Affordable event and monthly rain samplers: Improving isotopic datasets to understand meteorological processes.

RATIONALE: Water-stable isotopes in rainfall are powerful tracers of atmospheric processes at different spatial and temporal scales. However, commercially available rain samplers for isotopic analysis are prohibitively expensive, especially for high spatial resolution networks and studies conducted in developing countries. A low-cost, simple, and robust sampler was designed for event and monthly rainfall samplings. METHODS: Rainfall collectors were built based on existing designs provided in the literature and using easily accessible materials. Event samplers were filled with different volumes of reference water and left for 72 h in laboratory conditions to determine the minimum amount of rainfall to be collected to minimize isotopic fractionation, from both postsampling evaporation and equilibration. Samples were analyzed using dual-inlet isotope ratio mass spectrometry and cavity ring-down spectroscopy. RESULTS: For samples larger than 4% of the bottle's capacity, the evaporative enrichment due to Rayleigh distillation is negligible compared to the overall analytical uncertainty. Using a tube connecting the funnel to the water sample has proved to reduce postsampling evaporation by at least five times. To limit water self-diffusion, we recommend collecting the largest rainfall amount possible. Under these conditions, these collectors are suitable for rainfall sampling for isotopic analysis. CONCLUSIONS: This low-cost methodology will enable isotopic sampling of precipitation at high spatial resolutions and democratize the use of isotopes for hydrological studies in developing countries. All instructions for building and using these samplers are made openly accessible to the scientific community so they can be repeated and adapted to the needs of each project.

Identification of riverbank filtration sites at watershed scale: A geochemical and isotopic framework.

Identifying groundwater wells performing riverbank filtration (RBF) is crucial to ensure safe drinking water through vulnerability assessment plans adapted to these hybrid water sources. Nonetheless, RBF is often unintentional or insufficiently documented and official inventories are scarce. We developed a user-friendly geochemical and isotopic framework for the in-situ identification of RBF facilities. It includes an interpretation abacus for non-specialists. While most studies using tracers are site-specific and/or based on discrete samples, we propose a novel multi-site characterization where time-series of EC, δ2H and δ18O are directly used as proxies of surface water infiltration at the watershed-scale. The basic statement is that time varying signal of raw water from a groundwater pumping facility reveals a significant induced infiltration of surface water. The framework was applied on nearly 2000 samples from 40 pumping wells and 4 neighboring rivers (<500 m), collected through collaborative sampling on a weekly to monthly basis for 18 months. Despite proximity to surface water, two-third of the complete dataset (19 facilities) were revealed not to benefit from significant contribution of surface water, demonstrating location criteria to be insufficient to identify RBF sites. Permanent RBF was evidenced at 5 facilities, where year-long seasonal variation of tracers in raw groundwater highlighted a continuous high proportion of infiltrated surface water. Unexpectedly, time-series also unveiled a third category: occasional RBF, where induced infiltration occurred only when specific hydrodynamic conditions were met (4 facilities). This study also provided concrete illustrations on how climate change may impact the efficiency of RBF to naturally attenuate microbiological contaminants and how geochemical and isotopic time-series considerably help at anticipating the evolution of contaminant attenuation capacity of RBF sites. Finally, by highlighting the existence of occasional RBF, this study tackles the common oversimplification that groundwater facilities can be binarily and classified either as RBF or groundwater.

Optimizing short time-step monitoring and management strategies using environmental tracers at flood-affected bank filtration sites.

Bank filtration is a popular pre-treatment method to produce drinking water as it benefits from the natural capacity of the sediments to attenuate contaminants. Under flood conditions, bank filtration systems are known to be vulnerable to contamination, partly because flow patterns may evolve at short timescales and result in a rapid evolution of the origin and travel times of surface water in the aquifer. However, high frequency monitoring for water quality is not common practice yet, and water quality management decisions for the operation of bank filtration systems are typically based on weekly to monthly assays. The aim of this study is to illustrate how monitoring strategies of environmental tracers at flood-affected sites can be optimized and to demonstrate how tracer-based evidence can help to define adequate pumping strategies. Data acquisition spanned two intense flood events at a two-lake bank filtration site. Based on bacteriological indicators, the bank filtration system was shown to be resilient to the yearly recurring flood events but more vulnerable to contamination during the intense flood events. The origin of the bank filtrate gradually evolved from a mixture between the two lakes towards a contribution of floodwater and one lake only. Automatized measurements of temperature and electrical conductivity at observation wells allowed to detect changes in the groundwater flow patterns at a daily timescale, while the regulatory monthly monitoring for indicator bacteria did not fully capture the potential short timescale variability of the water quality. The recovery to pre-flood conditions was shown to be accelerated for the wells operating at high rates (i.e., ≥1000 m3/day), partly because of floodwater storage in the vicinity of the less active wells. These results establish new perspectives to anticipate water quality changes through selected pumping schemes, which depend on and must be adapted to site-specific water quality issues.

A portrait of wellbore leakage in northeastern British Columbia, Canada.

Oil and gas well leakage is of public concern primarily due to the perceived risks of aquifer contamination and greenhouse gas (GHG) emissions. This study examined well leakage data from the British Columbia Oil and Gas Commission (BC OGC) to identify leakage pathways and initially quantify incident rates of leakage and GHG emissions from leaking wells. Three types of leakage are distinguished: "surface casing vent flow" (SCVF), "outside the surface casing leakage" (OSCL), and "cap leakage" (CL). In British Columbia (BC), the majority of reported incidents involve SCVF of gases, which does not pose a risk of aquifer contamination but does contribute to GHG emissions. Reported liquid leakage of brines and hydrocarbons is rarer. OSCL and CL of gas are more serious problems due to the risk of long-term leakage from abandoned wells; some were reported to be leaking gas several decades after they were permanently abandoned. According to the requirements of provincial regulation, 21,525 have been tested for leakage. In total, 2,329 wells in BC have had reported leakage during the lifetime of the well. This represents 10.8% of all wells in the assumed test population. However, it seems likely that wells drilled and/or abandoned before 2010 have unreported leakage. In BC, the total GHG emission from gas SCVF is estimated to reach about 75,000 t/y based on the existing inventory calculation; however, this number is likely higher due to underreporting.

A New Technique to Determine the Phosphate Oxygen Isotope Composition of Freshwater Samples at Low Ambient Phosphate Concentration.

The oxygen isotope composition of dissolved inorganic phosphate (δ18Op) offers new opportunities to understand the sources and the fate of phosphorus (P) in freshwater ecosystems. However, current analytical protocols for determining δ18Op are unable to generate reliable data for samples in which ambient P concentrations are extremely low, precisely the systems in which δ18Op may provide new and important insights into the biogeochemistry of P. In this Article, we report the development, testing and initial application of a new technique that enables δ18Op analysis to be extended into such ecosystems. The twist spinning mode (TSM) protocol described here enables >1000 L of sample with a P concentration <0.016 mg P L-1 to be initially processed within the field in approximately 24 h. Combined with a new freeze-drying method to maximize the yield and minimize the contamination of silver phosphate generated for isotope ratio mass spectrometry, the TSM protocol is able to generate accurate and precise δ18Op data. We evaluated the TSM protocol using synthetic test solutions and subsequently applied the protocol to samples from locations around the Saint Lawrence River in Montreal, Canada. We believe that the novel technique reported here offers the methodological basis for researchers to extend the application of δ18Op into a much wider range of freshwater ecosystems than has been possible to date.

Assessing the potential of cross-contamination from oil and gas hydraulic fracturing: A case study in northeastern British Columbia, Canada.

This paper presents the various tools and data sources in British Columbia (Canada) that can be used by environmental consultants to assess the potential of cross-contamination between shale gas formation fluids and shallow aquifers from hydraulic fracturing and related oil and gas activities. A systematic approach for evaluating the potential of cross-contamination using these data sources is applied to a specific case study at an undisclosed location in the northeastern part of the province. This approach includes defining and then evaluating the basic criteria for assessing the potential of cross-contamination. These criteria are: a leak source; a driving force such as buoyancy or head differential and a leakage pathway. This study has revealed that there is a potential of cross-contamination due to hydraulic fracturing activities and wellbore integrity issues. Wellbore integrity can be compromised by induced seismic events or by unintentional communication with offset hydraulic fractured wells. Induced seismicity is linked to the activity of hydraulic fracturing as well as to the deep disposal of wastewater.

Improved accuracy and precision of water stable isotope measurements using the direct vapour equilibration method.

RATIONALE: A method to measure the δ2 H and δ18 O composition of pore water in soil samples using direct vapour equilibration and laser spectrometry was first described in 2008, and was rapidly adopted. Here, we describe an improved setup to measure pore water δ2 H and δ18 O values through direct vapour equilibration with a laser spectrometer, combining a liquid and a vapour mode for water isotope analyses, and resulting in improved accuracy. METHODS: We first tested new gas sampling bags as part of the equilibration protocol. Then, to assess measurement accuracy, vapour samples from equilibrated liquid waters of known isotope composition were measured in the liquid mode of the analyser using the new setup as well as the manufacturer's vapour mode. Various modes of preparing liquid water standards, namely equilibration, nebulisation, and vapourisation, were tested to determine the best calibration in terms of accuracy. Finally, the proposed modified liquid setup was validated by analysing water vapour equilibrated from soil pore water of a known composition. RESULTS: The δ2 H and δ18 O measurements were found to be more accurate by the modified liquid mode than by the factory-setup vapour mode. The strong and non-linear dependence of measured δ2 H and δ18 O values on H2 O concentration in vapour mode, especially at concentrations equal to the vapour pressure saturation typically found in laboratories, is problematic for corrections. Regarding calibration and standards, the use of two equilibrated liquid water standards was found to best calibrate measurements in the modified liquid setup. Finally, the modified liquid mode setup and its calibration, as described here, were shown to be appropriate for soil pore water analysis. CONCLUSIONS: The proposed modified setup results in more precise δ2 H and δ18 O soil pore water values than the usual protocols. An average standard deviation of 0.04‰ for δ18 O values and 0.3‰ for δ2 H values, based on 228 soil sample analyses, was obtained.

Regional assessment of concentrations and sources of pharmaceutically active compounds, pesticides, nitrate, and E. coli in post-glacial aquifer environments (Canada).

There is growing concern worldwide about the exposure of groundwater resources to pharmaceutically active compounds (PhACs) and agricultural contaminants, such as pesticides, nitrate, and Escherichia coli. For regions with a low population density and an abundance of water, regional contamination assessments are not carried out systematically due to the typically low concentrations and high costs of analyses. The objectives of this study were to evaluate regional-scale contaminant distributions in untreated groundwater in a rural region of Quebec (Canada). The geological and hydrogeological settings of this region are typical of post-glacial regions around the world, where groundwater flow can be complex due to heterogeneous geological conditions. A new spatially distributed Anthropogenic Footprint Index (AFI), based on land use data, was developed to assess surface pollution risks. The Hydrogeochemical Vulnerability Index (HVI) was computed to estimate aquifer vulnerability. Nine wells had detectable concentrations of one to four of the 13 tested PhACs, with a maximum concentration of 116ng·L-1 for benzafibrate. A total of 34 of the 47 tested pesticides were detected in concentrations equal to or greater than the detection limit, with a maximum total pesticide concentration of 692ng·L-1. Nitrate concentrations exceeded 1mg·L-1 N-NO3 in 15.3% of the wells, and the Canadian drinking water standard was exceeded in one well. Overall, 13.5% of the samples had detectable E. coli. Including regional-scale sources of pollutants to the assessment of aquifer vulnerability with the AFI did not lead to the identification of contaminated wells, due to the short groundwater flow paths between recharge and the sampled wells. Given the occurrence of contaminants, the public health concerns stemming from these new data on regional-scale PhAC and pesticide concentrations, and the local flow conditions observed in post-glacial terrains, there is a clear need to investigate the sources and behaviours of local-scale pollutants.

Impact of climate changes during the last 5 million years on groundwater in basement aquifers.

Climate change is thought to have major effects on groundwater resources. There is however a limited knowledge of the impacts of past climate changes such as warm or glacial periods on groundwater although marine or glacial fluids may have circulated in basements during these periods. Geochemical investigations of groundwater at shallow depth (80-400 m) in the Armorican basement (western France) revealed three major phases of evolution: (1) Mio-Pliocene transgressions led to marine water introduction in the whole rock porosity through density and then diffusion processes, (2) intensive and rapid recharge after the glacial maximum down to several hundred meters depths, (3) a present-day regime of groundwater circulation limited to shallow depth. This work identifies important constraints regarding the mechanisms responsible for both marine and glacial fluid migrations and their preservation within a basement. It defines the first clear time scales of these processes and thus provides a unique case for understanding the effects of climate changes on hydrogeology in basements. It reveals that glacial water is supplied in significant amounts to deep aquifers even in permafrosted zones. It also emphasizes the vulnerability of modern groundwater hydrosystems to climate change as groundwater active aquifers is restricted to shallow depths.