The Ngatamariki Geothermal Field is located 20 km north of Taupo in the Taupo Volcanic Zone and has a boundary of 12 km² as delineated by magneto-telluric surveys (Urzua 2008). Rhyolitic deposits, derived from the Maroa Volcanic Centre, dominate the geology of the area with the 186 AD (Wilson et al. 2009) Taupo pumice mantling stream valleys in the area. The majority of thermal features at Ngatamariki are located along the Orakonui Stream on the western boundary of the field; the stream area is dominated by a 50x30 m geothermal pool filling a hydrothermal eruption crater. This crater was formed during a hydrothermal eruption in 1948, with a subsequent eruption in April 2005. Orakei Korako is located 7 km north of Ngatamariki and has one of the largest collections of thermal features in New Zealand. The geology at Orakei Korako is similar to Ngatamariki, but the area is dominated by a series of south-west trending normal faults which create sinter terraces on the eastern bank of Lake Ohakuri. Water samples from springs and wells at Ngatamariki and Orakei Korako were taken to assess the nature of both fields. Spring waters at Ngatamariki have chloride contents of 56 to 647 mg/l with deep waters from wells ranging from 1183 to 1574 mg/l. This variation is caused by mixing of deep waters with a steam heated groundwater, above clay caps within the reservoir. Stable isotopic results (δ¹⁸O and δD) suggest that reservoir waters are meteoric waters mixed with magmatic (andesitic) water at Ngatamariki. Reservoir water chemistry at Orakei Korako exhibits low chloride contents, which is anomalous in the Taupo Volcanic Zone. Chloride content in well and spring waters is similar ranging from 546 to 147 mg/l, due to mixing of reservoir fluids with a ‘hot water’ diluent at depth. Isotopic compositions of spring waters suggest that they are meteoric waters which mix with magmatic (rhyolitic) water, more enriched in δ¹⁸O and δD than ‘andesitic’ water. Relationships between major ion concentrations and known subsurface geology suggest there is no hydraulic connection between the two fields.

The North Bank area lies on the north side of the Wairau River, Marlborough, New Zealand, bounded by the Richmond Ranges to the north and the Wairau River to the south. The North Bank is an interactive zone where groundwaters and surface waters from North Bank tributary valleys mix with waters of the Wairau River. This investigation aimed to define the nature and origin of groundwaters of the North Bank area. Stable isotopes of oxygen and hydrogen, along with hydrogeochemistry, were utilised in order to define the spatial extent of the North Bank riparian margin and delineate the Wairau River-groundwater interface. Distinct stable isotopic signatures differentiate ground and surface waters that come from high mountain catchments versus those that arrive more locally at lower altitude. The results gathered by this study demonstrated stable isotopes to be the most powerful forensic tool capable of distinguishing Wairau River water from North Bank tributary groundwater sources. In contrast, hydrogeochemical characteristics of the waters of the North Bank were young and chemically dilute in nature, which made them chemically indistinguishable from waters of the Wairau River. Geomorphological mapping was conducted in order to investigate the relationship between groundwater flow patterns and geomorphology upon the North Bank. Geomorphology, in the form of prominent fluvial terraces, was found to play a role in limiting the extent of Wairau River influence to groundwater to either low-lying Q2 Speargrass Formation, Q1 Rapaura Formation alluvium or the Wairau River channel itself. Aquifer pump testing and water level observation carried out in the Waikakaho Valley revealed a plentiful groundwater resource in the local context. Like other tributary valleys within the North Bank study area, surface water and groundwater were found to be chemically and isotopically linked to one another which points to an interconnected ground and surface water resource, larger than first thought. Driven by recharge by the Waikakaho River, the groundwater resource has development potential, and continued monitoring will further define the hydrogeological system and ensure long term sustainable use.

A hydrogeologic model, groundwater chemistry and stable isotopic analysis were used to establish recharge resources and outflows so a water balance could be developed for the Cromwell Terrace Aquifer (CTA) in Central Otago, New Zealand. Increased popularity of the Central Otago region for viticulture, orcharding and tourism, has resulted in an increased demand for water. Groundwater is a viable option to meet this demand for water. The CTA is a single unconfined aquifer contained within a thin veneer of permeable Quaternary glacial outwash gravels that range in thickness between 10 and 50m. These gravels rest unconformably on less permeable folded Tertiary sediments. The buried surface of the Tertiary sediments is irregular and provides the main hydrogeologic control in the CTA. Buried topographic highs in the Tertiary sediments impede groundwater flow, while the buried paleochannels at the southern end of the Cromwell Flat allow groundwater to flow unrestricted. The saturated thickness of the aquifer varies between 10 and 30 m. The direction of groundwater flow is in south easterly and south westerly directions toward both Lake Dunstan and the Kawarau Arm respectively. This indicates that recharge is from the Pisa Range. Annual fluctuations in groundwater levels show that there is a seasonal effect on the groundwater table. Annual fluctuations in groundwater level are in the range of 0.4 – 0.5 m, with lowest levels in winter and highest groundwater levels in late summer. The higher groundwater levels in summer correlate with when higher rainfall occurs, but could also be due to artificial recharge from irrigation during summer, and/or seepage from the Ripponvale Irrigation Scheme canals and storage ponds. Groundwater chemical analysis showed the dominant facies to be calcium bicarbonate waters. The source of the calcium bicarbonate is considered to be calcite in the Otago Schist, with concentrations of calcium bicarbonate being higher closer to the bedrock schist of the Pisa Range. Concentrations decreased toward Lake Dunstan, where calcium bicarbonate concentrations were lowest. The trend of calcium bicarbonate concentrations decreasing toward Lake Dunstan produces a similar pattern to the direction of groundwater flow. This would suggest that calcium bicarbonate concentrations are being diluted by rainwater infiltrating into the aquifer. However stable isotopic analysis showed that lake water infiltrates into the aquifer around the lake margin, and would also dilute calcium bicarbonate concentrations. Stable isotopic analysis found that groundwater was more depleted in both δ¹⁸O and δ²H than water from Lake Dunstan. The average δ¹⁸O for groundwater was -9.5‰, whereas the average δ¹⁸O for samples from Lake Dunstan was -8.1‰. The average δ¹⁸O value of Pisa Range snow, Pisa Range streams and Cromwell Flat precipitation gave values of -9.2‰ +/- 1.4‰, which is very similar to groundwater. This suggests recharge to the CTA is from a combination of snow melt and surface stream flow from the Pisa Range, and some direct rainfall infiltration on the Cromwell Flat. A water balance was calculated for the CTA groundwater system using the information from this study, and from a limited Otago Regional Council (O.R.C.) database. The main inputs to the CTA were found to be recharge precipitation and subsurface flows from the Pisa Range. The main outputs were identified as surface evaporation and discharge from the CTA to Lake Dunstan. The water balance showed that the total flow of water through the CTA is 93 Million cubic metres per year (Mm³/yr). At present the CTA has limited groundwater allocation measures in place. Using the information from the water balance, a volume of groundwater that could be abstracted sustainably was estimated. This volume was estimated using the O.R.C. method of allocating 50% of the mean annual precipitation that recharges the aquifer for groundwater abstraction. The total mean annual precipitation for the Cromwell Flat and Pisa Range is 20 Mm³/yr. Using the 50% of mean annual precipitation method, 10 Mm³/yr can be allocated for groundwater abstraction. The total volume of groundwater currently abstracted is 3 Mm³/yr, leaving 7 Mm³/yr of unallocated groundwater. Due to the small land area, types of land use, low population density of Cromwell Flat and availability of surface water (i.e. Lake Dunstan), it is unlikely that the total volume of 10 Mm³/yr will be fully allocated.

The unusual environmental conditions within caves provided unique opportunities for developing an understanding of ecosystem processes. However, relatively few studies have been conducted on the ecology of New Zealand cave systems. The primary aim of this research was to investigate changes in aquatic invertebrate communities along a longitudinal gradient from the surface into caves and investigate the fundamental drivers of cave communities. This study was carried out in three streams (two in pasture catchments and one in a forested catchment) flowing into caves in the Waitomo region, North Island, New Zealand. In order to address these aims I carried out a longitudinal survey of 12 sites in each stream, an experimental manipulation of food, and an isotopic study of a single stream. The longitudinal survey of the three cave streams revealed light intensity as well as algal and CPOM biomass all decreased significantly from outside the caves into caves. In contrast, water temperature, dissolved oxygen, stream width, depth, and velocity did not vary significantly with distance into caves. Benthic aquatic macroinvertebrate communities within the caves were a depauperate subset of surface communities, appearing to be structured by gradients in resources and colonisation through drift. However, some invertebrate taxa (primarily predators) were rarely found within caves, further suggesting that resource gradients were structuring cave communities. Surprisingly, the densities of some collector-browsers (primarily mayflies) increased within cave streams relative to surface densities. This may be due to a decrease in competition and predation, flexible feeding strategies, and high drift propensity. However, the benthic densities of most taxa within the caves appeared to be related to drift densities. Although surface forest and pastoral stream communities differed in community composition and density 32 meters within the caves invertebrate community diversity and density became similar, although specific taxa within communities varied. This convergence was attributed to similar environmental gradients within the caves. The resource addition experiment (adding leaf packs) indicated that cave streams were resource limited; the addition of leaves produced communities of similar richness and density across the environmental gradient. The isotopic survey suggested cave stream invertebrate communities were reliant upon similar basal resources to surface streams. However, within the cave epilithon appeared to be increasingly important while filamentous algae were absent. Cave aquatic invertebrates were also found to support terrestrial predators (spiders, harvestmen, and glow-worms), presumably increasing the abundance and diversity of terrestrial cave communities. In conclusion, aquatic cave communities were reliant upon surface derived resources and consequently strongly linked to surface land-use and managerial practices.

Water is a valuable and crucial resource, the protection of which poses environmental, social and economic challenges. Fundamental to the sustainable use of water is effective management. In the Canterbury region of New Zealand, nitrate contamination has become a resource management issue due to changes in land use and intensification, which have placed pressure on the region’s groundwater and surface water systems. The purpose of this study was to assess and track nitrate concentrations on the Central Canterbury Plains with specific emphasis on a local point source of nitrate, the Ashburton Meat Processors plant. To make this assessment review of historical data was followed by the collection of 131 groundwater and 25 surface water samples to analyse the geochemical properties of the water and the stable isotopic composition of nitrate in the water. It was hypothesised that nitrate concentrations at a regional scale have increased since regular records began and that the stable isotopic composition of different nitrate sources are not discernable. Nitrate concentrations across the Canterbury region were found to have increased, prompting concerns about water quality. Concentrations are elevated above natural background levels across much of the Canterbury Plains and extreme concentrations are associated with local point sources of nitrate. Nitrate concentrations down gradient of the Ashburton Meat Processing plant are shown to have declined approximately 5% per year for the past ten years, which is in contrast to the rest of the region, where average concentrations have nearly doubled in 20 years. The reduction of contamination from the point source is most likely the result of the implementation of better wastewater management practices in the early 21st century. The δ18O and δ15N values of nitrate were found to be relatively homogenous over the Canterbury Plains. Therefore, it is suggested by this study that the dual-isotope approach alone, is not a viable tool for nitrate source identification in the region. The uniform nitrate stable isotopic composition in Canterbury could be attributed to a single, principle source of nitrate, such as clover, that overprints other isotopic compositions of nitrate source, or may also be the result of soil processes and the farming techniques used in the region. This research presents important findings for the future of identifying and managing nitrate sources in the Canterbury region. Better management practices are required for the diffuse source(s) of nitrate contributing to the widespread contamination. Critical thinking and the willingness of stakeholders to engage in the identifying, documenting and solving problems is necessary to ensure the effective management and sustainability of this precious resource.

A novel tracer method has used 15N to label Escherichia coli and track the transport of bacteria, a common contaminant, through karst aquifers. Use of this method could provide valuable insight into the movement of bacteria in aquifers, which would help improve remediation methods and strategies. A wild strain of E. coli was isolated from the Cane Run/Royal Spring basin in the Inner Bluegrass region of Kentucky. The strain was serotyped O-:H- and virulence testing showed the strain did not have virulence factors of E. coli commonly pathogenic to humans. Five karst microcosms were filled with sterilized water collected from Royal Spring in Georgetown, Kentucky. Each microcosm was inoculated with wild-type E. coli, enriched in 15N, and incubated at 14° C for 130 days. The microcosms were periodically sampled for the concentration and nitrogen isotope composition of E. coli over 130 days. The E. coli survived at concentrations within one log of the average initial value of 5.62×1010 for the duration of the study. Statistical modeling showed no significant difference in δ15N values from day 1 and day 130. This strain is therefore recommended for traces in the Cane Run/Royal Spring basin.

Currently, bacterial movement in karst aquifers is not well understood. Use of stable isotopes to label non-pathogenic Escherichia coli as a particulate groundwater tracer in karst systems has been examined in previous studies. Loss of the stable isotope signal is anticipated in traces greater than 500 m in length. Potential loss of 15N due to predation by protozoa was examined. Filter-sterilized water from Royal Spring in Georgetown, Kentucky, was inoculated with a mixture of either Tetrahymena pyriformis or Colpoda steinii and 15N-enriched E. coli and stored in the dark at 14°C. Samples were analyzed for their nitrogen isotope composition (as δ15N values), and for population counts of bacteria and protozoa in a time course experiment, on days zero and seven after inoculation. Protozoan populations increased in the presence of E. coli, while bacterial populations decreased. δ15N values increased in T. pyriformis fed enriched E. coli but did not show values as high as the bacteria themselves, indicating that attenuation via predation may be a concern in future groundwater traces.

The long-term fate of hydrocarbons in the Gulf of Mexico (GOMx) following the 2010 Deepwater Horizon oil spill has yet to be fully characterized. Elemental (% C and % N), stable isotopes (δ13Corganic), and polycyclic aromatic hydrocarbon (PAH) molecular signatures were investigated in shelf and slope sediments collected in October 2010 and 2011 to gain insight into processes affecting the distribution and fate of spilled Macondo oil. Particulate organic carbon (POC) ranged between 1.55 and 2.22 wt. % in 2010 and 0.55 and 2.06 % in 2011 while the corresponding δ13Corganic ranges were from -23.37 to -20.77 ‰ (vs. PDB) in 2010, and -22.68 to -20.75 ‰ (vs. PDB) in 2011. Ranges of total polycyclic aromatic hydrocarbon (TPAH) concentrations were from 72.57 to 7,543.53 ng/g in 2010 and 25.55 to 16,582.77 ng/g in 2011. The range of measured values represented significant deviations from previous background measurements. This provided the basis for concluding that the Macondo spill altered the “background” organic carbon and hydrocarbon signature, that Macondo oil has weathered and/or biodegraded in the year following the spill, and that a significant spatial trend of hydrocarbons extended from the Macondo well across the northern GOMx in October 2010 and 2011.

Beluga whales (Delphinapterus leucas) and narwhals (Monodon monoceros) are arctic specialists. Both species show philopatry to their summer grounds, though the reason for this site tenacity is not well understood. Aside from migration routes, little is known about other aspects of monodontid ecology, such as their mating and feeding ecology. An understanding of the feeding ecology of a species may provide some insights into their mating ecology, and vice versa. The purpose of this thesis is to relative testes mass and dietary biomarkers to gain insights in the mating and feeding ecology of both species, as well as possible links between the two. Relative testes and brain masses and body masses of odontocetes were collected from the literature and analysed for correlations between sexual size dimorphism (SSD), relative brain mass, and relative testes mass. Results indicate that odontocete species follow a pattern of increasing SSD with decreasing testes mass. An examination of reproductive tracts from belugas and narwhal collected across the Canadian arctic was performed to examine differences in beluga and narwhal mating systems. Belugas were found to have larger relative testes masses, and narwhal testes masses were correlated with tusk length, indicating that sperm competition may play a larger role in the beluga mating system than for narwhal, and narwhal tusks may be honest indicators of male fitness. Investigations of narwhal and beluga feeding ecology using dietary biomarkers were conducted. In the summer, belugas appear to be congregating and feeding in the estuary plume during the summer, as opposed to along ice floe edges in the spring. Spring diets are representative of diets consumed during the beluga mating season, and no sexual segregation in carbon isotopes or fatty acids was apparent. There was no evidence for sexual segregation in feeding habits outside the mating season, either. Conversely, narwhal showed some evidence of sexual segregation outside the mating season, and the sexes may be feeding in different food webs. Results suggest that belugas may have a more promiscuous mating system, while narwhals are more polygynous. Implications for conservation for both species are discussed.

Mercury (Hg) is a global pollutant, yet Hg biomagnification, the increase in Hg with trophic level, remains poorly characterized in many regions, especially at subtropical latitudes. The present study assessed subtropical reservoirs of eastern China, which provided an opportunity to quantify Hg biomagnification under highly altered conditions that included high atmospheric Hg deposition, use of reservoirs for fisheries, manipulation of food webs through stocking and high fishing pressure, and increasing eutrophication. Despite China’s Hg emission and deposition rates that are among the highest worldwide, low fish Hg concentrations and Hg biomagnification rates were found; this was explained by food web structure and fish species characteristics. Stocked species occupied lower trophic levels and had significantly lower Hg concentrations relative to wild fishes. Evidence of decreased Hg concentrations with eutrophication (as indicated by chlorophyll-a) was observed, suggesting algal biodilution and/or somatic growth dilution. Relative to temperate lakes, zooplankton density dilution may also be causing reduced Hg concentrations in subtropical biota. Hydrogeomorphic features, such as water retention time and percent crop cover, explained Hg bioaccumulation factors and Hg concentrations at the base of the food web. Eutrophication and hydrogeomorphic features also influenced the bioavailability of selenium, which can protect against the toxicity of Hg at adequate concentrations, and the concentration of eicosapentaenoic acid, a beneficial fatty acid, in the planktivorous Bighead Carp (Hypophthalmichthys nobilis). This may indicate that the risk of exposure to the neurotoxicant methylmercury relative to benefits of fish consumption may increase with eutrophication in some fish species. Overall, the findings of this study suggest food web structure, eutrophication, and hydrogeomorphic features together explain low Hg concentrations in anthropogenically modified subtropical reservoirs in eastern China. / Thesis (Ph.D, Biology) -- Queen's University, 2014-07-01 11:35:12.637