John Spoelstra

Tracing the Sources of Exported Nitrate in the Turkey Lakes Watershed Using 15N/14N and 18O/16O isotopic ratios

Nitrate produced by bacterially mediated nitrification in soils is isotopically distinct from atmospheric nitrate in precipitation. 15N/14N and 18O/16O isotopic ratios of nitrate can therefore be used to distinguish between these two sources of nitrate in surface waters and groundwaters. Two forested catchments in the Turkey Lakes Watershed (TLW) near Sault Ste. Marie, Ontario, Canada were studied to determine the relative contributions of atmospheric and microbial nitrate to nitrate export. The TLW is reasonably undisturbed and receives a moderate amount of inorganic nitrogen bulk deposition (8.7 kg N · ha−1· yr−1) yet it exhibits unusually low inorganic nitrogen retention (average = 65% of deposition). The measured isotopic ratios for nitrate in precipitation ranged from +35 to +59‰ (VSMOW) for δ18O and −4 to +0.8‰ (AIR) for δ15N. Nitrate produced from nitrification at the TLW is expected to have an average isotope value of approximately −1.0‰ for δ18O and a value of about 0 to +6‰ for δ15N, thus, the isotopic separation between atmospheric and soil sources of nitrate is substantial. Nitrate produced by nitrification of ammonium appears to be the dominant source of the nitrate exported in both catchments, even during the snowmelt period. These whole catchment results are consistent with the results of small but intensive plot scale studies that have shown that the majority of the nitrate leached from these catchments is microbial in origin. The isotopic composition of stream nitrate provides information about N-cycling in the forested upland and riparian zones on a whole catchment basis.

Stable Oxygen Isotope Ratios of Nitrate Produced from Nitrification: 18O-Labeled Water Incubations of Agricultural and Temperate Forest Soils

In many nitrate (NO(3)(-)) source partitioning studies, the delta(18)O value for NO(3)(-) produced from nitrification is often assumed to reflect the isotopic compositions of environmental water (H(2)O) and molecular oxygen (O(2)) in a 2:1 ratio. Most studies that have measured or observed this microbial endmember have found that the delta(18)O-NO(3)(-) was more positive (up to +15 per thousand higher) than the assumed value. Current understanding of the mechanism(s) responsible for this discrepancy is limited. Incubations of one temperate forest soil (organic) and two agricultural soils (mineral) were conducted with (18)O-labeled H(2)O to apportion the sources of oxygen in NO(3)(-) generated from nitrification. The NO(3)(-) produced in all soils had delta(18)O values that could not be explained by a simple endmember mixing ratio of 2:1. A more comprehensive model describing the formation of microbial NO(3)(-) was developed, which accounts for oxygen exchange between H(2)O and NO(2)(-), and includes terms for kinetic and equilibrium isotope effects. Oxygen isotope exchange (i.e., the fraction of NO(3)(-)-oxygen that originates from the abiotic exchange of H(2)O and NO(2)(-)) varied widely between the temperate forest soil (0.37) and the two agricultural soils (0.52 and 0.88). At present, the microbial endmember for nitrification cannot be successfully predicted.

Natural attenuation of septic system nitrogen by anammox.

On-site disposal of sewage in septic systems can lead to groundwater plumes with NO(3)(-)-N concentrations exceeding the common drinking water limit of 10 mg/L. Currently, denitrification is considered as the principal natural attenuation process. However, at a large seasonal-use septic system in Ontario (256 campsites), a suboxic zone exists where nitrogen removal of up to 80% occurs including removal of NH(4)(+)-N. This zone has both NO(3)(-)-N and NH(4)(+)-N at >5 mg/L each. In the distal NH(4)(+)-rich zone, NH(4)(+)-N concentrations (8.1 ± 8.0 mg/L) are lower than in the proximal zone (48 ± 36 mg/L) and NH(4)(+)-N is isotopically enriched (concentration-weighted mean δ(15)N of +15.7‰) compared to the proximal zone (+7.8‰). Furthermore, δ(15)N-NH(4)(+) isotopic enrichment increases with depth in the distal zone, which is opposite to what would result if nitrification along the water table zone was the mechanism causing NH(4)(+) depletion. Bacterial community composition was assessed with molecular (DNA-based) analysis and demonstrated that groundwater bacterial populations were predominantly composed of bacteria from two Candidatus genera of the Planctomycetales (Brocadia and Jettenia). Together, these data provide strong evidence that anaerobic ammonium oxidation (anammox) plays an important role in nitrogen attenuation at this site.

Artificial sweeteners in a large Canadian river reflect human consumption in the watershed.

Artificial sweeteners have been widely incorporated in human food products for aid in weight loss regimes, dental health protection and dietary control of diabetes. Some of these widely used compounds can pass non-degraded through wastewater treatment systems and are subsequently discharged to groundwater and surface waters. Measurements of artificial sweeteners in rivers used for drinking water production are scarce. In order to determine the riverine concentrations of artificial sweeteners and their usefulness as a tracer of wastewater at the scale of an entire watershed, we analyzed samples from 23 sites along the entire length of the Grand River, a large river in Southern Ontario, Canada, that is impacted by agricultural activities and urban centres. Municipal water from household taps was also sampled from several cities within the Grand River Watershed. Cyclamate, saccharin, sucralose, and acesulfame were found in elevated concentrations despite high rates of biological activity, large daily cycles in dissolved oxygen and shallow river depth. The maximum concentrations that we measured for sucralose (21 µg/L), cyclamate (0.88 µg/L), and saccharin (7.2 µg/L) are the highest reported concentrations of these compounds in surface waters to date anywhere in the world. Acesulfame persists at concentrations that are up to several orders of magnitude above the detection limit over a distance of 300 km and it behaves conservatively in the river, recording the wastewater contribution from the cumulative population in the basin. Acesulfame is a reliable wastewater effluent tracer in rivers. Furthermore, it can be used to assess rates of nutrient assimilation, track wastewater plume dilution, separate human and animal waste contributions and determine the relative persistence of emerging contaminants in impacted watersheds where multiple sources confound the usefulness of other tracers. The effects of artificial sweeteners on aquatic biota in rivers and in the downstream Great Lakes are largely unknown.

From the Ground Up: Global Nitrous Oxide Sources are Constrained by Stable Isotope Values

Rising concentrations of nitrous oxide (N2O) in the atmosphere are causing widespread concern because this trace gas plays a key role in the destruction of stratospheric ozone and it is a strong greenhouse gas. The successful mitigation of N2O emissions requires a solid understanding of the relative importance of all N2O sources and sinks. Stable isotope ratio measurements (δ15N-N2O and δ18O-N2O), including the intramolecular distribution of 15N (site preference), are one way to track different sources if they are isotopically distinct. ‘Top-down’ isotope mass-balance studies have had limited success balancing the global N2O budget thus far because the isotopic signatures of soil, freshwater, and marine sources are poorly constrained and a comprehensive analysis of global N2O stable isotope measurements has not been done. Here we used a robust analysis of all available in situ measurements to define key global N2O sources. We showed that the marine source is isotopically distinct from soil and freshwater N2O (the continental source). Further, the global average source (sum of all natural and anthropogenic sources) is largely controlled by soils and freshwaters. These findings substantiate past modelling studies that relied on several assumptions about the global N2O cycle. Finally, a two-box-model and a Bayesian isotope mixing model revealed marine and continental N2O sources have relative contributions of 24–26% and 74–76% to the total, respectively. Further, the Bayesian modeling exercise indicated the N2O flux from freshwaters may be much larger than currently thought.

Glyphosate residues in rural groundwater, Nottawasaga River Watershed, Ontario, Canada

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.

Use of an Artificial Sweetener to Identify Sources of Groundwater Nitrate Contamination.

The artificial sweetener acesulfame (ACE) is a potentially useful tracer of waste water contamination in groundwater. In this study, ACE concentrations were measured in waste water and impacted groundwater at 12 septic system sites in Ontario, Canada. All samples of septic tank effluent (n = 37) had ACE >6 µg/L, all samples of groundwater from the proximal plume zones (n = 93) had ACE >1 µg/L and, almost all samples from the distal plume zones had ACE >2 µg/L. Mean mass ratios of total inorganic nitrogen/ACE at the 12 sites ranged from 680 to 3500 for the tank and proximal plume samples. At five sites, decreasing ratio values in the distal zones indicated nitrogen attenuation. These ratios were applied to three aquifers in Canada that are nitrate-stressed and an urban stream where septic systems are present nearby to estimate the amount of waste water nitrate contamination. At the three aquifer locations that are agricultural, low ACE values (<0.02-0.15 µg/L) indicated that waste water contributed <15% of the nitrate in most samples. In groundwater discharging to the urban stream, much higher ACE values (0.2-11 µg/L) indicated that waste water was the likely source of >50% of the nitrate in most samples. This study confirms that ACE is a powerful tracer and demonstrates its use as a diagnostic tool for establishing whether waste water is a significant contributor to groundwater contamination or not.

Stable Isotopes Reveal Rapid Cycling of Soil Nitrogen after Manure Application

Understanding the fate of applied nitrogen (N) in agricultural soils is important for agronomic, environmental, and human health reasons, but it is methodologically difficult to study at the field scale. Natural abundance stable isotope measurements (δN) were used in this field study with micrometeorological measurements of nitrous oxide (NO) emissions to identify the biogeochemical processes responsible for rapid N transformations immediately after application of liquid dairy manure. Fifteen samplings occurred between 16 Mar. 2012 and 5 Apr. 2013, with a focus on spring manure application (before and after) and a winter snowmelt period. Concentrations and δN values of ammonium (NH), nitrate (NO), NO, and total N were measured throughout the year. Approximately 56 (±7)% of the NH-N applied in the spring could not be accounted for 3 d after manure application and was presumably lost by ammonia volatilization before it was tilled into the soil and/or removed from the inorganic N pool by microbial assimilation. Almost all of the remaining manure-NH (95 ± 1.1%) was converted within 3 wk to NO and NO by nitrification and nitrifier-denitrification, respectively. The in situ N isotope effect for nitrification (ε) was calculated to be -32.0 (±5.3)‰. Overall, field-scale measurements of δN at natural abundance provided valuable information that was used to distinguish sources of NH (manure vs. soil organic N) and to follow the production and consumption of NO and the pathways of NO production in soil.

Artificial Sweeteners Reveal Septic System Effluent in Rural Groundwater

It has been widely documented that municipal wastewater treatment plant effluents are a major source of artificial sweeteners to surface waters. However, in rural areas, the extent to which septic systems contribute these same compounds to groundwater aquifers is largely unknown. We examined the occurrence of four commonly used artificial sweeteners in an unconfined sand aquifer that serves as a water supply for rural residents, as a receptor of domestic wastewater from septic systems, and as a source of baseflow to the Nottawasaga River, ON, Canada. Groundwater from the Lake Algonquin Sand Aquifer in the southern Nottawasaga River Watershed was collected from private domestic wells and as groundwater seeps discharging along the banks of the Nottawasaga River. Approximately 30% of samples had detectable levels of one or more artificial sweeteners, indicating the presence of water derived from septic system effluent. Using acesulfame concentrations to estimate the fraction of septic effluent in groundwater samples, ∼3.4 to 13.6% of the domestic wells had 1% or more of their well water being derived from septic system effluent. Similarly, 2.0 to 4.7% of the groundwater seeps had a septic effluent contribution of 1% or more. No relationship was found between the concentration of acesulfame and the concentration of nitrate, ammonium, or soluble reactive phosphorus in the groundwater, indicating that septic effluent is not the dominant source of nutrients in the aquifer. It is expected that the occurrence of artificial sweeteners in shallow groundwater is widespread throughout rural areas in Canada.