Wastewater contaminants in a fractured bedrock aquifer and their potential use as enteric virus indicators.

Domestic wastewater is a source of persistent organic pollutants and pathogens to the aquatic environment, including groundwater aquifers. Wastewater contaminants include a variety of personal care products, pharmaceuticals, endocrine disrupters, bacteria, and viruses. Groundwater from 22 wells completed in a semi-confined to confined, fractured Silurian dolostone aquifer in southern Wellington County, Ontario, Canada, was analyzed for 14 organic wastewater contaminants (4 artificial sweeteners, 10 pharmaceuticals) as well as E. coli, total coliforms, and 6 human enteric viruses. Enteric viruses were detected in 8.6% of 116 samples, and at least one organic wastewater contaminant was detected in 82% of the wells (in order of decreasing detection frequency: acesulfame, ibuprofen, sulfamethoxazole, triclosan, carbamazepine, and saccharin). Virus indicator metrics [positive and negative predictive values (PPV, NPV), sensitivity, specificity] were calculated at the sample and well level for the organic wastewater compounds, E. coli, and total coliforms. Fecal bacteria were not good predictors of virus presence (PPV = 0%-8%). Of the potential chemical indicators, triclosan performed the best at the sample level (PPV = 50%, NPV = 100%), and ibuprofen performed the best at the well level (PPV = 60%, NPV = 67%); however, no samples had triclosan or ibuprofen concentrations above their practical quantification limits. Therefore, none of the compounds performed sufficiently well to be considered reliable for assessing the potential threat of enteric viruses in wastewater-impacted groundwater in this bedrock aquifer. Future studies need to evaluate the indicator potential of persistent organic wastewater contaminants in different types of aquifers, especially in fractured rock where heterogeneity is strong.IMPORTANCEAssessing the potential risk that human enteric viruses pose in groundwater aquifers used for potable water supply is complicated by several factors, including: (i) labor-intensive methods for the isolation and quantification of viruses in groundwater, (ii) the temporal variability of these viruses in domestic wastewater, and (iii) their potentially rapid transport in the subsurface, especially in fractured rock aquifers. Therefore, aquifer risk assessment would benefit from the identification of suitable proxy indicators of enteric viruses that are easier to analyze and less variable in wastewater sources. Traditional fecal indicators (e.g., E. coli and coliforms) are generally poor indicators of enteric viruses in groundwater. While many studies have examined the use of pharmaceutical and personal care products as tracers of domestic wastewater and fecal pollution in the environment, there is a paucity of data on the potential use of these chemical tracers as enteric virus indicators, especially in groundwater.

Contribution of nitrogen sources to streams in mixed-use catchments varies seasonally in a cold temperate region.

Intensive agriculture and growing human populations are important nitrogen (N) sources thought to be associated with eutrophication. However, the contribution and seasonality of N delivery to streams from human activities is poorly understood and knowledge of the role of stream communities in the assimilation of N from human activities is limited. We used N and oxygen stable isotope ratios of dissolved inorganic N (DIN) and concentrations of artificial sweeteners to identify the relative contribution of key sources of anthropogenic N (i.e., fertilizers, human, and livestock waste) to tributaries of the Red River Valley (RRV), Manitoba, Canada. Water and algae were sampled in 14 RRV tributaries during snowmelt, spring, summer, and autumn; and water was sampled at three locations in the Red River in spring, summer, and autumn. δ15N values of DIN in tributary water differed seasonally and were greatest during snowmelt. Incorporation of ammonium δ15N provided evidence for the importance of manure N to tributaries during snowmelt. Fertilizer and municipal lagoons served as principal sources of N to streams in spring and summer. Human and livestock waste sources of N were the dominant contributor to algae at greater than 90% of sites and algae δ15N was greatest at sites downstream of municipal lagoons. We also showed that the tributaries contribute human and livestock waste N to the Red River, though much of the nitrate in the river originates outside of Manitoba. Overall, our study determined that the anthropogenic sources of N to RRV streams vary seasonally, likely due to regional hydrologic conditions. Our study also showed the potential of artificial sweeteners and ammonium δ15N as tools for identifying N sources to rivers. Moreover, we demonstrate the need for the management of N sources and the protection of stream function to control downstream transfer of N from landscapes to waterbodies.

Isotopic Characterization of Sulfate in a Shallow Aquifer Impacted by Agricultural Fertilizer.

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.

Fate of bioavailable nutrients released to a stream during episodic effluent releases from a municipal wastewater treatment lagoon.

Municipal wastewater lagoons are common across North America and, unlike larger mechanical wastewater treatment plants, typically release nutrient-rich effluent directly to rivers in intermittent pulses. However, little is known about the fate of nutrients from these episodic events, which may happen under varying hydrologic or thermal conditions. We assessed fate of nitrogen (N) and phosphorus (P) from lagoon effluent during three releases to Deadhorse Creek, Manitoba, Canada. Using net nutrient uptake lengths and natural abundance stable isotope ratios of dissolved inorganic nitrogen (DIN) and primary producers, we found that DIN was processed during the summer releases though the dominant mechanism was unclear. However, nitrate was largely exported in autumn. Primary producers assimilated lagoon N but did not appear to reduce DIN concentrations. The longitudinal pattern of soluble reactive phosphorus (SRP) varied between releases and in summer 2019 the stream became a net source of SRP despite concomitant processing of DIN. We hypothesize that low demand for P in Deadhorse Creek, as suggested by upstream SRP > 0.05 mg P L-1, and nutrient ratios indicative of N limitation, reduced instream processing of P. Furthermore, our results indicated that cool or high flow conditions may result in the export of much of the lagoon nutrient load downstream. Our findings suggest the processes that transform wastewater nutrients are overwhelmed during effluent releases. Managers should consider increasing effluent dilution via continuous release of effluent rather than pulsed delivery. However, management of upstream nutrient supply may also be needed when relying upon the self-purifying capacity of rivers.

Variable persistence of artificial sweeteners during wastewater treatment: Implications for future use as tracers.

For more than a decade the artificial sweeteners acesulfame (ACE) and sucralose (SUC) have been applied as tracers of the input of wastewater to environmental waters. Recently concerns have been raised that degradation of ACE during treatment may hinder or restrict its use as a wastewater tracer. In this study the value of ACE and SUC as tracers was reassessed based on samples of wastewater at 12 municipal wastewater treatment (MWWT) plants and from 7 septic systems and associated septic plumes in groundwater. The results indicated stability of SUC during MWWT at most plants, and variable removal of both sweeteners during some MWWT and in the septic wastewater systems. However, the residual concentrations of ACE and SUC in municipal effluent and in septic plumes indicate that both sweeteners remain valuable wastewater tracers. The mass ratio SUC/ACE was found to be a useful parameter for examining the relative persistence of these sweeteners.

Unprocessed Atmospheric Nitrate in Waters of the Northern Forest Region in the U.S. and Canada.

Little is known about the regional extent and variability of nitrate from atmospheric deposition that is transported to streams without biological processing in forests. We measured water chemistry and isotopic tracers (δ18O and δ15N) of nitrate sources across the Northern Forest Region of the U.S. and Canada and reanalyzed data from other studies to determine when, where, and how unprocessed atmospheric nitrate was transported in catchments. These inputs were more widespread and numerous than commonly recognized, but with high spatial and temporal variability. Only 6 of 32 streams had high fractions (>20%) of unprocessed atmospheric nitrate during baseflow. Seventeen had high fractions during stormflow or snowmelt, which corresponded to large fractions in near-surface soil waters or groundwaters, but not deep groundwater. The remaining 10 streams occasionally had some (<20%) unprocessed atmospheric nitrate during stormflow or baseflow. Large, sporadic events may continue to be cryptic due to atmospheric deposition variation among storms and a near complete lack of monitoring for these events. A general lack of observance may bias perceptions of occurrence; sustained monitoring of chronic nitrogen pollution effects on forests with nitrate source apportionments may offer insights needed to advance the science as well as assess regulatory and management schemes.

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.

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. © 2016 Her Majesty the Queen in Right of Canada Pest Management Science © 2016 Society of Chemical Industry.

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.

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 (2.4 µg/L) [corrected], 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.

Stable oxygen isotope ratios of nitrate produced from nitrification: (18)O-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.

Effect of storage on the isotopic composition of nitrate in bulk precipitation.

Stable isotopic analysis of atmospheric nitrate is increasingly employed to study nitrate sources and transformations in forested catchments. Large volumes have typically been required for delta18O and delta15N analysis of nitrate in precipitation due to relatively low nitrate concentrations. Having bulk collectors accumulate precipitation over an extended time period allows for collection of the required volume as well as reducing the total number of analyses needed to determine the isotopic composition of mean annual nitrate deposition. However, unfiltered precipitation left in collectors might be subject to microbial reactions that can alter the isotopic signature of nitrate in the sample. Precipitation obtained from the Turkey Lakes Watershed was incubated under conditions designed to mimic unfiltered storage in bulk precipitation collectors and monitored for changes in nitrate concentration, delta15N, and delta18O. Results of this experiment indicated that no detectable nitrate production or assimilation occurred in the samples during a two-week incubation period and that atmospheric nitrate isotopic ratios were preserved. The ability to collect unfiltered precipitation samples for an extended duration without alteration of nitrate isotope ratios is particularly useful at remote study sites where daily retrieval of samples may not be feasible.