Spatiotemporal investigation of geochemical and hydrological controls on release of soluble reactive phosphorus from the shallow aquifer of a riparian zone.

Phosphorus (P) that accumulates in agricultural riparian zones can be released under certain hydrological and biogeochemical conditions, thereby limiting the effectiveness of these zones in reducing P loads from field to stream. The study objective was to explore factors that may be contributing to, or limiting, high soluble reactive phosphorus (SRP) concentrations in the shallow aquifer of an alluvial upland riparian zone located in a continental climate. Field investigations including porewater sampling from six vertical nests, soil sampling, and continuous soil moisture, groundwater table, and redox measurements were conducted over 19 months. Porewater SRP concentrations were generally low in the aquifer considering all sampling times (median = 14.7 µg/L; interquartile range [IQR] = 11.1 µg/L, 287 samples). The overall low SRP may be due to low reducible labile soil P (median = 21.1 µgP/g dw, IQR = 10.9 µgP/g dw, 21 samples). However, high SRP concentrations (>52 µg/L, 95% quartile) did occur intermittently in space and time with no clear spatial or temporal patterns. Analyses indicate that most high concentrations were likely not associated with factors previously reported to influence SRP release in riparian aquifers, including redox conditions, pH, and soil drying and wetting. Further, data indicate that internally released or externally supplied SRP may undergo rapid (re-) sequestration within the aquifer, limiting its vertical or horizontal transport. The study findings highlight the complexity of P behavior in riparian zones and the need for caution when assessing the effectiveness of conservation practices and in interpreting potential impacts of subsurface water quality on stream water quality when monitoring locations are distant from the stream.

Characterization of subsurface pathways contributing to freshwater salinization of urban streams using electrical and electromagnetic imaging techniques.

Salinization of inland fresh surface waters in temperate climates is a growing concern due to increasing salt inputs from sources including chloride (Cl)-containing road salt de-icers, industrial waste, and landfill leachate. Groundwater pathways play an important role in the year-round delivery of Cl to streams, but quantifying this pathway, including spatiotemporal variability and amount of Cl mass stored in the subsurface, is challenging. The objective of this study was to demonstrate, evaluate, and compare the potential applications of the geoelectrical techniques - electromagnetics (EM) and direct current (DC) resistivity - for mapping salt contamination in shallow urban groundwater and characterizing the groundwater pathways delivering Cl to urban streams. EM and DC surveys were conducted (3D mapping and 2D time-lapse) across a 20 m salt-impacted stream section and surrounding riparian zone that is located near an arterial road and parking lot. Groundwater samples and soil cores were also collected to validate the geoelectrical results. Both the EM and DC surveys detected high salt concentrations in the shallow subsurface (up to 3 m depth) near the road, parking lot, and stream; however, DC more accurately represented groundwater Cl concentrations. DC results were used to calculate the total Cl mass in the subsurface, with the spatial mass distribution used to infer the temporal variability in the subsurface salt plume. Finally, time-lapse DC showed that the highest groundwater salt concentrations existed near the stream between June and October - this is expected to contribute to the elevated salt concentrations in the stream during summer months. This study has shown that EM and DC can be useful for identifying groundwater salt concentration, storage, and transport in a non-intrusive and efficient manner, making them valuable field tools for characterizing and quantifying groundwater salt pathways to urban streams.

Multizone Aquatic Ecological Exposures to Landfill Contaminants from a Groundwater Plume Discharging to a Pond.

While it is recognized that groundwater contaminant plumes can impact surface waters, there remains little information on the magnitude, spatial extent, and especially temporal variability of the resulting exposure to the variety of aquatic organisms, particularly for stagnant surface waters (e.g., ponds). The present study of a historic landfill plume discharging to a pond investigated contaminant exposure to multiple aquatic zones (endobenthic, epibenthic, pelagic) over approximately 1 year within a temperate climate. Landfill tracers included the artificial sweetener saccharin, ammonium, chloride, and specific conductance. Sampling of pond sediment porewater (upwelling groundwater) and continuous geophysical imaging of the subsurface showed a relatively stable plume footprint covering approximately 26% of the pond, although with spatially varying leachate composition, revealing year-round exposure to endobenthic (within sediments) organisms. Substantial and variable contaminant exposure to epibenthic organisms within the plume footprint was shown by elevated specific conductance measured directly above the sediment interface. Exposure varied daily at times and increased through winter to values representing undiluted plume groundwater. Exposure to pelagic organisms (overlying water) covered a larger area (~50%) due to in-pond circulation. The stream outlet concentrations were stable at approximately 10 times dilution for chloride and saccharin, but were substantially less in summer for ammonium due to in-pond processes. Whereas groundwater contaminants are typically assumed elevated at base flows, the outlet stream contaminant mass discharges to downstream receptors were notably higher in winter than summer, following stream flow patterns. Insights from the present study into the timings and locations of contaminant plume exposure to multiple ecological zones of a pond can provide guidance to contaminated site and aquatic ecosystem managers on improved monitoring, assessment, and remediation protocols. Environ Toxicol Chem 2023;42:1667-1684. © 2023 His Majesty the King in Right of Canada and The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC. Reproduced with the permission of the Minister of Environment and Climate Change Canada.

The acute toxicity of bitumen-influenced groundwaters from the oil sands region to aquatic organisms.

The extraction of surface mined bitumen from oil sands deposits in northern Alberta, Canada produces large quantities of liquid tailings waste, termed oil sands process-affected water (OSPW), which are stored in large tailings ponds. OSPW-derived chemicals from several tailings ponds migrating past containment structures and through groundwater systems pose a concern for surface water contamination. The present study investigated the toxicity of groundwater from near-field sites adjacent to a tailings pond with OPSW influence and far-field sites with only natural oil sands bitumen influence. The acute toxicity of unfractionated groundwater and isolated organic fractions was assessed using a suite of aquatic organisms (Pimephales promelas, Oryzias latipes, Daphnia magna, Hyalella azteca, Lampsilis spp., Ceriodaphnia dubia, Hexagenia spp., and Vibrio fischeri). Assessment of unfractionated groundwater demonstrated toxicity towards all invertebrates in at least one far-field sample, with both near-field and far-field samples with bitumen influence toxic towards P. promelas, while no toxicity was observed for O. latipes. When assessing the unfractionated groundwater and isolated organic fractions from near-field and far-field groundwater sites, P. promelas and H. azteca were the most sensitive to organic components, while D. magna and L. cardium were most sensitive to the inorganic components. Groundwater containing appreciable amounts of dissolved organics exhibited similar toxicities to sensitive species regardless of an OSPW or natural bitumen source. The lack of a clear distinction in relative acute toxicities between near-field and far-field samples indicates that the water-soluble chemicals associated with bitumen are acutely toxic to several aquatic organisms. This result, combined with the similarities in chemical profiles between bitumen-influenced groundwater originating from OSPW and/or natural sources, suggests that the industrial bitumen extraction processes corresponding to the tailings pond in this study are not contributing unique toxic substances to groundwater, relative to natural bitumen compounds present in groundwater flow systems.

Variation in septic system effluent inputs to tributaries in multiple subwatersheds and approaches to distinguish contributing pathways and areas.

Quantifying the contribution of septic systems to contaminant, including nutrient, loading to streams is needed in many watersheds to inform water quality management programs. However, this quantification is challenging due to the distributed locations of septic systems and uncertainties regarding the pathways delivering effluent from septic systems (functioning and failing) to a stream. The objectives of this study were firstly to evaluate how septic effluent inputs to streams vary with stream discharge conditions for multiple subwatersheds with different characteristics (i.e., geology, septic system density, and typical age), and secondly to examine new approaches for distinguishing the pathways and the contributing areas delivering septic effluent to streams. These approaches use the artificial sweetener acesulfame as a conservative tracer for septic effluent in applications of: (i) stream concentration-discharge (C-Q) relationships using low frequency sampling data, (ii) hysteresis behavior in event-based C-Q relationships, and (iii) longitudinal stream sampling. For all nine subwatersheds studied, the amount of septic effluent reaching the subwatershed outlets was considerably higher during high stream discharge (event) conditions compared to low discharge (baseflow) conditions, suggesting pathways other than groundwater may also be important. Generally, the percentage of septic effluent reaching the outlets was less for subwatersheds with newer households compared to those with older households. The combined interpretation of low frequency and event-based C-Q relationships indicate that complex pathways control the delivery of septic effluent to the subwatershed outlets. The interpretations suggest that groundwater pathways may dominate in some subwatersheds, while more rapid pathways associated with failing septic systems (e.g., overland runoff) may be important in others. Finally, longitudinal stream sampling illustrate the potential of acesulfame data to identify key areas contributing septic effluent to the stream. The novel approaches used here can be applied to guide future investigations aiming to quantify and manage water quality impairment from septic systems.

Organic contaminants of emerging concern in leachate of historic municipal landfills.

Many types of contaminants of emerging concern (CECs), including per- and poly-fluoroalkyl substances (PFAS), have been found in leachate of operating municipal landfills. However, there is only limited information on CECs presence in leachate of historic landfills (≥3 decades since closure, often lacking engineered liners or leachate collection systems) at concentrations that may pose a risk to nearby wells and surface water ecosystems. In this study, 48 samples of leachate-impacted groundwater were collected from 20 historic landfills in Ontario, Canada. The CECs measured included artificial sweeteners (ASs), PFAS, organophosphate esters (OPE), pharmaceuticals, bisphenols, sulfamic acid, perchlorate, and substituted phenols. The common presence of the AS saccharin, a known indicator of old landfill leachate, combined with mostly negligible levels of the AS acesulfame, an indicator of modern wastewater, revealed that most samples were strongly influenced by leachate and not cross-contaminated by wastewater (which can contain these same CECs). Several landfills, including ones closed in the 1960s, had total PFAS concentrations similar to those previously measured at modern landfills, with a maximum observed here of 12.7 µg/L. Notably elevated concentrations of several OPE, sulfamic acid, cotinine, and bisphenols A and S were found at many 30-60 year-old landfills. There was little indication of declining concentrations with landfill age, suggesting historic landfills can be long-term sources of CECs to groundwater and that certain CECs may be useful tracers for historic landfill leachate. These findings provide guidance on which CECs may require monitoring at historic landfill sites and wastewater treatment plants receiving their effluent.

Non-target profiling of bitumen-influenced waters for the identification of tracers unique to oil sands processed-affected water (OSPW) in the Athabasca watershed of Alberta, Canada.

RATIONALE: The objective of this study was to identify unique chemical tracers of oil sands process-affected water (OSPW) to enable definitive discrimination of tailings pond seepage from natural bitumen-influenced waters from the Canadian Alberta McMurray formation. METHODS: The approach involved comparing unknowns from an unprecedented sample set of OSPW (n = 4) and OSPW-affected groundwaters (n = 15) with natural bitumen-influenced groundwaters (n = 20), using high-performance liquid chromatography/electrospray ionisation high-resolution mass spectrometry (HPLC/ESI-HRMS) operated in both polarities. RESULTS: Four unknown chemical entities were identified as potential tracers of OSPW seepage and subsequently subjected to structural elucidation. One potential tracer, tentatively identified as a thiophene-containing carboxylic acid [C15 H23 O3 S]- , was only detected in OSPW and OSPW-affected samples, thereby showing the greatest diagnostic potential. The remaining three unknowns, postulated to be two thiochroman isomers [C17 H25 O3 S]+ and an ethyl-naphthalene isomer [C16 H21 ]+ , were detected in one and two background groundwaters, respectively. CONCLUSIONS: We advanced the state of knowledge for tracers of tailings seepage beyond heteroatomic classes, to identifying diagnostic substances, with structures postulated. Synthesis of the four proposed structures is recommended to enable structural confirmations. This research will guide and inform the Oil Sands Monitoring Program in its efforts to assess potential influences of oil sands development on the Athabasca River watershed.

Use of mature willows (Salix nigra) for hydraulic control of landfill-impacted groundwater in a temperate climate.

Phreatophytic trees such as willows and poplars have a large capacity for extracting shallow groundwater, as evidenced by diurnal water table fluctuations corresponding to intensified transpiration during the day. As a result, they have been employed for phytoremediation of shallow contaminated groundwater. In this study, the water extraction (i.e. pumping) capacity of mature willows (Salix nigra) to capture shallow polluted groundwater in Belle Park, the site of a former landfill in Kingston, Ontario (Canada), was assessed using continuous field measurements of sap flow and water table levels associated with a single willow tree, combined with a transient numerical model (FEFLOW). On an annual basis, the sapflow averaged 2.3 m3d-1, with 70% of the cumulative sap flow occurring during the active growing season (May to September). The calibration showed a good fit (0.91 < R2<0.97) between measured groundwater levels from three shallow wells installed near the willow and the calculated water table level fluctuations, thus confirming that the water extraction rate based on sap flow data for the willow was appropriate. At stand level, additional modelling suggests that 3.4-4.7 ha of mature willows (i.e. between 7.8% and 10.6% of the Park area), could compensate for the current water volumes extracted by the municipality using a conventional pump and treat system. The results of this study indicate that willows can play a significant role in capturing contaminated groundwater underlying Belle Park, and potentially at other sites where removal of contaminants from shallow aquifers is desired.

Advances in Distinguishing Groundwater Influenced by Oil Sands Process-Affected Water (OSPW) from Natural Bitumen-Influenced Groundwaters.

The objective of this study was to advance analytical methods for detecting oil sands process-affected water (OSPW) seepage from mining containments and discriminating any such seepage from the natural bitumen background in groundwaters influenced by the Alberta McMurray formation. Improved sampling methods and quantitative analyses of two groups of monoaromatic acids were employed to analyze OSPW and bitumen-affected natural background groundwaters for source discrimination. Both groups of monoaromatic acids showed significant enrichment in OSPW, while ratios of O2/O4 containing heteroatomic ion classes of acid extractable organics (AEOs) did not exhibit diagnostic differences. Evaluating the monoaromatic acids to track a known plume of OSPW-affected groundwater confirmed their diagnostic abilities. A secondary objective was to assess anthropogenically derived artificial sweeteners and per- and polyfluoroalkyl substances (PFAS) as potential tracers for OSPW. Despite the discovery of acesulfame and PFAS in most OSPW samples, trace levels in groundwaters influenced by general anthropogenic activities preclude them as individual robust tracers. However, their inclusion with the other metrics employed in this study served to augment the tiered, weight of evidence methodology developed. This methodology was then used to confirm earlier findings of OSPW migrations into groundwater reaching the Athabasca River system adjacent to the reclaimed pond at Tar Island Dyke.

Endobenthic Organisms Exposed to Chronically High Chloride from Groundwater Discharging along Freshwater Urban Streams and Lakeshores.

Chloride, especially from road salt, is one of the most ubiquitous contaminants of urban groundwater in temperate climates. The discharge of chloride-laden groundwater to freshwater ecosystems may pose a heightened risk to endobenthic organisms (buried in sediments), which may experience high concentrations prior to dilution from the overlying water. However, available exposure data is limited. Presented here are 22 chloride data sets from 15 urban sites across Canada, encompassing >1300 samples of shallow discharging groundwater collected principally during summer through autumn. Over half of the sites had an average chloride concentration above the long-term aquatic life guideline (120 mg/L), while 14% of each site's samples, on average, surpassed the short-term guideline (640 mg/L). Chloride concentrations frequently varied substantially (even >1000 mg/L) between adjacent locations (mostly <20 m separation), indicating patchy exposure. Chloride/bromide ratios, artificial sweeteners, and other tracers suggest a predominant contribution from road salt, with wastewater and landfill leachate important at some sites. Overall, these concentrations exceed those typically reported for urban wells and streams (even during the snowmelt period) in similar climates. These findings suggest that high chloride concentrations in shallow groundwater, largely from road salt, present a long-term threat to endobenthic organisms of urban surface waters in cold-region countries.

Anaerobic biodegradation of dissolved ethanol in a pilot-scale sand aquifer: Gas phase dynamics.

Groundwater contamination from ethanol (e.g., alternative fuels) can support vigorous biodegradation, with many possible reactions producing dissolved gases. The objective of this study was to improve the understanding of the development and evolution of trapped gas phase changes occurring within an ethanol plume undergoing biodegradation. The experiment performed involved highly detailed spatial and temporal monitoring of gas phase saturations using Time Domain Reflectometry probes embedded in a 2-dimensional (175 cm high × 525 cm long) synthetic aquifer (homogeneous sand tank with horizontal groundwater flow). Ethanol injection immediately promoted gas-producing reactions, including: fermentation, denitrification, sulphate-reduction and iron(III)-reduction, with methanogenesis developing between 69 and 109 days. Substantial in situ increases in trapped gas were observed over ~330 days, with maximum gas saturations reaching 27% of the pore volume. Despite sustained gas production, this maximum was never exceeded, likely due to the onset of gas phase mobilization (i.e., ebullition) upon reaching a buoyancy-capillarity threshold. Reductions in the quasi-saturated hydraulic conductivity, resulting from the gas phase accumulation, were restricted by ebullition to a factor of ≤2; but still appeared to alter the groundwater flow field. Overall, trapped gas saturations exhibited high spatial and temporal variability, including declines within the plume and increases outside of the plume. Influential factors included vertically-shifting ethanol inputs and resultant secondary redox reactions, microbial controls on redox zonation, ebullition, and altered groundwater flows. These observations have implications for the transport of gases and volatile compounds within plumes and above the water table at sites with groundwater contamination from ethanol or other highly degradable organics.

Anaerobic biodegradation of dissolved ethanol in a pilot-scale sand aquifer: Variability in plume (redox) biogeochemistry.

The use of ethanol in alternative fuels has led to contamination of groundwater with high concentrations of this easily biodegradable organic compound. Previous laboratory and field studies have shown vigorous biodegradation of ethanol plumes, with prevalence of reducing conditions and methanogenesis. The objective of this study was to further our understanding of the dynamic biogeochemistry processes, especially dissolved gas production, that may occur in developing and aging plume cores at sites with ethanol or other organic contamination of groundwater. The experiment performed involved highly-detailed spatial and temporal monitoring of ethanol biodegradation in a 2-dimensional (175cm high×525cm long) sand aquifer tank for 330days, with a vertical shift in plume position and increased nutrient inputs occurring at ~Day 100. Rapid onset of fermentation, denitrification, sulphate-reduction and iron(III)-reduction occurred following dissolved ethanol addition, with the eventual widespread development of methanogenesis. The detailed observations also demonstrate a redox zonation that supports the plume fringe concept, secondary reactions resulting from a changing/moving plume, and time lags for the various biodegradation processes. Additional highlights include: i) the highest dissolved H2 concentrations yet reported for groundwater, possibly linked to vigorous fermentation in the absence of common terminal electron-acceptors (i.e., dissolved oxygen, nitrate, and sulphate, and iron(III)-minerals) and methanogenesis; ii) evidence of phosphorus nutrient limitation, which stalled ethanol biodegradation and perhaps delayed the onset of methanogenesis; and iii) the occurrence of dissimilatory nitrate reduction to ammonium, which has not been reported for ethanol biodegradation to date.

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.

Patterns of entrapped air dissolution in a two-dimensional pilot-scale synthetic aquifer.

Past studies of entrapped air dissolution have focused on one-dimensional laboratory columns. Here the multidimensional nature of entrapped air dissolution was investigated using an indoor tank (180 × 240 × 600 cm(3) ) simulating an unconfined sand aquifer with horizontal flow. Time domain reflectometry (TDR) probes directly measured entrapped air contents, while dissolved gas conditions were monitored with total dissolved gas pressure (PTDG ) probes. Dissolution occurred as a diffuse wedge-shaped front from the inlet downgradient, with preferential dissolution at depth. This pattern was mainly attributed to increased gas solubility, as shown by PTDG measurements. However, compression of entrapped air at greater depths, captured by TDR and leading to lower quasi-saturated hydraulic conductivities and thus greater velocities, also played a small role. Linear propagation of the dissolution front downgradient was observed at each depth, with both TDR and PTDG , with increasing rates with depth (e.g, 4.1 to 5.7× slower at 15 cm vs. 165 cm depth). PTDG values revealed equilibrium with the entrapped gas initially, being higher at greater depth and fluctuating with the barometric pressure, before declining concurrently with entrapped air contents to the lower PTDG of the source water. The observed dissolution pattern has long-term implications for a wide variety of groundwater management issues, from recharge to contaminant transport and remediation strategies, due to the persistence of entrapped air near the water table (potential timescale of years). This study also demonstrated the utility of PTDG probes for simple in situ measurements to detect entrapped air and monitor its dissolution.

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 Survey's National Water-Quality Assessment (NAWQA) Program ( Dubrovsky, N. M.; et al. The Quality of Our Nation's Water: Nutrients in the Nation's 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.

Profiling oil sands mixtures from industrial developments and natural groundwaters for source identification.

The objective of this study was to identify chemical components that could distinguish chemical mixtures in oil sands process-affected water (OSPW) that had potentially migrated to groundwater in the oil sands development area of northern Alberta, Canada. In the first part of the study, OSPW samples from two different tailings ponds and a broad range of natural groundwater samples were assessed with historically employed techniques as Level-1 analyses, including geochemistry, total concentrations of naphthenic acids (NAs) and synchronous fluorescence spectroscopy (SFS). While these analyses did not allow for reliable source differentiation, they did identify samples containing significant concentrations of oil sands acid-extractable organics (AEOs). In applying Level-2 profiling analyses using electrospray ionization high resolution mass spectrometry (ESI-HRMS) and comprehensive multidimensional gas chromatography time-of-flight mass spectrometry (GC × GC-TOF/MS) to samples containing appreciable AEO concentrations, differentiation of natural from OSPW sources was apparent through measurements of O2:O4 ion class ratios (ESI-HRMS) and diagnostic ions for two families of suspected monoaromatic acids (GC × GC-TOF/MS). The resemblance between the AEO profiles from OSPW and from 6 groundwater samples adjacent to two tailings ponds implies a common source, supporting the use of these complimentary analyses for source identification. These samples included two of upward flowing groundwater collected <1 m beneath the Athabasca River, suggesting OSPW-affected groundwater is reaching the river system.

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.

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.

Changes in entrapped gas content and hydraulic conductivity with pressure.

Water table fluctuations continuously introduce entrapped air bubbles into the otherwise saturated capillary fringe and groundwater zone, which reduces the effective (quasi-saturated) hydraulic conductivity, K(quasi), thus impacting groundwater flow, aquifer recharge and solute and contaminant transport. These entrapped gases will be susceptible to compression or expansion with changes in water pressure, as would be expected with water table (and barometric pressure) fluctuations. Here we undertake laboratory experiments using sand-packed columns to quantify the effect of water table changes of up to 250 cm on the entrapped gas content and the quasi-saturated hydraulic conductivity, and discuss our ability to account for these mechanisms in ground water models. Initial entrapped air contents ranged between 0.080 and 0.158, with a corresponding K(quasi) ranging between 2 and 6 times lower compared to the K(s) value. The application of 250 cm of water pressure caused an 18% to 26% reduction in the entrapped air content, resulting in an increase in K(quasi) by 1.16 to 1.57 times compared to its initial (0 cm water pressure) value. The change in entrapped air content measured at pressure step intervals of 50 cm, was essentially linear, and could be modeled according to the ideal gas law. Meanwhile, the changes in K(quasi) with compression-expansion of the bubbles because of pressure changes could be adequately captured with several current hydraulic conductivity models.