The Minesing Wetlands contain Canada’s only known population of Hine’s emerald dragonfly (HED), a species listed as endangered since 2011. The HED relies on groundwater discharge areas to complete its life cycle and therefore the population is potentially sensitive to changes in groundwater. The goals of this study were to, (1) characterize groundwater discharge to the eastern portion of the Minesing Wetlands, which corresponds to the HED habitat, (2) document any significant changes in groundwater chemistry since a 1998 study, and (3) establish a comprehensive baseline water quality data set to facilitate future comparisons. Consistent with HED habitats in the USA, the chemistry of Minesing Wetlands groundwater was dominated by calcium and bicarbonate. Low groundwater chloride and nitrate concentrations indicated minimal impact from activities such as road salt application and fertilizer use. Nitrate was generally only found at the wetland margin where groundwater springs emerged from the base of the uplands. The dominant form of inorganic nitrogen in wetland groundwater was ammonium (max = 1.5 mg N/L), and soluble reactive phosphorus concentrations were also relatively high (8 to 122 µg/L). The most consistent change in wetland groundwater chemistry between the 1998 study and samples collected in 2015–2017 was that chloride concentrations in 10 of 23 wells increased over time, however the maximum mean well chloride (11.6 mg/L) remained well below the guideline for the protection of aquatic life (120 mg/L). To preserve HED habitat, potential impacts to groundwater need to be considered during land use planning for the recharge area.

The stable isotope ratios of groundwater sulfate (34 S/32 S, 18 O/16 O) are often used as tracers to help determine the origin of groundwater or groundwater contaminants. In agricultural watersheds, little is known about how the increased use of sulfur as a soil amendment to optimize crop production is affecting the isotopic composition of groundwater sulfate, especially in shallow aquifers. We investigated the isotopic composition of synthetic agricultural fertilizers and groundwater sulfate in an area of intensive agricultural activity, in Ontario, Canada. Groundwater samples from an unconfined surficial sand aquifer (Lake Algonquin Sand Aquifer) were analyzed from multi-level monitoring wells, riverbank seeps, and private domestic wells. Fertilizers used in the area were analyzed for sulfur/sulfate content and stable isotopic composition (δ18 O and/or δ34 S). Fertilizers were isotopically distinct from geological sources of groundwater sulfate in the watershed and groundwater sulfate exhibited a wide range of δ34 S (-6.9 to +20.0‰) and δ18 O (-5.0 to +13.7‰) values. Quantitative apportionment of sulfate sources based on stable isotope data alone was not possible, largely because two of the potential fertilizer sulfate sources had an isotopic composition on the mixing line between two natural geological sources of sulfate in the aquifer. This study demonstrates that, when sulfate isotope analysis is being used as a tracer or co-tracer of the origin of groundwater or of contaminants in groundwater, sulfate derived from synthetic fertilizer needs to be considered as a potential source, especially when other parameters such as nitrate independently indicate fertilizer impacts to groundwater quality.

BACKGROUND The objective of this study was to investigate the occurrence of glyphosate residues (glyphosate and its metabolite AMPA) in shallow groundwater in a catchment dominated by agriculture, and to examine the potential for this groundwater to store and transmit these compounds to surface waters. RESULTS Glyphosate residues were found in some of the groundwater samples collected in riparian (surface seeps), upland (mostly <20 m below ground) and wetland settings (<3 m below ground). Overall, glyphosate and AMPA were detected in 10.5 and 5.0%, respectively, of the groundwater samples analyzed as part of this study. All concentrations of glyphosate were well below Canadian guidelines for drinking water quality and for protection of aquatic life. Seasonal differences in concentrations in riparian seeps were possibly related to cycles of weather, herbicide application and degradation of glyphosate. Highest concentrations were at upland sites (663 ng L(-1) of glyphosate, 698 ng L(-1) of AMPA), apparently related to localized applications. Most glyphosate detections in wetlands were >0.5 km distant from possible areas of application, and, combined with other factors, suggest an atmospheric transport and deposition delivery mechanism. In both upland and wetland settings, highest glyphosate concentrations were sometimes not at the shallowest depths, indicating influence of hydrological factors. CONCLUSION The glyphosate/AMPA detections in riparian seeps demonstrated that these compounds are persistent enough to allow groundwater to store and transmit glyphosate residues to surface waters. Detections in the wetlands support earlier evidence that atmospheric transport and deposition may lead to glyphosate contamination of environments not intended as targets of applications. This interpretation is further supported by detections of both glyphosate and AMPA in precipitation samples collected in the same watershed. © 2016 Her Majesty the Queen in Right of Canada Pest Management Science © 2016 Society of Chemical Industry.