertically connected fractures. Soil moisture content played a pivotal role in determining the onset and extent of preferential flow, with initially wet soils much more prone to macropore flow and deep contaminant migration. Simulations showed that surface applied tracers were able to reach the base of 2 m thick fractured soil profiles under wetter soil conditions (i.e., shallow water table). Likewise, long-duration, low-intensity rainfall events that caused the soil to wet up more resulted in proportionately more contaminant flux at depth. Fractured soils were particularly susceptible to rapid colloid movement with particle travel times to depths of 2 m on the order of minutes. The main implication is that the vulnerability of shallow groundwater is related more to vertical macropore continuity and moisture conditions in the soil profile, rather than traditional factors such as soil thickness and permeability. Macropore flow and transport processes under field conditions were investigated using small-scale infiltration experiments at sites in Elora and Walkerton, Ontario. A series of equal-volume infiltration experiments were conducted at both sites using a tension infiltrometer (TI) to control the (negative) infiltration pressures and hence the potential for macropore flow. A simulated rainfall experiment was also conducted on a small plot at Walkerton for comparison with the TI tests. Brilliant Blue FCF dye and fluorescent microsphere tracers were applied in all tests as surrogates for dissolved and colloidal contaminant species, respectively. Upon completion of infiltration, excavations were completed to examine and photograph the dye-stained flow patterns, map soil and macropore features, and collect soil samples for analysis of microspheres. Cylindrical macropores, in the form of earthworm burrows, were the most prevalent macropore type at both sites. In the TI tests, there was a clear relationship between the vertical extent of infiltration and the maximum pressure head applied to the TI disc. Larger infiltration pressures resulted in increased infiltration rates, more spatial and temporal variability in soil water content, and increased depths of dye penetration, all of which were attributed to preferential flow along macropores. Preferential flow was limited to tests with applied pressure heads greater than -3 cm. Under the largest applied pressures (greater than -1.0 cm), dye staining was observed between 0.7 and 1.0 m depth, which is near the seasonal maximum water table depth at both field sites. The tension infiltrometer was also used to infiltrate dye along an exposed vertical soil face, thereby providing a rare opportunity to directly observe transient macropore flow processes. The resulting vertical flow velocities within the macropores were on the order of tens of meters per day, illustrating the potential for rapid subsurface flow in macropores, even under partially saturated conditions. The results suggest that significant flow occurred in partially saturated macropores and this was supported by simple calculations using recent liquid configuration models for describing flow in idealized macropores. On all excavated sections, microspheres were preferentially retained (relative to the dye) in the top five centimeters of the soil profile. Below this zone, dye patterns correlated well with the presence of microspheres in the soil samples. There was evidence for increased retention of microspheres at lower water contents as well as a slightly greater extent of transport for smaller microspheres. In general, the microsphere and dye distributions were clearly dictated by vadose zone flow processes. As in the numerical experiments, water storage in the soil matrix and related macropore-matrix interaction were important factors. Mass transfer of water through the macropore walls promoted flow initiation in the macropores near surface. Deeper in the soil, water drawn away from the macropores into the matrix significantly retarded the downward movement of water along the macropores. Imbibition of dye from the macropores into the matrix was repeatedly observed on excavated soil sections and during the transient dye test. Microspheres were also transported laterally into the soil matrix indicating that conceptual models for colloid transport in the vadose zone need to account for this mass transfer process. Overall, the tension infiltrometer performed extremely well as a tool for controlling macropore flow under field conditions and, together with the dye and microsphere tracers, provided unique and valuable insights into small-scale flow and transport behavior. The field experiments raise concerns about the vulnerability of shallow groundwater in regions with thin, macroporous soils. Only a fraction of the visible macropores contributed to flow and transport at depths greater than 40 cm. However, with dye and microsphere transport observed to more than 1.0 m depth, rapid macropore flow velocities, and the sheer number of macropores present, there was clearly potential for significant flow and transport to depth via macropores. Under the right conditions, it is reasonable to speculate that macropores may represent a significant pathway for migration of surface applied contaminants to groundwater over the course of a single rainfall event.

The Carrizo-Wilcox aquifer is a valuable groundwater resource, situated in a semi-arid landscape of Southwest Texas, where over-use by dependent farming practices has lowered aquifer levels. In semi-arid regions, rates of groundwater recharge are predominantly low due to high potential evapotranspiration rates; however, least understood is the role that vegetation plays in soil-plant-water dynamics. Vegetation management potentially plays a major role in countering the loss to recharge because evapotranspiration (ET) varies with vegetation type and cover. The conversion from shrubland to grassland likely reduces rooting depths and total plant cover. Subsequently, deep drainage (percolation below the root zone) will likely increase and lead to groundwater recharge, at least temporarily. The primary aims of the study were to identify those biotic and abiotic factors facilitating deep drainage and to examine differences in recharge for the years following clearing of natural shrub vegetation. Soil chloride was examined to estimate long-term recharge rates, since its concentration in the soil is influenced by the movement of water. Short-term soil moisture trends were also monitored for any water movement deep in the soil profile in response to individual rain events. Rooting depths decreased following removal of vegetation; yet root biomass unexpectedly increased due to successful grass establishment during the first five years after treatment. Soil properties did not vary between treatments, indicating that the majority of chloride differences seen were a consequence of vegetation change. Peak and total soil chloride concentrations were expected to decrease and occur deeper in the soil profile 15-30 years following the clearing of woody vegetation. Total chloride decreased by up to 65% after 30 years and resulted in an estimated 14.9 mm/yr more recharge compared to adjacent untreated controls. Evidence in this study suggest that much of this chloride is leached during the first five years following treatment and that more leaching occurs in especially wet periods. During the wet 2007 growing season, soil moisture below the root zone increased by up to 17% after vegetation clearing. The results of this study indicate that hydrologic changes following brush removal were evident in this system and are likely to positively influence groundwater recharge in the long-term.

Increasing demand for water supplies in semi-arid regions, such as San Antonio, has sparked an interest in potential recharge management through brush control. Two shallow caves under woody plant cover in northern Bexar County, Texas were chosen as study sites where a detailed water budget would be developed. The Headquarters Cave site measures natural rainfall and cave recharge while the Bunny Hole site is instrumented to measure throughfall, stemflow, surface runoff, and cave recharge. Large scale rainfall simulation was used at Bunny Hole to apply water directly above the cave footprint allowing us to determine how recharge differs between natural and simulated rainfall events. Under natural conditions, Headquarters Cave recharged 15.05% of the annual rainfall while Bunny Hole received 4.28%. Natural canopy throughfall measured 59.96% of the water budget; stemflow accounted for 0.48% and canopy interception was 39.56%; no surface runoff was measured. Rainfall simulations conducted at Bunny Hole resulted in an average of 74.5% throughfall, 5.3% stemflow, 20.2% canopy interception, 2.8% surface runoff, and 6.9% cave recharge; simulation intensities were typically higher than natural event intensities. General water budgets across the Edwards Plateau have concluded that evapotranspiration represents 65% of total annual rainfall while percolation and storage accounts for 30% and the remaining 5% is runoff. These studies have been focused on broad water budget parameters while this study looks at more detailed components. No other study to date has been able to combine throughfall, stemflow, surface runoff, and vertical recharge monitoring to quantify the water budget in the Edwards Plateau; these parameters are instrumental in determining a detailed water budget in juniper rangelands. Results from this study illustrate the significance of all aspects of the water budget and are the first to yield a firm measurement of actual upland recharge.

Over the last 30 years, lignite has become an important energy resource for the State of Texas. Production of lignite involves strip mining large areas of land in the Texas Gulf Coast region. Lignite at the Big Brown Mine, Freestone County, Texas, is produced from fluvial-deltaic sediments of the Calvert Bluff Formation of the Paleocene-Eocene Wilcox Group. Mining processes mix overburden material resulting in a spoil that is more homogeneous than the original unmined material over the area of the mine. The effects of mining on the environment are wide and varied, but mining is especially disruptive to the groundwater system. Groundwater recovery begins immediately after the spoil is placed, but occurs at highly variable rates. Hydrogeologic properties change rapidly in the first few years after mining and much of the groundwater recovery is dependent on the infiltration capacity of the spoil material. Resaturation of shallow spoil aquifers at the Big Brown Mine occurs at rates ranging from 0.6 to 3.0 m/yr (2-10 ft/yr). Recharge to the groundwater system is principally from direct infiltration of precipitation with variable resaturation rates attributed to variations in infiltration. For this study, four sites at the Big Brown mine were chosen for characterization. Three sites, designated fields C-13, C-24 and C-32, are located in reclaimed areas of the mine and range in age from 9 to 14 years old, while the fourth site is located in an unmined area (UM) between the two active mining pits. Infiltration rates were quantified using a drip infiltrometer to simulate rainfall. Results show that mining and reclamation processes can reduce infiltration rates by as much as 53 percent from the unmined values. Unmined areas show infiltration rates ranging from 12 to 30 cm/hr (4.7-11.8 in/hr) with a mean value of 20 cm/hr (7.9 in/hr). Mined areas show infiltration rates ranging from 3 to 22 cm/hr (1.2-8.7 in/hr) with a mean value of 9 cm/hr (3.5 in/hr). These rates vary significantly over the area of a single field resulting in high standard deviations, but a comparison of mean infiltration rates between the three mined areas show much less variation. It is unlikely that the small variations seen in the infiltration rates of fields C-13 and C-24 can, by themselves, account for the large variations in resaturation rates for these fields. Infiltration rates vary in response to changes in soil moisture content, spoil heterogeneity, soil mineralogy, and method of spoil placement. Higher values of infiltration occur when the soils are dry, generally from late spring to early fall. Differences in soil texture had less effect on infiltration rates than was hypothesized, with both coarse and fine grained soils showing similar values. Tracer tests, using sodium bromide as a conservative tracer and the red dye Rhodamine WT, were performed to determine if channeling of water occurs in the reclaimed soils. Trenches, cut in the dyed areas, were inspected for fractures and macropores and sampled at regular intervals for analysis of bromide concentration. Rhodamine WT showed some fractures in the soil structure, but due to a chemical reaction, sorbed strongly to the soil surface with little movement into the soil column. Concentration plots of bromide proved much more useful in determining mechanisms of flow and showed good vertical flow paths in fields C-13 and C-32. Lateral flow dominates in field C-24. Differences in flow mechanisms may best account for the variable resaturation rates seen in these fields. / text

published_or_final_version / Applied Geosciences / Master / Master of Science

No description available.

The Upper San Pedro River aquifer in Southern Arizona has been modeled using MODFLOW several times. The current model improves upon previous models by switching stream packages, adding a third season to represent the summer monsoon, and thereby creating a seasonalized steady-state oscillatory model. Recharge was seasonalized using a method to develop seasonal recharge estimates using ratios of seasonal precipitation to seasonal actual or potential evapotranspiration (ET). Maximum ET was seasonalized according to estimates of riparian groundwater consumption by vegetation in the study area. The model was run with inputs of 80%, 100% and 120% of base values for recharge and maximum ET rates to assess the sensitivity of the groundwater system and river to the seasonal timing and quantity of recharge and ET. The greatest amount of baseflow, 47%, occurred during the wet winter season, 35% occurred during the dry summer, and 18% during the wet summer (monsoon) season.