Oil sands mining operations in northeastern Alberta are rapidly expanding. Upgrading and extracting the bitumen from the sand requires large volumes of water generating large quantities of oil sands process water/materials (OSPM) which is high in organic content. Some of the major organic components found in OSPM include unrecovered bitumen, polycyclic aromatic compounds (PACs), naphthenic acids (NAs) and humic acids. Concerns of acute and chronic toxicity resulting from OSPM have led to provincial legislation preventing the discharge of OSPM into local water and mandating the reclamation of areas affected by oil sands mining. To date, OSPM is stored on lease in settling basins while the mining companies evaluate reclamation strategies. One of the reclamation strategies involves the use of wetlands constructed with differing amounts of OSPM and organic amendments such as peat. Currently, numerous wetlands, both natural and constructed, are present on oil sands leases. To determine the sustainability of these wetlands for reclamation, the assimilation and flow of carbon and nitrogen within the systems need to be defined. Stable isotope analysis can enhance this understanding. To effectively use stable isotopes in the field, there is the need to determine the changes in stable isotope values occurring from the microbial degradation of organic components such as NAs which contribute a significant portion to the dissolved organic carbon (DOC) in reclamation sites. This study examined the microbial degradation of commercial and oil sands derived NAs by oil sands derived microbial cultures. Changes in stable isotopes values in the biomass (δ13C, δ15N), DOC and dissolved inorganic carbon (DIC) (δ13C) arising from degradation of the DOC were tracked in both static and semi-continuous tests. Utilization of commercial and oil sands derived NAs resulted in minimal change of the DOC stable isotope values. The biomass was 13C enriched for both the commercial (0.3 to 2.9 per mil (‰)) and oil sands derived NAs (3.7 to 8.5 ‰) relative to the DOC stable isotope values. DIC stable isotope values showed higher variability (-5 to +5.5 ‰). The semi-continuous tests showed biomass that was 15N enriched (3.8 to 8.4 ‰) with the assimilation of ammonium. Isotope trends established in the laboratory study provide further understanding into assimilation of carbon and nitrogen compounds in the field. DOC and DIC concentration and carbon stable isotope values were determined for water sampled from 13 oil sands aquatic reclamation sites varying in age, construction and organic material. Both DOC and DIC concentrations were elevated in OSPM affected sites, by an average of 40 mg/L for DOC and 83 mg/L for DIC concentrations. DOC concentrations were also elevated by approximately 10 mg/L at high organic sites. δ13C DOC values were slightly 13C enriched in young sites: 0.6 ‰ compared to δ13C DOC values at the mature sites. Also, from June to July 13C enrichment (0.3 to 1.9 ‰) of the DOC for all sites was seen. Corresponding with the enrichment seen in the DOC, 13C depletion (-8.8 to -0.3 ‰) of the DIC was seen for most sites from June to July. The trends seen from June to July may be a result of the release of readily degradable organics from the spring thaw stimulating the microbial community. The baseline values determined for DOC and DIC may assist future field food web studies.

Nitrate (NO3) contamination in agricultural watersheds is a widespread problem that threatens local drinking supplies and downstream ecology. Dual isotopes of NO3- (d15N and d18O) have been successfully used to identify sources of NO3 contamination and nitrogen (N)-cycle processes in agricultural settings. From 1998 to 2000, tile drainage and stream waters at the Strawberry Creek Catchment were sampled for NO3- concentration and isotopes. The results suggest that tile NO3 were mainly derived from soil organic matter and manure fertilizers, and that they were not extensively altered by denitrification. NO3- concentrations and isotopes in the stream oscillated between the influence of tile inputs, during periods of higher basin discharge, and groundwater inputs, during low basin discharge. The affect of denitrification was evident in stream NO3- samples. Sources and processes of dissolved NO3- and N2O were explored using concentrations and stable isotopes during the 2007 Springmelt and 2008 mid-winter thaw events. Tiles are a source of NO3- to the stream during both events and concentrations at the outflow are above the 10 mg N/L drinking water limit during the 2008 mid-winter thaw. The stream was a source of N2O to the atmosphere during both events. d15N and d18O of N2O reveal that N2O is produced from denitrification during both events. d18O:d15N slopes measured in N2O were due to the influence of substrate consumption (tiles) and gas exchange (stream). The stable isotopes of dissolved NO3- and N2O were also characterized during non-melt conditions (October 2006 to June 2007 and Fall 2007) at the Strawberry Creek catchment. Again, the purpose was to determine the sources and processes responsible for the measured concentrations and isotopic signatures. The isotope data suggests that N2O was produced by denitrification. Furthermore, NO3- consumption and gas exchange altered the original N2O signature. Isotopic distinction between soil gas N2O and dissolved N2O is suggestive of different production mechanisms between the unsaturated and saturated zones. Since the range of dissolved N2O isotopes from the Strawberry Creek catchment are relatively constraned, definition of the local isotopic signature of secondary, agricultural N2O sources was possible.

Dissolved oxygen (DO) is one of the most important environmental factors necessary to sustain aquatic life. The Southern Grand River is characterized with extensive marshes. This study focuses on the Dunnville Marsh in the Southern Grand River. The spatial and temporal variation in dissolved oxygen was studied in the Dunnville Marsh and the Grand River over a one year cycle during 2007 to 2008. Dunnville Marsh exhibited little influence on the oxygen regime of the river. The Grand River; however, could influence the oxygen regime in the marsh during the spring when waters are high but exerts little influence during the rest of the year. There were no great differences in DO between the wetland and the river during the high water spring melt period; however notable differences occurred in the summer and fall. Oxygen stable isotopes and diel O2 measurements showed that ecological factors probably were influencing the DO cycle in Dunnville Marsh, whereas both ecological and weather factors influenced the cycle in the Grand River. Monthly δ18O-DO data from the river revealed a shift towards atmospheric equilibrium compared to the wetland. These data exhibited less photosynthetic activity in the fall and more photosynthetic activity during the summer. The wetland showed higher photosynthetic activities in the summer than the river. Nitrogen input from the agricultural areas was low at most of the time and had minimal influence on the DO in the Dunnville Marsh. Despite low nitrogen input the attenuation ability of the Dunnville Marsh was apparent, presumably due to plant uptake, especially in the northern part of the marsh. Based on the δ18O-water signature in late April (after the flood season) it appears river water extended about two-thirds along the main stream well into Dunnville Marsh. River water, probably inundates a significant part of the Dunnville Marsh in early April (flood peak), when water flow was more than 10 fold higher than later in April following the peak flood season. River water can be intruded into the marsh and brought the DO to similar saturations as in the river in spring.

Tree-ring analyses have contributed significantly to investigations of climate change and climate cycles, including the North Atlantic Oscillation (NAO), Pacific Decadal Oscillation (PDO) and El Niño/Southern Oscillation (ENSO). Stable isotope climate proxies (?18O, ?D, and ?13C) have enhanced traditional ring-width data, although poor preservation of ancient wood has generally constrained reconstruction of stable isotope proxy records to the Holocene and Late Pleistocene. An opportunity to apply these stable isotope methods to older wood has been presented by recovery of remains of Mixed-Coniferous Boreal Vegetation, in Early Pliocene (4-5 Ma) deposits at Strathcona Fiord, Ellesmere Island, Canada (~79°N). An exceptionally well-preserved tree trunk, identified as Larix (larch) through wood anatomical characteristics, from this high Arctic site provided a 203-year tree-ring record, from which we present the first high-resolution, secular isotope record of Pliocene climate. ?18O, ?D, and ?13C isotope values indicate a variable climate with alternating intervals of cool/wet to warm/dry weather. These fluctuations in climate may be attributable to phase changes in climate cycles observed in the record. A growing season mean temperature of 14.4 °C was calculated from isotopic analysis of gastropod shells. Palaeoclimatic modeling of tree isotope values has revealed growing season temperatures of 11-15 °C, and estimated isotope values of precipitation of 18.3 (?18O) and 228 (?D). Both palaeotemperature estimates and source water calculations are comparable to those found in a modern Boreal Forest. Time-series wavelet analysis was applied to these data revealing prominent short (<10 years), intermediate (16-35 years) and long-term (~45-50 years) cyclicity. These are the highest resolution climate cycles recovered from the pre-Holocene terrestrial record, providing evidence for decadal scale cyclicity similar to the NAO and/or PDO 4-5 million years ago.

Oxygen isotopes and major and trace element geochemistry have been used to evaluate the geochemical and tectonic history of a Franciscan hornblende-amphibolite and a eclogite block from Ring Mountain, Tiburon and three eclogite/blueschist blocks from Jenner Beach, California, all blocks have experienced varying amounts of retrogression. Relative to the presumed basaltic protolith, enrichments in large ion lithophile elements (LILEs) indicate interaction with sediment derived fluids in the retrograde eclogite and retrograde blueschist samples and high Mg, Cr, and Ni in actinolite rind indicate interaction with ultramafic rock. The [delta]¹⁸O values of chlorite from the Ring Mountain hornblende-amphibolite and the eclogite block have a narrow range of [delta]¹⁸O values (+7.7-8.2%₀, n=8) and actinolite from actinolite rind on the eclogite block from Ring Mountain and the blueschist/eclogite blocks from Jenner Beach are (+7.8-8.5%₀, n=5). Chlorite-actinolite geothermometry yields temperatures of 200-280°C for actinolite rind formation. Additionally, the [delta]¹⁸O values of both chlorite and actinolite at these temperatures indicates equilibrium with the measured value of Tiburon serpentinites, (7.6 to 8.1%₀, n = 3 Wenner and Taylor, 1974). Oxygen isotope analyses of garnet mineral separates from the eclogite and hornblende-amphibolite from Ring Mountain have [delta]¹⁸O values of +6.8±0.3%₀ (n=7), and +8.2±0.2%₀ (n=7), respectively. Garnets from the three eclogite/blueschist blocks at Jenner Beach have a [delta]¹⁸O value of +9.8±0.7%₀, (n=23). The difference in [delta]¹⁸O values of garnets between the high-grade blocks is likely due to in situ hydrothermal alteration of the seafloor basalt prior to subduction. The geochemical trends can be explained by a model in which during the early stages of subduction pieces of altered oceanic crust are detached from the downgoing slab and incorporated into the mantle wedge soon after reaching peak eclogite or amphibolite facies conditions. As subduction continues, the hanging wall cools and fluids released from subducted sediments infiltrate the overlying mantle wedge. As the blocks cool they develop a retrograde blueschist facies overprint under relatively static conditions. With cooling of the hanging wall and infiltration of sedimentary fluids, serpentinization induces reaction between the blocks and surrounding mantle wedge and Mg-rich actinolite rind is formed. The blocks are then plucked from the mantle wedge and incorporated into the subduction channel where they flow back to the surface via corner flow. / text

The rate of carbon turnover in soil is a balance between the input of carbon by plants through their roots and associated fungi and the loss of carbon due to plant and microbial respiration, oxidation and leaching. Soil carbon dynamics are notoriously difficult to measure, and being able to separate total soil respiration into its autotrophic and heterotrophic components would help understanding of carbon cycling processes. Where autotrophic respiration originates from roots and their associated mycorrhizal fungi, using newly fixed carbon, and heterotrophic respiration originates from the breakdown of older soil organic matter. By calculating the δ¹³C signature of respired CO₂ (the ratio of the abundances of C isotopes ¹²C and ¹³C) it is possible to determine whether it is of heterotrophic or autotrophic origin. In this study a 6 chamber, constant CO₂ concentration measuring apparatus was developed to determine both the rate of CO₂ efflux and to collect undisturbed CO₂ samples for isotope analysis. This apparatus was tested using live soil samples with different δ¹³C values (-22 ‰ to -27 ‰) and respiration rates (2 – 8 µmol m⁻² s⁻¹) obtained from various locations in New Zealand. Testing involved taking samples using the respiration apparatus, then incubating the same samples in a bag, and then comparing the two. There was no difference between the results from the soil respiration apparatus and the bags (R²=0.96, p=0.0002). Twelve microcosms including soil and grass were extracted from a newly converted dairy farm and placed into in growth cabinets. Diurnal courses of partitioned soil respiration were made over 24 hours with constant soil temperature to eliminate temperatures effect on soil respiration. Half were then covered with 90% shade cloth for 12 days to test if a reduction in light (and therefore newly fixed carbon) would have any effect on soil respiration. There was a significant reduction in soil respiration, yet no detectable change in the δ¹³C of soil respired CO₂ under heavily shaded treatment. There was however there was a shift towards heterotrophic dominated respiration. This shows that while L. perenne is resilient to surrounding conditions it is susceptible to change if exposed to different conditions for prolonged periods of time. The use of this new technique in the field will allow improved understanding of factors effecting soil C efflux.

Understanding the paleoclimate of a region is important, especially when trying to determine the extent of natural climate variability within the context of anthropogenic impacts. Recent anomalous periods of climate change in the Late Holocene, including the Little Ice Age and Medieval Warm Period, could possibly repeat in the future, having significant worldwide consequences. This holds especially true for tropical and subtropical karst environments, where limited paleoclimate proxies provide minimal data regarding past climate change. An investigation into past climate change in Belize using fulvic acids from cave sediments shows periods of drought during the collapse of the Maya society around 1400 years ago. Comparison of changes in the carbon isotope data from the fulvic acids agree with speleothem records, but more closely reflect changes in the vegetation above the cave, showing Maya population decline through waning agriculture. Further investigation of using fulvic and other organics acids are examined from cave sediments in Florida. The data show fulvic acid carbon isotopes are the most robust recorders of climate change, agreeing with several nearby speleothem d¹8O and d¹³C records from west-central Florida. A more detailed record of climate change in Florida through a calibration study of precipitation and cave dripwater oxygen and hydrogen isotopes revealed that the amount effect dominates rainfall in west-central Florida. Homogenization of epikarst dripwater gives average d¹8O values representative of the annual amount-weighted average of precipitation d¹8O for the area, suggesting speleothem isotope records reflect changes in rainfall amount. Examination of two speleothems from west-central Florida show complex teleconnection and solar forcing mechanisms responsible for past climate changes. A high-resolution stable isotope, trace element, and time series analysis study for the last 1500 years shows variability during the LIA and MWP, pointing to a combined influence of Pacific and Atlantic teleconnection mechanisms, especially the ITCZ, NAO and PDO, being responsible for precipitation variability. Long-term reconstruction of the mid-Holocene and Late Pleistocene from another speleothem reveals differences in temperature and precipitation between glacial and interglacial conditions in Florida. Climate proxies from the tropics and subtropics provide additional clues to global climate change crucial to understanding future water availability.

Sulfate, nitrate, and certain trace elements are common groundwater contaminants observed at mining sites. Their source, fate, and remediation were investigated at a former uranium mining site. First, groundwater samples collected across the site were analyzed for geochemistry, stable isotopes, and trace elements. Then, two pilot-scale ethanol injection tests were conducted for biostimulation of nitrate and sulfate reduction. Groundwater was monitored in the test area before and after the tests. The results showed a mixing of two discrete sources of sulfate. Quantification of these two sources using two methods showed that sulfide-mineral oxidation of the mine tailings served as a steady but low-discharge source while sulfuric acid (applied during ore processing in the 1960s) served as a variable, strong source. It appears that sulfuric acid served as a sustained source of sulfate for approximately 40 years. This source may be from accumulation of sulfate salts (formed from sulfuric acid) in the source zone due to the arid climate of the site. Results showing correspondence of isotopic compositions of ammonium and nitrate confirmed the generation of nitrate via nitrification. Moreover, it was observed that ammonium concentration is closely related to concentrations of uranium and a series of other trace elements including chromium, selenium, vanadium, iron, and manganese. It is hypothesized that ammonium-nitrate transformation processes influence the disposition of the trace elements through mediation of redox potential, pH, and possibly aqueous complexation and solid-phase sorption. As for the biostimulation, sulfate reduction condition has been maintained for a period of approximately 3 years after a single input. Atypical fractionation behavior of the delta34S in sulfate was hypothesized to be caused by release of sulfate from sulfate minerals associated with the sediments. Elevated hydrogen sulfide concentrations were not observed until approximately four months after the start of the test. This behavior, in concert with the observed changes in aqueous iron and manganese species, suggests that hydrogen sulfide produced from sulfate reduction was precipitated, presumably in the form of iron sulfides, until the exhaustion of readily reducible iron oxides. Hydrogen sulfide produced thereafter appears to have been in part re-oxidized.

Coal beds are one of the most promising reservoirs for geologic carbon dioxide (CO₂) sequestration, as CO₂ can strongly adsorb onto organic matter and displace methane; however, little is known about the long-term fate of CO₂ sequestered in coal beds. The "2800' sand" of the Olla oil field is a coal-bearing, oil and gas-producing reservoir of the Paleocene–Eocene Wilcox Group in north-central Louisiana. In the 1980s, this field, specifically the 2800' sand, was flooded with CO₂ in an enhanced oil recovery (EOR) project, with 9.0×10⁷m³ of CO₂ remaining in the 2800' sand after injection ceased. This study utilized isotopic and geochemical tracers from co-produced natural gas, oil and brine from reservoirs located stratigraphically above, below and within the 2800' sand to determine the fate of the remaining EOR-CO₂, examining the possibilities of CO₂ migration, dissolution, mineral trapping, gas-phase trapping, and sorption to coal beds, while also testing a previous hypothesis that EOR-CO₂ may have been converted by microbes (CO₂-reducing methanogens) into methane, creating a microbial "hotspot". Reservoirs stratigraphically-comparable to the 2800' sand, but located in adjacent oil fields across a 90-km transect were sampled to investigate regional trends in gas composition, brine chemistry and microbial activity. The source field for the EOR-CO₂, the Black Lake Field, was also sampled to establish the δ¹³C-CO₂ value of the injected gas (0.9‰ +/- 0.9‰). Four samples collected from the Olla 2800' sand produced CO₂-rich gas with δ¹³C-CO₂ values (average 9.9‰) much lower than average (pre-injection) conditions (+15.9‰, average of sands located stratigraphically below the 2800' sand in the Olla Field) and at much higher CO₂ concentrations (24.9 mole %) than average (7.6 mole %, average of sands located stratigraphically below the 2800' sand in the Olla Field), suggesting the presence of EOR-CO₂ and gas-phase trapping as a major storage mechanism. Using δ¹³C values of CO₂ and dissolved organic carbon (DIC), CO₂ dissolution was also shown to be a major storage mechanism for 3 of the 4 samples from the Olla 2800' sand. Minor storage mechanisms were shown to be migration, which only affected 2 samples (from 1 well), and some EOR-CO₂ conversion to microbial methane for 3 of the 4 Olla 2800' sand samples. Since methanogenesis was not shown to be a major storage mechanism for the EOR-CO₂ in the Olla Field (CO₂ injection did not stimulate methanogenesis), samples were examined from adjacent oil fields to determine the cause of the Olla microbial "hot-spot". Microbial methane was found in all oil fields sampled, but indicators of methanogenesis (e.g. alkalinity, high δ¹³C-DIC values) were the greatest in the Olla Field, and the environmental conditions (salinity, pH, temperature) were most ideal for microbial CO₂ reduction in the Olla field, compared to adjacent fields.

A dearth of reliably-dated paleolake records from the southern Basin and Range has limited knowledge of past water balance changes there, precluding a more complete understanding of late Pleistocene atmospheric circulation across western North America. Paleoshorelines in closed basins throughout the region can provide accurately dated records of local effective moisture variations, representing a largely untapped source of paleohydrologic information. This dissertation presents paleohydrologic reconstructions from depositional successions in two basins at 32°N, approximately 100 km apart: Willcox basin, in southeastern Arizona, and Playas Valley, in southwestern New Mexico. Also presented are the results of ¹⁴C dating of charcoal samples from the El Fin del Mundo Clovis archaeological site, in northwestern Sonora, Mexico. In depth analysis of these results allowed constraint of the "small sample effect" on the charcoal ages, found to be smaller than 1σ of analytical uncertainty. The magnitude of the problem in ages from miniscule shell samples in the Willcox and Playas chronologies was found to be similar. The successions record moist pluvial conditions from ~20-13 ka in Playas, and>37-11 ka in Willcox, with most dates younger than 19 ka--before which there is no solid evidence for lake transgressions. There is clear evidence for overlapping highstands between ~18.3 and 17.9 ka and a brief highstand of Cochise at ~12.9 ka, coinciding with Heinrich events H1b and H0, respectively. Temporal concordance between wet periods and perturbations in the North Atlantic ocean and/or southern Laurentide ice sheet supports the idea that abrupt paleoclimatic changes in the southwestern U.S. occurred in response to large-scale atmospheric linkages to the northern high latitudes. The H1b highstands fill a hiatus in ¹⁴C dates compiled from paleoshorelines throughout the western U.S., and correspond to the first part of a lowstand in paleo-Lake Estancia (35°N), in north-central New Mexico. Anti-phasing within New Mexico suggests that the newly documented highstands resulted from an increase in southerly-sourced precipitation. This is consistent with paleoenvironmental evidence from southern Arizona and New Mexico that points toward periodic intensification of the summer monsoon during the late Pleistocene.