Michael Nightingale

Occurrence and origin of methane in groundwater in Alberta (Canada): Gas geochemical and isotopic approaches

To assess potential future impacts on shallow aquifers by leakage of natural gas from unconventional energy resource development it is essential to establish a reliable baseline. Occurrence of methane in shallow groundwater in Alberta between 2006 and 2014 was assessed and was ubiquitous in 186 sampled monitoring wells. Free and dissolved gas sampling and measurement approaches yielded comparable results with low methane concentrations in shallow groundwater, but in 28 samples from 21 wells methane exceeded 10mg/L in dissolved gas and 300,000 ppmv in free gas. Methane concentrations in free and dissolved gas samples were found to increase with well depth and were especially elevated in groundwater obtained from aquifers containing coal seams and shale units. Carbon isotope ratios of methane averaged -69.7 ± 11.1‰ (n=63) in free gas and -65.6 ± 8.9‰ (n=26) in dissolved gas. δ(13)C values were not found to vary with well depth or lithology indicating that methane in Alberta groundwater was derived from a similar source. The low δ(13)C values in concert with average δ(2)HCH4 values of -289 ± 44‰ (n=45) suggest that most methane was of biogenic origin predominantly generated via CO2 reduction. This interpretation is confirmed by dryness parameters typically >500 due to only small amounts of ethane and a lack of propane in most samples. Comparison with mud gas profile carbon isotope data revealed that methane in the investigated shallow groundwater in Alberta is isotopically similar to hydrocarbon gases found in 100-250 meter depths in the WCSB and is currently not sourced from thermogenic hydrocarbon occurrences in deeper portions of the basin. The chemical and isotopic data for methane gas samples obtained from Alberta groundwater provide an excellent baseline against which potential future impact of deeper stray gases on shallow aquifers can be assessed.

Determination of the stable isotope composition and total dissolved solids of Athabasca oil sands reservoir porewater: Part 1. A new tool for aqueous fluid characterization in oil sands reservoirs

We present a new method to determine the total dissolved solids (TDS) concentration and the stable isotope composition of drill-core-derived Porewater in oil sands reservoirs of northeastern Alberta, Canada. The technique described here uses two end-member mixing relationships between the stable isotope compositions of drilling fluids and formation waters from mechanically extracted porewater samples to calculate the formation water TDS, , and values. Analysis of water samples extracted directly from McMurray Formation drill core provides an inexpensive and robust advance in the ability to characterize the properties of reservoir pore waters that can be widely deployed because of the ubiquity of drill-core sampling. Porewater data from three oil sands wells from different locations within the Athabasca region are presented in this study. Water derived from these wells had TDS values of 860 to 45,000 mg/L, values of −172 to −149‰, and values of −22.4 to −19.3‰. These values are consistent with regional trends in formation water salinity and stable isotope compositions, and illustrate the wide range of TDS values that can be found in McMurray Formation waters. The ability to characterize aqueous fluids within bitumen-saturated reservoirs is a new development that enables measurement of aqueous fluid properties that is not easily obtained by other sampling means. This methodology provides a tool to understand the origin and movement of reservoir water related to natural groundwater flow, or to anthropogenic influence by steam injection. Novel in situ extraction technologies that use electromagnetic heating systems may also benefit from detailed characterization of aqueous reservoir fluids to accurately determine the properties of the reservoir porewater.

Identifying sources and processes controlling the sulphur cycle in the Canyon Creek watershed, Alberta, Canada

Sources and processes affecting the sulphur cycle in the Canyon Creek watershed in Alberta (Canada) were investigated. The catchment is important for water supply and recreational activities and is also a source of oil and natural gas. Water was collected from 10 locations along an 8 km stretch of Canyon Creek including three so-called sulphur pools, followed by the chemical and isotopic analyses on water and its major dissolved species. The δ2H and δ18O values of the water plotted near the regional meteoric water line, indicating a meteoric origin of the water and no contribution from deeper formation waters. Calcium, magnesium and bicarbonate were the dominant ions in the upstream portion of the watershed, whereas sulphate was the dominant anion in the water from the three sulphur pools. The isotopic composition of sulphate (δ34S and δ18O) revealed three major sulphate sources with distinct isotopic compositions throughout the catchment: (1) a combination of sulphate from soils and sulphide oxidation in the bedrock in the upper reaches of Canyon Creek; (2) sulphide oxidation in pyrite-rich shales in the lower reaches of Canyon Creek and (3) dissolution of Devonian anhydrite constituting the major sulphate source for the three sulphur pools in the central portion of the watershed. The presence of H2S in the sulphur pools with δ34S values ∼30 ‰ lower than those of sulphate further indicated the occurrence of bacterial (dissimilatory) sulphate reduction. This case study reveals that δ34S values of surface water systems can vary by more than 20 ‰ over short geographic distances and that isotope analyses are an effective tool to identify sources and processes that govern the sulphur cycle in watersheds.

The use of ion exchange membranes for isotope analyses on soil water sulfate: Laboratory experiments

To investigate the potential use of anion exchange membranes (plant root simulator [PRS] probes) for isotope investigations of the soil sulfur cycle, laboratory experiments were performed to examine the sulfate exchange characteristics and to determine the extent of sulfur and oxygen isotope fractionation during sulfate sorption and desorption on the probes in aqueous solutions and simulated soil solutions. The sulfate-exchange tests in aqueous solutions under varying experimental conditions indicated that the amount of sulfate exchanged onto PRS probes increased with increasing reaction time, initial sulfate concentration, and the number of probes used (= surface area), whereas the percentage of removal of available sulfate was constant irrespective of the initial sulfate concentration. The competition of nitrate and chloride in the solution lowered the amount of exchanged sulfate. The exchange experiments in a simulated soil under water-saturated and water-unsaturated conditions showed that a considerable proportion of the soil sulfate was exchanged by the PRS probes after about 10 d. There was no evidence for significant sulfur and oxygen isotope fractionation between soil sulfate and sulfate recovered from the PRS probes. Therefore, we recommend the use of PRS probes as an efficient and easy way to collect soil water sulfate for determination of its isotope composition.

Determination of the stable isotope composition and total dissolved solids of Athabasca oil sands reservoir porewater: Part 2. Characterization of McMurray Formation waters in the Suncor–Firebag field

A new stable isotope approach was used to determine the total dissolved solids concentration and stable isotope composition for oil sands drill core extracted porewater at the Suncor–Firebag oil sands field in northeastern Alberta, Canada. A stable isotope mixing approach was used to correct for contamination by drilling fluids in the porewater samples. The mean isotopic compositions of oxygen () and hydrogen () in water for fluid samples from 12 wells at Firebag were −20.5 ± 1.4‰ and −157 ± 11‰, respectively. The mean total dissolved solids (TDS) concentration of the reservoir formation water in 12 sampled wells was 1100 ± 400 mg/L (1σ). These results suggest that the McMurray Formation water at Firebag is primarily derived from Holocene groundwater recharge, and that the water within the bitumen reservoir is similar to groundwater well samples obtained within the McMurray Formation at Firebag. The results obtained in this study are consistent with regional trends and previously proposed local hydrogeological flow conditions.

Water and sediment as sources of phosphate in aquatic ecosystems: The Detroit River and its role in the Laurentian Great Lakes

Eutrophication of freshwater ecosystems and harmful algal blooms (HABs) are an ongoing concern affecting water quality in the Great Lakes watershed of North America. Despite binational management efforts, Lake Erie has been at the center of dissolved reactive phosphate driven eutrophication research due to its repeated cycles of algae blooms. We investigated the Detroit River, the largest source of water entering Lake Erie, with the objectives to (1) characterize Detroit River phosphate levels within water and sediment, and (2) use multiple chemical and isotopic tracers to identify nutrient sources in the Detroit River. Riverine water and sediment samples were collected at 23 locations across 8 transects of the Detroit River. The bulk δ15N values from sediments were enriched compared the δ15N values of nitrate from water samples, consistent with biogeochemical cycling in the sediment. Principle component analysis of multiple chemical tracers from water samples found spatial variation consistent with multiple sources including synthetic and manure-derived fertilizers and wastewater effluent. The concentrations of phosphate dissolved in water were within regulatory guidelines; however, sediments had elevated concentrations of both water- and acid-extractable phosphate. Sediment-sequestered legacy phosphorus historically deposited in the Detroit River may be transported into Lake Erie and, if mobilized into the water column, be an unrecognized internal-load that contributes to algal bloom events. Globally, freshwater ecosystems are impacted by numerous non-point source phosphorus inputs contributing to eutrophication and the use of multiple tracer approaches will increase our ability to effectively manage aquatic ecosystems.