Thesis (M. Sc.)--York University, 2001. Graduate Programme in Physics and Astronomy. / Typescript. Includes bibliographical references (leaves 119-126). Also available on the Internet. MODE OF ACCESS via web browser by entering the following URL: http://wwwlib.umi.com/cr/yorku/fullcit?pMQ66411.

The purpose of this study was to provide new insights into the interpretation of speleothem (cave calcite deposit) δ13C values. We studied two caves in central Texas, which have been actively monitored for over 12 years. We compared δ13C values of soil CO2 (δ13Cs), cave drip water (δ13CDIC), and modern cave calcite (δ13Ccc). Measured average δ13C values of soil CO2 were -13.9 ± 1.4‰ under mixed, shallowly-rooted C3-C4 grasses and were -18.3 ± 0.7‰ under deeply-rooted ashe juniper trees (C3). The δ13CDIC value of minimally-degassed drip water in Natural Bridge Caverns was -10.7 ± 0.3‰. The carbon isotope composition of CO2 in equilibrium with this measured drip water is -18.1 ± 0.3‰. The agreement between juniper soil CO2 and drip water (within ~0.2‰) suggests that the δ13C value of drip water (δ13CDIC) that initially enters the cave is controlled by deeply-rooted plants and may be minimally influenced by host-rock dissolution and/or prior calcite precipitation (PCP). At Inner Space Caverns, δ13CDIC values varied with vegetation above the drip site, distance from the cave entrance, and distance along in-cave flow paths. Whereas CO2 derived from deeply-rooted plants defines the baseline for drip water δ13CDIC entering the caves, kinetic effects associated with the degassing of CO2 and simultaneous precipitation of calcite account for seasonal variability in δ13CDIC and δ13Ccc. We documented increases in δ13CDIC at a rate of up to 0.47‰/hour during the season of peak degassing (winter), suggesting that δ13CDIC variations may be controlled by total elapsed time of CO2 degassing from drip water (Ttotal). We also observed seasonal shifts in the δ13C values of modern calcite grown on glass substrates that are correlated with shifts in drip water δ13CDIC values and drip-rate. Therefore, we suggest that increased aridity at the surface above a given cave results in, slower drip-rates, higher Ttotal, and therefore higher δ13CDIC values. We propose that large variability (>2‰) in speleothem δ13Ccc values dominantly reflect major vegetation changes, and/or increasing Ttotal by slowing drip-rates. Based on these findings, variability in speleothem carbon isotope records may serve as a proxy for paleoaridity and/or paleovegetation change. / text

This thesis is concerned with the measurement and interpretation of isotope shifts. The first part describes an experimental determination of isotope shifts in the 4s^{2 1}S<subo</sub> - 4s5s¹ S_o transition of neutral calcium. This measurement was performed using the method of Doppler-free two-photon absorption spectroscopy in an atomic beam of the natural mixture of calcium isotopes. The laser was stabilized and scanned by means of an external, pressure-swept etalon, and its scan was calibrated by recording the transmission fringes of the laser through a confocal etalon, 2m in length. This calibration etalon was stabilized with reference to an I₂-stabilized Helium- Neon laser. The isotope shifts of all the stable isotopes of calcium were measured; the results are believed to be free from systematic error and so the standard deviations are derived from the scatter of the results. A Isotope Shift ^δv^A-44/MHz 40 -1169.99(28) 42 -563.66(7) 43 -263.67(6) 46 534.34(70) 48 1023.50(7) These results are compared with other accurate measurements of isotope shifts in calcium by laser spectroscopy, by means of the King plot. All the measurements are consistent except for the only odd isotope ⁴³Ca, which, in this transition, unlike those in the other experiments, is free from hyperfine structure. The best values of the isotope shifts are thus determined by a least squares procedure. The mass and field shifts are separated using the values of δ<r²> determined from muonic isotope shifts, and this leads to more accurate values of δ<r²>. The second part of the thesis concerns the interpretation of anomalous isotope shifts in samarium. Pairs of spectral lines had been found for which the shifts of even-even isotopes did not lie on a straight line on a King plot. These deviations are interpreted as evidence for the insufficiency of first-order perturbation theory for the treatment of isotope shifts in a number of levels of the samarium spectrum. By comparing shifts in transitions connecting these levels with shifts in transitions connecting levels for which first-order perturbation theory appears to be a good approximation, values of off-diagonal matrix elements are found. These are not required to be unreasonably large to explain the observed deviations.

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Determining sustainable water resource utilization rates is an important problem faced by regulatory agencies all around the world. One of the key parameters in determining accurate water budgeting schemes is the rate of water resource replenishment, or ‘recharge’ in groundwater systems. Fundamental questions regarding groundwater recharge include: What is the source of recharge? What is the spatial distribution of recharge? What is the annual average recharge rate, from potentially disparate sources in disparate areas? Answers to these questions can be gained through combining physical and chemical hydrogeological research tools, including stable isotopic compositions. Land-use intensification, including significant increases in dairying, has placed a priority on developing water resource management practices throughout New Zealand. Here we present the first compilation of delta oxygen-18 and delta hydrogen-2 values from individual precipitation events, local surface waters, depression springs, and groundwaters from the greater-Christchurch area. A variety of analytical methods were used in an effort to evaluate the potential use of stable isotopic compositions as tracers of surface-groundwater interaction in the local hydrologic cycle. The results of this thesis found the isotopic variability of Christchurch precipitation to be highly varied. Back-trajectory analysis of single precipitation events exhibit pathways arriving from three principal sources: the Southern Pacific Ocean, the Tasman Sea, and the Tropical Pacific Ocean. Separately, delta oxygen-18 and delta hydrogen-2 values values from these sources show three distinct local meteoric water lines, which are determined to be largely affected by the environmental conditions present in these areas at the time water vapour formation. Intra-storm variation of extra-tropical cyclones support these findings as significant changes in deuterium excess as moisture sources change with southward movement of the low pressure system. Three line-conditioned tests were subsequently developed to compare the relationship between monthly surface rainfall, surface water, and groundwater samples to the respective moisture origins. Surface rainfall, rainfall infiltration, surface waters, and groundwaters all exhibit the least amount of deviation from the Southern Pacific Ocean local meteoric water line. These observations suggest the principle moisture source to Christchurch to be from west-south westerly flow from the mid-latitudes. However, these similarities do not make partitioning their relative contributions to the groundwater system easy. Previous physical and isotopic investigations have shown the dominant sources of recharge to the Christchurch Groundwater System (CGS) are alpine rivers and local precipitation of which there is statistically significant difference with respect to delta oxygen-18 values. A binary single-isotope mixing model allows for quantification of the relative contributions of alpine river and precipitation derived inputs to local depression springs. The isotopic model indicates that approximately 80% of spring discharge was derived from alpine rivers, in good agreement with recently published physical mass balance model results. Deep groundwater flow paths however show groundwater to flow from the Central Canterbury Plains to the CGS. Potentially including losses from the upper Waimakariri River reaches. If included, this places a net recharge amount to the CGS water budget, which if using losses from only the lower Waimakariri River, there is a net loss. Losses from the upper reaches and subsequent groundwater flow into the CGS are likely as there have been no observed declines in groundwater levels even though there is currently a net loss by only using recharge components within the CGS. Ultimately, recharge from groundwater movement from the Central Canterbury Plains may play significant role; however, a much more sophisticated geochemical model is needed to test these theories and determine contributions. This research demonstrates the utility of stable isotopes as tracers of hydrogeological processes, particularly in shallow groundwater, and their potential contributions to the water resource allocation decision making process.

Recently, the growth and condition of Lake Whitefish (Coregonus clupeaformis), an important commercial fishery commodity, has declined in some areas of the Great Lakes. As Lake Whitefish are benthic feeders, historically the bulk of their diet was made up of the energy rich Diporeia hoyi, an amphipod whose abundances declined concurrently with reductions in Lake Whitefish growth and condition. Lake Whitefish populations from lakes Michigan, Erie and Superior have been used to determine whether there is a plausible link between the declines in Lake Whitefish condition and Diporeia abundance as indicated by stable isotope analysis, dietary and condition indices for Lake Whitefish. The first study was Lake Michigan specific and tested the hypothesis that condition, in terms of relative weight, percent lipid and docosahexaenoic acid (DHA), improved as the proportion of high quality prey (e.g., Diporeia) in the diet increased. Samples of spawning whitefish from four regions (northwest, Naubinway, Elk Rapids and southeast) around Lake Michigan had distinct mean carbon and nitrogen isotope signatures. The signatures indicated Lake Whitefish may be using a variety of prey items, especially the Naubinway population where fish occupy the largest isotopic niche space. Relative weight was significantly higher in the southeast and lower for all northern regions. The mean measured lipid from Lake Whitefish dorsal skinless muscle biopsies was highest for northwest region fish. DHA was significantly different among studied regions, with higher mean values in Elk Rapids and the northwest. No linear relationships between stable isotope measures and condition metrics were found. These results suggest that Lake Whitefish are coping with declining Diporeia abundances by feeding on alternate prey. Results do not substantiate the hypothesis of a relationship between condition and prey use, although Lake Whitefish from Elk Rapids and the northwest had high quality prey and good condition. The second study incorporated eight spawning populations around lakes Michigan, Erie and Superior to determine if there were differences in energy available to female Lake Whitefish. The hypotheses tested were three fold: (1) observed differences in growth and reproduction among populations were driven by energy availability, (2) populations with low energy reserves exhibit reproductive trade-offs and (3) high energy reserves are related to Diporeia consumption. Lake Whitefish from lakes Erie and Superior both displayed high growth and no trade-offs between egg size and number. Populations from Lake Michigan all had low investment in growth, significantly lower gonadosomatic index (GSI) and four of these populations displayed significant trade-offs between egg size and number. Growth and GSI tended to increase with mean total lipid stored in muscle and populations displaying reproductive trade-offs had significantly lower muscle lipid, however, these trends were not evident when using DHA as a measure of good nutrition. No relationship was evident between Diporeia consumption and populations with high muscle lipid stores. Overall, my results suggest that while changes in the availability of prey resources has had an effect on Lake Whitefish populations, the impact of declining abundances of Diporeia alone cannot explain the systemic changes in Lake Whitefish condition across the Great Lakes basin.

The use of δ18O- PO4 analysis was assessed for the Grand River, a highly impacted river in Southern Ontario that receives inputs from 30 WWTPs. Significant nutrient inputs within the watershed have led to prolific aquatic plant growth, particularly within the central Grand River where this study is focused. Two of the largest WWTPs in the watershed fall within this region and these plants are in close proximity to each other (approximately 20 km apart). Various laboratory tests were carried out to assess the suitability of several DOM removal methods on Grand River water and WWTP effluent prior to mass spectrometric analysis with varying results. Sample analysis showed all river sites to possess δ18O- PO4 values that were elevated relative to equilibrium. These sites are not equilibrium-controlled and, instead, possess δ18O- PO4 signatures controlled by either source inputs, or isotopic fractionation. The second WWTP was shown to deliver PO43- that was elevated relative to equilibrium. WWTP effluent in this study displayed a large δ18O -PO4 range, ranging from 10.4 to 22.9‰. Most of the variation in isotopic composition was found at the second plant, which had high soluble reactive phosphorus (SRP) and a range of 12.5 to 22.8‰ (n = 3). The first plant showed little variation with much lower SRP and a mean value of 11.4 (SD ± 1.0‰, n = 2). The elevated δ18O- PO4 signatures collected from the second WWTP suggest that this plant is supplying the Grand River with isotopically distinct PO43-. This could be used as a way to establish the effect of the second WWTP on the downstream PO43- pool. Phosphate uptake and release by the epilithon and seston were measured using 32P-PO4 additions in recirculating beaker experiments. Two sites, one downstream of the first WWTP and one below the second WWTP, were assessed for gross and net PO43- uptake rates. The gross uptake rates at both sites were low (0.04 to 0.10 µg P cm-2 h-1), with long turnover times for the dissolved phosphate pool (12 to 40 h). Long uptake lengths (30 to 144 km) were measured, indicating low nutrient retention capabilities downstream of the two WWTPs. These significant P contributions appear to have large-scale effects on the river’s P-kinetics, limiting its ability to act as a net nutrient sink even in the more productive summer months. The biomass response below the WWTPs is insufficient to compensate for the elevated PO43- concentrations and low rates of PO43- uptake. Due to the limited use of δ18O -PO4 analysis in river systems, no model exists for predicting the response of δ18O -PO4 with distance downstream of a point source. Coupling rates of PO43- uptake and release with the effluent δ18O -PO4 values provides such a model and generates guidance for future use of this method in lotic environments. WWTP “plume chases” were previously carried out in the Grand River, and involved measuring SRP at several sites downstream of the WWTP discharge points. SRP was used as a proxy for PO43- concentration in this study, and is operationally defined by what passes through a 0.20-µm membrane filter and is molybdate reactive. Best-fit estimates of PO43- uptake and release were determined using these plume chase events. The rates calculated using the 32P-PO4 uptake and release beaker experiments were up to 50 times lower than the best-fit parameters. This exercise illustrates the unsuitability of relaying estimates of P kinetics collected through beaker experiments to an ecosystem level. Model predictions for the river reach below the second WWTP show that effluent δ18O -PO4 signatures should be observable many kilometres from the plant. Because of the unique mean isotopic composition observed for the second WWTP, sampling could occur at a variety of locations downstream to observe the effect of this plant on the river. The river reach below the first WWTP reduces the incoming P loads much quicker than the second reach, which is in part due to the much lower effluent SRP released by the first plant. It is still possible to isolate effluent derived δ18O-PO4 values downstream of this plant. The return to equilibrium is projected to occur several kilometers from the first plant’s confluence, suggesting the applicability of this method in both stream reaches. It would appear δ18O -PO4 could be a valuable tool for eliciting information on P cycling in effluent-impacted river ecosystems, with the Grand River possessing elevated but seemingly typical uptake lengths amongst eutrophic streams.

名古屋大学年代測定総合研究センターシンポジウム報告

This thesis examines both surface water and shallow groundwater connections in boreal watersheds at two study sites in the Athabasca Oil Sands Region using conventional hydrological techniques as well as stable water isotope techniques. Increased emissions due to oil sands development are expected to contribute significantly to acidifying airborne emissions. Specifically, nitrogen is forecasted to be deposited on the surrounding area within approximately 100 km of operations. The purpose of the research is to provide background information for predicting how individual terrain units such as fens, bogs, and uplands will respond to increased nitrogen loads, and to assess whether or not these units will act as sources or sinks of nitrogen under higher nitrogen deposition. Two study sites situated within 100 km of Fort McMurray, Alberta were instrumented with a total of 30 nested piezometers, 26 water table wells, 4 micro-meteorological stations, and two gauging stations (weirs) at outflow points. Monitoring occurred during the open water season of 2011 and 2012. This study estimates evaporation through a simplified energy balance, documents hydraulic conductivity of shallow aquifers, utilizes stable isotopes of water to assist in mapping seasonal flow patterns, and calculates a vertical water balance for the sites. Bogs and fens were hydrologically connected, as bogs fed fens laterally at shallow depths within the acrotelm during wet years. Upland terrain units were found to have more variable connections. In spring, upland runoff recharged the wetlands at both sites. At JPH groundwater flowed towards the fen, whereas in ML limited connections were observed between the uplands and the fen. Also, no connections were seen to indicate that the wetlands recharged the uplands. A conceptual model is developed that emphasizes the role of connectivity in the boreal landscape. The main implication for nitrogen cycling is that it is difficult to quantify one landscape as a source or sink for additional nitrogen as its role may vary depending on seasonality and temporal scales. Further work is needed to identify if nitrogen loadings will have adverse affects on geochemistry of water at the sites. / Graduate / 0366 / amyvallarino@gmail.com