Studies of carbon's evolutionary path have been conducted via millimeter and submillimeter observations of circumstellar envelopes (CSEs), planetary nebulae (PNe), molecular clouds and comets. The 12C/13C isotope ratio was measured in Galactic molecular clouds using the CN isotopologs. A gradient of 12CN/13CN was determined to be 12C/13C = 6.01 DGC +12.28, where DGC is distance from the Galactic center. The results of CN are in agreement with those of CO and H2CO indicating a true ratio not influenced by fractionation effects or isotope-selective photodissociation. The 12C/13C isotope ratios in the envelopes of various types of stars were also measured from both CO and CN isotopologs. Such objects as carbon and oxygen-rich asymptotic giant branch (AGB) stars, supergiants, planetary nebulae, and S-type stars were observed. Results from this study indicate 12C/13C values for supergiants ~ 10 and AGB stars 12C/13C ~ 20- 76. Theory would suggest a lower ratio for objects undergoing third dredge-up, though this is seemingly not the case. Multiple carbon-bearing species including CO, HCN, HNC, CN, CS, and HCO+ have also been observed towards the oxygen-rich supergiant, VY CMa. This object has recently revealed a unique chemistry where carbon is not solely contained in CO, and may play a more important role in the chemical network of oxygen-rich circumstellar envelopes. Additionally, observations of species with carbon- carbon bonds, such as CCH and c-C3H2, have been conducted towards evolved planetary nebulae, such as the Helix and Ring nebulae. There is a close agreement in the inventories of species found in PNe and diffuse clouds, suggesting a potential molecular precursor to the interstellar medium. Observations of carbon-bearing species (H2CO and CO) in comets C/1995 O1 (Hale-Bopp), C/2001 Q4 (NEAT), and C/2002 T7 (LINEAR) have been conducted. Formaldehyde is known to have an extended distribution in these objects, likely arising from silicate-organic grains. Evidence of cometary fragmentation was also obtained for H2CO in comet T7 LINEAR as well as for HNC and HCO+ in Hale-Bopp. Such events could contribute to planetary distribution of organics.

I use microchemistry in fish otoliths to test the hypothesis that diverting Colorado River flow from reaching the Gulf of California has impacted two endemic fish: the threatened gulf Corvina, (Cynoscion othonopterus) and the endangered totoaba (Totoaba macdonaldi). The oxygen and carbon stable isotope ratios in otoliths help to reconstruct conditions of the environment during key life history stages before and after the damming and diverting the Colorado River. The δ¹⁸O in otoliths illustrate that both C. othonopterus and T. macdonaldi seek out brackish habitat provided by the Colorado River during their early life history. The δ¹⁸O of C. othonopterus otolith have a strong negative correlation with Colorado River flow. I found that previously published relationships between otolith δ¹⁸O and ambient temperature along with δ¹⁸O of the water are sufficient to predict ranges of expected δ¹⁸O values for T. macdonaldi in the field. The δ¹⁸O in pre-dam T. macdonaldi otoliths show significant divergence from modern T. macdonaldi otoliths’ values, indicating that these fish used the brackish waters of the Colorado River estuary. The δ¹³C in T. macdonaldi otoliths has a significant proportion of its δ¹³C derived from diet. Pre-dam T. macdonaldi juveniles have a significantly different diet, which reflects that the Colorado River estuary had higher productivity before diversion of the river. Lastly, T. macdonaldi grew faster before the dams and in association with Colorado River flow measured by the δ¹⁸O.

Iron (Fe) exerts strong control over environmental biogeochemistry. As the fourth most abundant element, Fe is present in nearly all earth environments, where it plays important roles in governing the transformation and movement of organic and inorganic constituents, and in microbial respiration. Consequently, the body of work on Fe biogeochemistry is vast. This study is specifically concerned with the dynamic changes in the oxidation state of Fe (i.e., redox cycling) and their impact on the inorganic, organic and microbial components in soil. I constructed a special apparatus to fluctuate redox potential on soil slurries while concurrently sampling a wide range of biogeochemical variables (pH, redox potential, major and trace elements, CO2 release, DNA community composition charges, etc.). Previous research has documented redox fluctuations along a climate gradient in Hawaii and a primary goal of this dissertation was to reconstruct these redox fluctuations, subjected to experimental constraints afforded by a laboratory setting, with minimal disruption to the biogeochemical processes controlling Fe redox cycling. By recasting the spatial and temporal characteristics of in situ Fe redox cycling in the laboratory, I was able to form testable hypotheses regarding the importance of Fe redox oscillations to soil mineral transformations, colloid composition/dynamics and microbial community structure. A second goal of this dissertation was to explore the utility of Fe isotopic composition for providing information on soil weathering processes along age and climate gradients at the field scale in Hawaii. This portion of the study tested emerging theories of Fe isotope fractionation during mineral dissolution using well-characterized sequences in soil weathering intensity.The principal findings of the laboratory redox fluctuation experiments are that Fe redox oscillations: (1) trigger an increase in the crystallinity of Fe-oxides; (2) mobilize colloids containing refractory elements (e.g., Zr, Nb, U, etc.); (3) reveal redox sensitive rare earth element (REE) anomalies in the aqueous phase; and (4) induce changes in the microbial community favoring microbes capable of growth under both oxic and anoxic conditions. The principal finding of the Fe isotope measurements is that isotopic composition is directly related to weathering intensity in the field, consistent with theoretical predictions.

Understanding wolf (Canis lupus) food habits provides critical information for boreal woodland caribou (Rangifer tarandus caribou; forest-dwelling ecotype) recovery strategies. By incorporating the stable isotope ratios of different caribou ecotypes into a stable isotope mixing model, I determined the relative importance of boreal woodland caribou in the summer diet of wolves in northern Manitoba, Canada. Boreal woodland caribou were primary summer prey for wolves collected in winter in registered trapline (RTL) districts where these caribou are considered rare, suggesting migratory behaviour in some wolves. Moose were primary prey in other RTL districts, followed by boreal woodland caribou, with beaver providing important contributions. Recovery strategies for woodland caribou should investigate annual wolf, caribou, and moose movement in the region to complement these findings and gain a better insight into this complex ecosystem.

This study explores the use of N2O and its isotopic composition to investigate nitrogen processes in groundwater aquifers. Groundwater sampling was undertaken in 2008-2009 at two septic system sites (Long Point site and Lake Joseph site) and two agricultural sites (Strathroy site and Woodstock site). All of these four sites have been studied previously, and denitrification zones were identified by using NO3- isotopes. Extremely broad ranges of N2O-N concentrations are present at septic system sites (1 to 1071 μg/L at Long Point and 0.1 to 106 μg/L at Lake Joseph). N2O concentrations at the agricultural sites show lower levels and narrower ranges (0.1 to 3.3 μg/L at Strathroy and 14.6 to 40.5 μg/L at Woodstock site). However, N2O-N concentrations at four sites except Strathroy are higher than the atmospheric equilibrium values (0.27 to 0.37 μg/L at 8 to 17°C) as well as N2O-N values in surface water (0.2 to 1.2 μg/L, Grand River). This provides indication of N2O production in subsurface in both septic system sites and agricultural sites. Using reported enrichment factors and measured ranges for NH4+ and NO3- isotopic values, ranges were calculated for the isotopic composition expected for N2O produced by nitrification and denitrification. At Long Point site, δ15N-N2O and δ18O-N2O ranging from -43.9 to +24.9 ‰ and +20.6 to +89.4 ‰ indicates that nitrification is mainly responsible for N2O accumulation in both proximal shallow and deep zones while some N2O at the bottom of the aquifer is presumably produced from denitrification. After N2O is produced in the plume core, δ15N and δ18O in N2O reveal that N2O is further consumed to N2. Also, N2O isotopic values cleanly show seasonal N2O production shifted from mostly nitrification in early season to primarily denitrification in late season. At Lake Joseph, δ15N-N2O and δ18O-N2O varying from -4.4 to -43.2 ‰ and +24.7 to +56.7 ‰ reveal that nitrification N2O was mainly present in aerobic zone whereas denitrification zone was found in downgradient anaerobic area. At Strathroy site, δ15N-N2O (+1.7 to -29.7 ‰) and δ18O-N2O (+33 to +65 ‰) show that N2O in shallow aquifer (< 5m depth) is presumably derived from atmosphere and nitrification whereas in deep aquifer (>5m depth), N2O formation occurs during denitrification. At Woodstock site, δ15N-N2O (-4.7 to -15.9 ‰) and δ18O-N2O (+30.7 to +37.1 ‰) at Woodstock provide indication of N2O production from a mixing of denitrification N2O and tropospheric N2O. N2O isotopic signatures are highly useful to identify N2O sources which include nitrification, denitrification, and dissolution of atmospheric N2O at both septic system sites and agricultural sites. Further, at Lake Joseph site and Woodstock site, denitrification evidence from NO3- concentration/isotopes is lacking but N2O isotopes suggest the occurrence of denitrification. At Long Point site, N2O isotopes indicated N2O production was by denitrification occurred early in the season; however, no NO3- isotopic enrichment was t that depth until in late season. These sites provide evidence that N2O is an early and sensitive indicator of denitrification in groundwater at both septic system and agricultural sites. Additionally, N2O isotopes are valuable for detecting N2O consumption whereas NO3- isotopes cannot provide insight into this process.

This study used the isotope pool dilution method to estimate gross rates of mineralization, nitrification, NH4+ and NO3- consumption, and denitrification emissions over two growing seasons within a conventional barley-red clover-potato crop rotation on Prince Edward Island. Gross rates within the 2010 season were, in most cases, not significant across crop species or sampling date. In comparison, gross nitrification, NH4+ consumption, and NO3- consumption rates in 2011 were greatest within the potato crop following planting and hilling. However, rates were highly variable within both seasons. Error analysis indicated that variation in soil mineral nitrogen concentrations between duplicate cores was the greatest source of error. The use of the isotope pool dilution method to estimate gross nitrogen transformation rates using intact cores was not viable within this production system due to high and variable soil mineral nitrogen concentrations, particularly following fertilizer application.

This thesis attempted to determine whether precipitation at CFB Borden, Ontario Canada is derived from recycled or marine source water using δ18O and to explore the enrichment of leaf water in three temperate forest trees. The d-excess values and rainfall intensity were used as indicators of recycled water and were found to suggest that precipitation at Borden is not derived from recycled water. The leaves of ash, aspen and maple showed significant enrichment in δ18O over xylem water. Maple leaves were significantly more enriched over the leaves of ash and aspen (p-value = 0.0019), despite source water not being significantly different (p-value = 0.1782). Modelling leaf water demonstrated the need for the inclusion of the Peclet effect in the steady state model for ash and aspen leaves, however for maple, the Peclet effect is insignificant. The non-steady state model used measured values of δET, which were uncertain and lead to poor model predictions. / NSERC Strategic Project #351040

This thesis is an investigation of the relative differences of acid ionization constants and ion mobility in D2O versus H2O under hydrothermal conditions, for acetic acid and phosphoric acid. Values of specific conductivity were measured for each acid in H2O and D2O, as well as for a series of strong electrolytes using a high-temperature high-pressure AC conductivity flow cell that was originally designed at the University of Delaware. The Fuoss-Hsai-Fernández-Prini (FHFP) equation was fitted to the experimental values of molar conductivity, Λ, to obtain molar conductivities at infinite dilution, Λo. The molar conductivities at infinite dilution for each acid were used to calculate degrees of dissociation and ionization constants in D2O versus H2O from 298 K to 571 K. Measured values of differences in pKaq in D2O vs H2O, ΔpKaq = [pKaq,D2O – pKaq,H2O], become relatively independent of temperature above 423 K, with values of: ΔpKaq 0.45 for acetic acid and ΔpKaq 0.35 for phosphoric acid. The Density Model was then fitted to the values of pKaq in H2O and D2O to represent their temperature dependence to a precision of ± 0.01 in ΔpKaq. Comparisons of the molar conductivities and ionic molar conductivities at infinite dilution for the strong electrolytes in H2O and D2O as a function of temperature have also been made, based on Walden’s rule correlations, (λ°•η)D2O / (λ°•η)H2O. Changes in values of (λ°•η)D2O / (λ°•η)H2O as a function of temperature are consistent with a change in the relative hydration behavior of ions, where the effective Stokes’ radii of the ions in D2O versus H2O changes at temperatures above ~ 450 K. Changes in values of (λ°•η)D2O / (λ°•η)H2O for D+/H+ and OD-/OH- suggest that proton hopping “Grotthuss” mechanisms become more efficient in D2O versus H2O with increasing temperature. / University Network of Excellence in Nuclear Engineering, Ontario Power Generation Ltd, Natural Science and Engineering Research Council of Canada

Statistical models like Transition State Theory (TST) and Rice-Ramsperger-Kassel-Marcus (RRKM) Theory have generally been successful in predicting the rates and selectivities of chemical reactions. However, these statistical models can fail to explain experimental results of ordinary organic reactions. For these reactions, consideration of nonstatistical dynamic effects or the detailed motion and momenta of the atoms is necessary to account for the experimental observations. Dynamic effects have been found to be important in a growing number of reactions and the nature of these effects can be varied. One of the most interesting reactions investigated is the ozonolysis of vinyl ethers. Ozonolysis of a homologous series of vinyl ethers in solution exhibit experimental product ratios wherein the selectivity among cleavage pathways increases with the size of the alkyl group to an extent that is far less than RRKM theory would predict. Trajectory studies account for the observed selectivities and support a mechanism involving a competition between cleavage of the primary ozonide and intramolecular vibrational energy redistribution. A recent theoretical study from our group predicted that a highly asynchronous organocatalytic Diels-Alder (DA) reaction, which is concerted in the potential energy surface, is stepwise in the free energy surface. Kinetic isotope effects (KIEs) were measured for three DA reactions. We envision that the entropic barrier may have several experimental consequences such as unusual isotope effects due to extensive recrossing. Preliminary results for the organocatalytic reaction show an intramolecular KIE close to unity that cannot be reconciled with statistical theories. This is in contrast with Lewis-acid catalyzed and thermal DA reactions, which exhibit substantial "normal" intramolecular KIEs that are in accord with TST predictions. Finally, the Baeyer-Villiger oxidation of cylohexanone in water was investigated. KIEs were measured for the oxidation of cyclohexanone with peracetic acid and trifluoroperacetic acid. When using peracetic acid as the oxidant, the alkyl migration was determined to be the rate-determining step based on significant intermolecular KIEs on the carbonyl and alpha-methylene carbons. A change in the rate-determining step is seen when trifluoroperacetic acid is used. Only the carbonyl carbon exhibits a significant isotope effect. Theoretical predictions provide an experimental picture of the transition states and qualitatively support these conclusions.

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