Greg Bickerton

An artificial sweetener and pharmaceutical compounds as co-tracers of urban wastewater in groundwater.

Groundwater in urban areas can be affected by numerous wastewater sources. Distinguishing these sources can facilitate better management of urban water resources and wastewater, and protection of urban aquatic environments. A single wastewater tracer, even if ideal (i.e. low background levels, non-reactive, low detection limits, etc.), would be unable to accomplish this task. Here, we investigated the potential advantages of using a suite of anthropogenic chemicals as co-tracers to distinguish wastewater sources that contribute to groundwater contamination at two urban sites. We considered both relatively ubiquitous and non-ubiquitous tracers in wastewater. At the Jasper (Alberta, Canada) site, concentrations of an artificial sweetener, two pharmaceutical compounds, and a degradate of nicotine in groundwater were strongly correlated as co-tracers. This evidence, along with the similar spatial distributions of these co-tracers could be used to delineate and distinguish a single municipal wastewater plume. At the Barrie (Ontario, Canada) site, there was moderate to strong correlation of the wastewater co-tracers, but local differences in their distributions and in the ratios of their concentrations could be used to infer that mixtures of two or more domestic septic plumes were present in the groundwater at this site. This study demonstrates the benefit of applying a suite of tracers to urban groundwater affected by wastewater contamination. This approach should be applicable at other urban sites.

Toxic Groundwater Contaminants: An Overlooked Contributor to Urban Stream Syndrome?

Screening for common groundwater contaminants was performed along eight urban stream reaches (100s-1000s of m) at approximately 25-75 cm below the streambeds. Four sites had known or suspected chlorinated-solvent plumes; otherwise no groundwater contamination was known previously. At each site, between 5 and 22 contaminants were detected at levels above guideline concentrations for the preservation of aquatic life, while several others were detected at lower levels, but which may still indicate some risk. Contaminants of greatest concern include numerous metals (Cd, Zn, Al, Cu, Cr, U), arsenic, various organics (chlorinated and petroleum), nitrate and ammonium, and chloride (road salt likely), with multiple types occurring at each site and often at the same sampling location. Substantial portions of the stream reaches (from 40 to 88% of locations sampled) possessed one or more contaminants above guidelines. These findings suggest that this diffuse and variable-composition urban groundwater contamination is a toxicity concern for all sites and over a large portion of each study reach. Synergistic toxicity, both for similar and disparate compounds, may also be important. We conclude that groundwater contaminants should be considered a genuine risk to urban stream aquatic ecosystems, specifically benthic organisms, and may contribute to urban stream syndrome.

Residues of the herbicide glyphosate in riparian groundwater in urban catchments

The herbicide glyphosate and its putative metabolite aminomethylphosphonic acid (AMPA) have been found in urban streams, but limited information is available on their presence in urban riparian groundwater. Information is also lacking regarding the source of AMPA in these urban settings (glyphosate metabolite or wastewater), and whether, if present, glyphosate residues in urban riparian groundwater contribute significantly to urban streams. Glyphosate and AMPA were detected in shallow riparian groundwater at 4 of 5 stream sites in urban catchments in Canada and each were found in approximately 1 in 10 of the samples overall. Frequency of observations of glyphosate and AMPA varied substantially between sites, from no observations in a National Park near the Town of Jasper Alberta, to observations of both glyphosate and AMPA in more than half of the samples along two short reaches of streams in Burlington, Ontario. In these two catchments, AMPA was correlated with glyphosate, rather than the artificial sweetener acesulfame, suggesting that the AMPA is derived mainly from glyphosate degradation rather than from wastewater sources. Land use, localized dosage history, depth below ground and other factors likely control the occurrence of detectable glyphosate residues in groundwater.

Proactive screening approach for detecting groundwater contaminants along urban streams at the reach-scale.

Here we outline and demonstrate a screening approach for the detection of groundwater contaminants along urban streams within unconsolidated beds. It involves the rapid acquisition of groundwater samples along urban stream reaches at a spacing of about 10 m and from depths of about 25-75 cm below the streambed, with analyses for a suite of potential contaminants. This screening approach may serve two functions: a) providing information for assessing and mitigating the toxicity and eutrophication risks to aquatic ecosystems posed by groundwater contaminants and b) detecting and identifying groundwater contamination in urban settings more rapidly and inexpensively compared to land-based well installations. The screening approach was tested at three urban streams, each affected by a known chlorinated-solvent plume. All three known groundwater plumes were detected and roughly delineated. Multiple, previously unknown, areas or types of groundwater contamination were also identified at each stream. The newly identified contaminants and plumes included petroleum hydrocarbons (BTEX, naphthalene, MTBE), 1,4-dioxane, nitrate and phosphate, road salt, and various metals (including arsenic, cadmium, chromium, copper, lead) at elevated concentrations compared to background values and relevant Canadian water quality guidelines. These findings suggest that this screening approach may be a useful tool for both ecologists performing ecological assessments and stream restorations and for hydrogeologists undertaking groundwater protection activities. Given the numerous contaminants detected, it may be appropriate to apply this technique proactively to better determine the pervasiveness of urban groundwater contaminants, especially along urban streams.

Artificial sweeteners as potential tracers of municipal landfill leachate.

Artificial sweeteners are gaining acceptance as tracers of human wastewater in the environment. The 3 artificial sweeteners analyzed in this study were detected in leachate or leachate-impacted groundwater at levels comparable to those of untreated wastewater at 14 of 15 municipal landfill sites tested, including several closed for >50 years. Saccharin was the dominant sweetener in old (pre-1990) landfills, while newer landfills were dominated by saccharin and acesulfame (introduced 2 decades ago; dominant in wastewater). Cyclamate was also detected, but less frequently. A case study at one site illustrates the use of artificial sweeteners to identify a landfill-impacted groundwater plume discharging to a stream. The study results suggest that artificial sweeteners can be useful tracers for current and legacy landfill contamination, with relative abundances of the sweeteners potentially providing diagnostic ability to distinguish different landfills or landfill cells, including crude age-dating, and to distinguish landfill and wastewater sources.

Elevated Dissolved Phosphorus in Riparian Groundwater along Gaining Urban Streams

Findings of low concentrations of dissolved phosphorus in groundwater in large surveys [e.g., United States Geological Surveys National Water-Quality Assessment (NAWQA) Program ( Dubrovsky, N. M.; et al. The Quality of Our Nations Water: Nutrients in the Nations Streams and Groundwater, 1992-2004 . U.S. Geological Survey Circular 1350; USGS : Reston, VA , 2010 . ); >5000 wells] support the common perception that groundwater is generally of little importance for transporting phosphorus. Here, we address whether this applies to urban riparian settings, where discharging groundwater may potentially contribute to urban stream syndrome and downstream eutrophication problems. This survey study includes 665 samples of groundwater collected along gaining stream reaches at six urban sites. Considering the combined sample set, 27% had soluble reactive phosphorus (SRP) concentrations >0.1 mg L(-1), which is more than double that determined in the NAWQA Program (12%), while for individual sites the range was 12-52%, excluding one site with consistently low SRP (0%). None of the sites showed significant correlation between SRP and the artificial sweetener acesulfame, a promising wastewater indicator, including two with known wastewater contamination (but the lowest SRP). Rather, high SRP concentrations were associated with geochemically reducing conditions. This could mean that natural aquifer or stream sediment materials were a primary contributor of the elevated SRP observed in this study.

Assessing potential toxicity of chloride-affected groundwater discharging to an urban stream using juvenile freshwater mussels (Lampsilis siliquoidea)

Groundwater contaminants, such as chloride from road salt, pose a threat to aquatic ecosystems when and where they discharge to surface waters. Here we study the application of a laboratory toxicity bioassay to field-collected samples from contaminated groundwater discharging to an urban stream. The objectives were to assess the potential toxicity of the discharging groundwater, while also exploring the suitability of such standard tests to site groundwater. Juvenile freshwater mussels were chosen as a groundwater-appropriate (endobenthic) test organism. Groundwater was sampled from 6 sites at approximate depths of 0, 10, and 50 cm below the sediment. Concentrations of chloride and several metals were above aquatic life guidelines in some samples. Exposure (96-h) to site groundwater resulted in survival of 90-100% and 80-100% for the 0-cm and deeper samples, respectively, indicating that groundwater may pose a toxicological threat to freshwater mussels. Several samples with high chloride had a survival rate of 80%, but generally there was poor correlation between survival and individual contaminants. Parallel juvenile mussel exposures using reconstituted water and NaCl predicted survival in the natural groundwater below 50% based on chloride concentrations. This indicates some protective ability of groundwater, possibly associated with water hardness. Finally, some technical issues with performing bioassays with groundwater were noted. First, aeration of previously anoxic groundwater samples caused marked changes in water quality (especially metal concentrations). Second, calcite crystals formed on the mussel shells in samples with elevated chloride and water hardness, though with no apparent negative effects.

Natural Attenuation of Perchlorate in Denitrified Groundwater

Monitoring of a well-defined septic system groundwater plume and groundwater discharging to two urban streams located in southern Ontario, Canada, provided evidence of natural attenuation of background low level (ng/L) perchlorate (ClO4⁻) under denitrifying conditions in the field. The septic system site at Long Point contains ClO4⁻ from a mix of waste water, atmospheric deposition, and periodic use of fireworks, while the nitrate plume indicates active denitrification. Plume nitrate (NO3⁻ -N) concentrations of up to 103 mg/L declined with depth and downgradient of the tile bed due to denitrification and anammox activity, and the plume was almost completely denitrified beyond 35 m from the tile bed. The ClO4⁻ natural attenuation occurs at the site only when NO3⁻ -N concentrations are <0.3 mg/L, after which ClO4⁻ concentrations decline abruptly from 187 ± 202 to 11 ± 15 ng/L. A similar pattern between NO3⁻ -N and ClO4⁻ was found in groundwater discharging to the two urban streams. These findings suggest that natural attenuation (i.e., biodegradation) of ClO4⁻ may be commonplace in denitrified aquifers with appropriate electron donors present, and thus, should be considered as a remediation option for ClO4⁻ contaminated groundwater.