Concentrations of Artificial Sweeteners and Their Ratios with Nutrients in Septic System Wastewater

This study reports the first comprehensive data set of characteristic concentrations of four artificial sweeteners: acesulfame (ACE), sucralose (SUC), saccharin (SAC), and cyclamate (CYC), and their ratios with nutrients, for untreated septic system wastewater. Samples were collected from the tanks of 19 different septic systems from across Ontario, Canada; these had a variety of usages, from single‐family cottages to multiple‐dwelling (campground or resort) facilities and had no additional treatment systems. The artificial sweetener concentrations and their relative proportions were highly variable in some cases, both temporally for several individual tanks and from site‐to‐site. Variability tended to be lower for multiple‐dwelling compared to single‐dwelling systems. This variability likely reflects differing use of artificial sweetener‐containing products. The median concentrations for the complete data set of all four artificial sweeteners (in a range of 10 to 60 μg/L) were of a similar order of magnitude, but slightly higher, than has generally been reported for wastewater treatment plant influent (though these vary substantially globally). Both SUC and ACE provided adequate positive linear relationships for dissolved nitrogen and phosphorus in the septic tanks, while a summation of ACE and SUC concentrations also gave a strong correlation. In contrast, CYC and SAC showed poor linear correlation with these nutrients. These reported ranges for artificial sweetener concentrations and ratios with nutrients may be used in future studies to estimate the contributions of nutrients or other wastewater constituents (e.g., pharmaceuticals, bacteria, and viruses) from domestic septic systems to groundwater, including water supply or irrigation wells, and nearby surface water bodies.     

Assessing the Transport of Pharmaceutical Compounds in a Layered Aquifer Discharging to a Stream

A groundwater plume containing high concentrations of pharmaceutical compounds, mainly sulfonamides, barbiturates, and ethyl urethane, in addition to chlorinated ethenes and benzene was investigated. The contamination originating from a former pharmaceutical industry discharges into a multilayered aquifer system and a downgradient stream. In this study, geological and hydrogeological data were integrated into a numerical flow model to examine identified trends using statistical approaches, including principal component analysis and hierarchal cluster analysis. A joint interpretation of the groundwater flow paths and contaminant concentrations in the different compartments (i.e., groundwater and hyporheic zone) provided insight on the transport processes of the different contaminant plumes to the stream. The analysis of historical groundwater concentrations of pharmaceutical compounds at the site suggested these compounds are slowly degrading. The pharmaceutical compounds migrate in both a deep semiconfined aquifer, as well as in the shallow unconfined aquifer, and enter the stream along a 2-km stretch. This contrasted with the chlorinated ethenes, which mainly discharge to the stream as a focused plume from the unconfined aquifer. The integrated approach developed here, combining groundwater flow modeling and statistical analyses of the contaminant concentration data collected in groundwater and the hyporheic zone, lead to an improved understanding of the observed distribution of contaminants in the unconfined and semiconfined aquifers, and thus to their discharge to the stream. This approach is particularly relevant for large and long-lasting contaminant sources and plumes, such as abandoned landfills and industrial production sites, where field investigations may be very expensive.     

Storage and Preservation of Artificial Sweeteners in Groundwater Samples

Compound‐specific standardized sampling and storage methods are not available for artificial sweeteners found in groundwater. This study aimed to understand: (1) the appropriate length of storage time for samples containing acesulfame (ACE), sucralose (SUC), saccharin (SAC), and cyclamate (CYC) in simulated groundwater (SGW); (2) conditions of their stability; and (3) which sampling materials are appropriate for sample collection. The evaluated storage conditions included acidification, headspace, exposure to light, and refrigeration; the evaluated sampling materials included steel, stainless steel, aluminum, polyvinyl chloride, polyamide (nylon), polypropylene (PharMed BPT?) tubing, styrene‐ethylene‐butylene co‐polymer (MasterFlex?) tubing, and polytetrafluoroethylene (Teflon?) tubing. All compounds evaluated were stable in storage at 4 °C for 241 d (8 months). Concentrations of artificial sweeteners were consistently within 60% to 120% of original concentrations, except ACE and SAC that were substantially lower under acidified conditions at 25 °C after 241 d. Artificial sweetener concentrations remained nearly constant while in contact with all sampling materials except steel. SEM and TEM images showed oxidation of steel occurred; moreover, removal of all artificial sweetener compounds from aqueous solution had occurred after 289 d. These results suggest artificial sweetener analyses conducted within 14 d of sample collection produce optimal results; however, longer storage times may be acceptable under certain conditions. The results also suggest concentrations of artificial sweeteners in SGW are not affected by contact with typical well casing, sampling, and storage materials, with the exception of steel. The findings from this study will improve the use of artificial sweeteners as tracers in environmental studies.     

Bioattenuation in groundwater impacted by landfill leachate traced with δ13C

The impact on groundwater imparted by the infiltration of high dissolved organic carbon (DOC) leachate from capped, unlined landfills can be attenuated by biogeochemical reactions beyond the waste source, although such reactive loss in the aquifer is difficult to distinguish from conservative advective dispersion. Compound-specific measurement of δ(13)C in carbon species, including CH(4), dissolved inorganic carbon (DIC), and the major DOC compounds (acetate, humic acid, and fulvic acid) provides a constraint in this assessment that can assist in exercises of modeling and prediction of leachate transport. The Trail Road municipal landfill near Ottawa, Ontario, Canada, hosts an unlined sector which produces a highly enriched leachate (DOC >4500 mg/L) that provides a good site to examine reactive attenuation within the receptor aquifer. Acetate, a sentinel component of leachate DOC (~1000 mg C/L), is absent in impacted groundwater. Mass balance calculations together with reaction modeling suggest continued acetate fermentation with calcite control on DIC and δ(13)C(DIC) evolution. In groundwater within 50 m of the landfill, methane concentrations are elevated (~10 mg/L), consistent with acetate fermentation, whereas δ(13)C(CH4) measurements in deeper groundwater range down to -51‰ compared with -60‰ in the landfill demonstrating oxidative loss. DOC in the deep aquifer is remarkably depleted to values less than -40‰ suggesting methanotrophic bacteria selectively consume isotopically light CH(4) to fix carbon. Continued reaction of leachate DOC in groundwater is demonstrated by evolution away from conservative mixing lines on diagrams of δ(13)C vs. concentrations of DIC and DOC.     

Evidence of Spatio-Temporal Variations in Contaminants Discharging to a Peri-Urban Stream

Xenobiotic organic compounds can be discharged from contaminated groundwater inflow and may seep into streams from multiple pathways with very different dynamics, some not fully understood. In this study, we investigated the spatio-temporal variation of chlorinated ethenes discharging from a former industrial site (with two main contaminant sources, A and B) into a stream system in a heterogeneous clay till setting in eastern Denmark. The investigated reach and near-stream surroundings are representative of peri-urban settings, with a mix of high channel alteration and more natural stream environment. We therefore propose an approach for risk assessing impacts arising from such complex contamination patterns, accounting for potential spatio-temporal fluctuations and presence of multiple pathways. Our study revealed substantial variations in pathway contributions and overall contaminant mass discharge to the stream. Variable contaminant contributions arising from both groundwater seepage and urban drains were identified in the channelized part of the north stream, primarily from source A. Furthermore, variations in the hyporheic and shallow groundwater flows were found to enhance contaminant transport from source B. These processes result in an increase of the overall mass of contaminant discharged, correlating with the channels' flow. Thus, an in-stream control plane approach was found to be an effective method for integrating multiple and variable discharge contributions quantitatively, although information on specific contaminant sources is lost. This study highlights the complexity and variability of contaminant fluxes occurring at the interface between groundwater and peri-urban streams, and calls for the consideration of these variations when designing monitoring programs and remedial actions for contaminated sites with the potential to impact streams.     

Groundwater monitoring strategies for variable contaminant migration boundaries

Abstract

Detection efficiencies of alternative groundwater monitoring networks were evaluated in relation to distance to a buffer zone (contaminant migration) boundary. This boundary establishes a distance limit within which contaminant plumes should pass through monitoring wells, located on curvilinear segments (monitoring loci) near a waste storage facility. Alternative strategies allocated monitoring wells to loci at specified distances, measured parallel to groundwater flow, from the downgradient boundaries of a landfill. One approach constrained wells to equal spacing, measured perpendicular to groundwater flow. Compressing well locations 10% closer to the downgradient corner of the landfill rendered alternative monitoring configurations. Computations by a monitoring efficiency model indicated: (a) networks largely maintained detection efficiency for different contaminant migration boundaries; (b) one network most efficiently attained a target detection capability for all contaminant migration boundaries; and (c) compressed networks slightly outperformed equal-spaced counterparts. Compressed networks with more wells along closer monitoring loci best maintained the detection efficiency when shifting the contaminant migration boundary closer to the landfill. Procedures described in this paper may be useful for examining trade-offs between monitoring efficiency and distance limits of contaminant travel at landfills posing potential hazards to underlying groundwater.     

Investigating landfill‐impacted groundwater seepage into headwater streams using stable carbon isotopes

The impact of landfill contaminated groundwater along a reach of a small stream adjacent to a municipal landfill was investigated using stable carbon isotopes as a tracer. Groundwater below the stream channel, groundwater seeping into the stream, groundwater from the stream banks and stream water were sampled and analysed for dissolved inorganic carbon (DIC) and the isotope ratio of DIC (δ¹³C_DIC). Representative samples of groundwater seeping into the stream were collected using a device (a ‘seepage well’) specifically designed for collecting samples of groundwater seeping into shallow streams with soft sediments. The DIC and δ¹³C_DIC of water samples ranged from 52 to 205 mg C/L and ?16·9 to +5·7‰ relative to VPDB standard, respectively. Groundwater from the stream bank adjacent to the landfill and some samples of groundwater below the stream channel and seepage into the stream showed evidence of δ¹³C enriched DIC (δ¹³C_DIC = ?2·3 to +5·7‰), which we attribute to landfill impact. Stream water and groundwater from the stream bank opposite the landfill did not show evidence of landfill carbon (δ¹³C_DIC = ?10·0 to ?16·9‰). A simple mixing model using DIC and δ¹³C_DIC showed that groundwater below the stream and groundwater seeping into the stream could be described as a mixture of groundwater with a landfill carbon signature and uncontaminated groundwater. This study suggests that the hyporheic zone at the stream–groundwater interface probably was impacted by landfill contaminated groundwater and may have significant ecological implications for this ecotone. Copyright © 2004 John Wiley & Sons, Ltd.     

Elements in Cottonwood Trees as an Indicator of Ground Water Contaminated by Landfill Leachate

Ground water at the Norman Landfill Research Site is contaminated by a leachate plume emanating from a closed, unlined landfill formerly operated by the city of Norman, Oklahoma, Ground water contaminated by the leachate plume is known to be elevated in the concentration of many, organic and inorganic constituents. Specific conductance, alkalinity, chloride, dissolved organic carbon, boron, sodium, strontium, and deuterium in ground water are considered to be indicators of the leachate plume at this site.
Leaf samples of broad-leafed cottonwood, Populus deltoides , were collected from 57 sites around the closed landfill. Cottonwood, a phreatophyte or "well plant," functions as a & surrogate well and serves as a ground water quality sampler. The leaf samples were combusted to ash and analyzed by instrumental neutron activation for 35 elements and by prompt-gamma instrumental neutron activation, for boron. A monitoring well was located within a few meters of a sampled cottonwood tree at 15 of the 57 sites, and ground water samples were collected from these monitoring wells simultaneously with a leaf sample. The chemical analyses of the ground water and leaf samples from these 15 sites indicated that boron, bromine, sodium, and strontium concentrations in leaves were significantly correlated with leachate indicator constituents in ground water. A point-plot map of selected percentiles indicated high concentrations of boron, bromine, and sodium in leaf ash from sites downgradient of the most recent landfill and from older landfills nearby.
Data from leaf analysis greatly extended the known areal extent of the leachate plume previously determined from a network of monitoring wells and geophysical surveys. This phytosgeochemical study provided a cost-effective method for assessing the extent of a leachate plume from an old landfill. Such a method may be useful as a preliminary sampling tool to guide the design of hydrogeochemical and geophysical studies.     

A Method for Predicting Chloride Concentrations in Leachate at Natural Attenuation Landfills in the Precambrian Shield Regions of Ontario, Canada

Natural attenuation landfill sites continue to be the preferred method of domestic waste disposal in the Precambrian Shield regions of Ontario due to economic factors. The main challenge in siting these landfills is ensuring that there will be no adverse impact on off-site water resources. Impact risk assessments are generally based on estimated volumes and strengths of chloride in the leachate. While volumes can be estimated using simple water balances, peak chloride concentration predictions are based on judgment and are quite variable. Since design chloride strengths dictate the size of the required attenuation zone, overestimating concentrations will typically make it impossible to find a suitable site, while underestimating concentrations increases the potential for adverse off-site impacts occurring.
Hydrogeological data from active and closed landfills in the Precambrian Shield region were collected to help develop a reliable method of predicting peak chloride concentrations in leachate. This study focused on 21 sites located on relatively permeable sandy soils since landfills underlain by low permeability clayey soils retain leachate similar to lined facilities.
Linear regression analyses were conducted to determine if source chloride concentrations at the "sand" sites are significantly influenced by waste thickness, fill area, waste volume, waste deposition rate, hydraulic conductivity, upgradient flow length, depth to the water table, and moisture surplus.
A strong relationship (R = 0.957) was found to exist between source chloride concentrations and waste volume. This empirical volume versus chloride regression equation can be used as the basis for establishing design chloride concentrations at new natural attenuation landfills developed over sandy soils in the Precambrian Shield regions of Ontario. An alternative risk assessment approach is required for sites developed over clay soils.     

Seasonal mixing from intermittent flow drives concentration-discharge behaviour in a stream affected by coal mine drainage

Abandoned mining operations continue to severely degrade many ecosystems worldwide by releasing acidic water and/or heavy metals into surface and groundwater. Contaminant concentrations in affected streams vary with discharge in patterns that reflect both geochemical reactions and variable mixing of contaminated and non-contaminated waters. However, controls on concentration-discharge (C-Q) patterns remain unclear, particularly for constituents that experience changing solubility across redox and pH gradients. Understanding the C-Q behaviour of contaminants aids in predicting both downstream transport and effects on aquatic life under variable flow. Here, we examined the C-Q behaviours of non-reactive (Na, K, Ca, Mg, Cl⁻) and reactive (Fe, Mn, Al, H⁺, SO₄²⁻) solutes in a stream contaminated with acid mine drainage in northeastern Ohio, USA. Concentration-discharge patterns at the watershed outlet primarily reflected mixing of contaminated baseflow with intermittent inputs of high pH water draining from a passive limestone treatment system into the stream. The treatment system acted as an ephemeral tributary that mitigated contamination in the stream by diluting solutes, raising pH, and driving metal precipitation, but only when flow was present during wet seasons. Consequently, AMD-derived reactive solutes (H⁺, Fe, Mn, Al) decreased with increasing stream discharge while relatively conservative solutes (e.g., Ca, Mg, K, Na) decreased only slightly or were chemostatic. This study highlights both the unique C-Q patterns of reactive solutes when compared to those of non-reactive solutes and the potential for intermittent streams to control C-Q behaviour in headwater catchments.     

Innovative Contaminant Mass Flux Monitoring in an Aquifer Subject to Tidal Effects

Exposure from groundwater contamination to aquatic receptors residing in receiving surface water is dependent upon the rate of contaminated groundwater discharge. Characterization of groundwater fluxes is challenging, especially in coastal environments where tidal fluctuations result in transient groundwater flows towards these receptors. This can also be further complicated by the high spatial heterogeneity of subsurface deposits enhanced by anthropogenic influences such as the mixing of natural sediments and backfill materials, the presence of subsurface built structures such as sheet pile walls or even occurrence of other sources of contaminant discharge. In this study, the finite volume point dilution method (FVPDM) was successfully used to characterize highly transient groundwater flows and contaminant mass fluxes within a coastal groundwater flow system influenced by marked tides. FVPDM tests were undertaken continuously for more than 48 h at six groundwater monitoring wells, in order to evaluate groundwater flow dynamics during several tide cycles. Contaminant concentrations were measured simultaneously which allowed calculating contaminant mass fluxes. The study highlighted the importance of the aquifer heterogeneity, with groundwater fluxes ranging from 10⁻⁷ to 10⁻³ m/s. Groundwater flux monitoring enabled a significant refinement of the conceptual site model, including the fact that inversion of groundwater fluxes was not observed at high tide. Results indicated that contaminant mass fluxes were particularly higher at a specific monitoring well, by more than three orders of magnitude, than at other wells of the investigated aquifer. This study provided crucial information for optimizing further field investigations and risk mitigation measures.     

Characterization and identification of na-cl sources in ground water

Elevated concentrations of sodium (Na+) and chloride (Cl-) in surface and ground water are common in the United States and other countries, and can serve as indicators of, or may constitute, a water quality problem. We have characterized the most prevalent natural and anthropogenic sources of Na+ and Cl- in ground water, primarily in Illinois, and explored techniques that could be used to identify their source. We considered seven potential sources that included agricultural chemicals, septic effluent, animal waste, municipal landfill leachate, sea water, basin brines, and road deicers. The halides Cl-, bromide (Br), and iodide (I) were useful indicators of the sources of Na+-Cl- contamination. Iodide enrichment (relative to Cl-) was greatest in precipitation, followed by uncontaminated soil water and ground water, and landfill leachate. The mass ratios of the halides among themselves, with total nitrogen (N), and with Na+ provided diagnostic methods for graphically distinguishing among sources of Na+ and Cl- in contaminated water. Cl/Br ratios relative to Cl- revealed a clear, although overlapping, separation of sample groups. Samples of landfill leachate and ground water known to be contaminated by leachate were enriched in I and Br; this provided an excellent fingerprint for identifying leachate contamination. In addition, total N, when plotted against Cl/Br ratios, successfully separated water contaminated by road salt from water contaminated by other sources.     

Effect of Temporal Changes in Air Injection Rate on Air Sparging Performance Groundwater Remediation

Air sparging (AS) is a commonly applied method for treating groundwater contaminated with volatile organic compounds (VOCs). When using a constant injection of air (continuous mode), a decline in remediation efficiency is often observed, resulting from insufficient mixing of contaminants at the pore scale. It is well known that turning the injection on and off (pulsed mode) may lead to a better remediation performance. In this article, we investigate groundwater mixing and contaminant removal efficiency in different injection modes (i.e., continuous and pulsed), and compare them to those achieved in a third mode, which we denote as “rate changing.” In this mode, injection is always on, and its rate is varying with time by abrupt changes. For the purpose of this investigation, we conducted two separate sets of experiments in a laboratory tank. In the first set of experiments, we used dye plume tracing to characterize the mixing induced by AS. In the second set of experiments, we contaminated the tank with a VOC and compared the remediation efficiency between the different injection modes. As expected, we observed that time‐variable injection modes led to enhanced mixing and contaminant removal. The decrease in contaminant concentrations during the experiment was found to be double for the “rate changing” and “pulsed” modes compared to the continuous mode, with a slightly preferable performance for the “rate changing” mode. These results highlight the critical role that mixing plays in AS, and support the need for further investigation of the proposed “rate changing” injection mode.     

Utilizing Natural Liner Materials for Heavy Metal Removal in Simulated Landfill Conditions

Inorganic industrial waste landfills have the potential to contaminate subsurface groundwater supplies through migration of leachates down to the water table and into groundwater aquifers, despite the use of compacted low permeability clay or polyethene liners. This paper aims the removal of Cu²⁺ and Zn²⁺ in the leachate from an industrial waste landfill using natural materials (natural zeolite, expanded vermiculite, pumice, illite, kaolinite, and bentonite) as a liner material. Cu²⁺ and Zn²⁺ concentrations for all treatments decreased during the process. Of all the different natural materials, natural zeolite, expanded vermiculite and pumice, with bentonite, were effective in removing Cu²⁺ and Zn²⁺ present in the leachate. However, the use of illite and kaolinite with bentonite as liner materials could be of disadvantage in Cu²⁺ and Zn²⁺ removal from leachate. The adsorption kinetic models were also tested for the validity. The second order kinetics with the high correlation coefficients best described adsorption kinetic data.     

基于水文-地球物理模型的地下水污染磁电阻率异常动态监测仿真

We present a forward-modeling investigation of time-dependent ground magnetometric resistivity （MMR） anomalies associated with transient leachate transport in groundwater systems. Numerical geo-electrical models are constructed based on the hydrological simulation results of leachate plumes from a highly conceptualized landfill system and the resultant MMR responses are computed using a modified finite difference software MMR2DFD. Three transmitter configurations （i.e., single source, MMR-TE, and MMR-TM modes） and two hydrological models （i.e., uniform and faulted porous media） are considered. Our forward modeling results for the uniform porous medium indicates that the magnetic field components perpendicular to the dominant current flow contain the most information of the underground targets and the MMR-TE mode is an appropriate configuration for detecting contaminant plumes. The modeling experiments for the faulted porous medium also confirm that the MMR method is capable of mapping and monitoring the extent of contaminant plumes in aroundwater systems.     

Biogeochemical evolution of a landfill leachate plume, Norman, Oklahoma

Leachate from municipal landfills can create groundwater contaminant plumes that may last for decades to centuries. The fate of reactive contaminants in leachate-affected aquifers depends on the sustainability of biogeochemical processes affecting contaminant transport. Temporal variations in the configuration of redox zones downgradient from the Norman Landfill were studied for more than a decade. The leachate plume contained elevated concentrations of nonvolatile dissolved organic carbon (NVDOC) (up to 300 mg/L), methane (16 mg/L), ammonium (650 mg/L as N), iron (23 mg/L), chloride (1030 mg/L), and bicarbonate (4270 mg/L). Chemical and isotopic investigations along a 2D plume transect revealed consumption of solid and aqueous electron acceptors in the aquifer, depleting the natural attenuation capacity. Despite the relative recalcitrance of NVDOC to biodegradation, the center of the plume was depleted in sulfate, which reduces the long-term oxidation capacity of the leachate-affected aquifer. Ammonium and methane were attenuated in the aquifer relative to chloride by different processes: ammonium transport was retarded mainly by physical interaction with aquifer solids, whereas the methane plume was truncated largely by oxidation. Studies near plume boundaries revealed temporal variability in constituent concentrations related in part to hydrologic changes at various time scales. The upper boundary of the plume was a particularly active location where redox reactions responded to recharge events and seasonal water-table fluctuations. Accurately describing the biogeochemical processes that affect the transport of contaminants in this landfill-leachate-affected aquifer required understanding the aquifer's geologic and hydrodynamic framework.     

Seasonal cycles of dissolved constituents in streamwater in two forested catchments in the mid-Atlantic region of the eastern USA

Streamwater discharge and chemistry of two small catchments on Catoctin Mountain in north-central Maryland have been monitored since 1982. Repetitive seasonal cycles in stream-water chemistry have been observed each year, along with seasonal cycles in the volume of stream discharge and in groundwater levels. The hypothesis that the observed streamwater chemical cycles are related to seasonal changes in the hydrological flow paths that contribute to streamflow is examined using a combination of data on groundwater levels, shallow and deep groundwater chemistry, streamwater discharge, streamwater chemistry, soil-water chemistry, and estimates of water residence times. The concentrations of constituents derived from rock weathering, particularly bicarbonate and silica, increase in streamwater during the summer when the water table is below the regolith-bedrock interface and stream discharge consists primarily of deep groundwater from the fractured-bedrock aquifer. Conversely, the concentrations in streamwater of atmospherically derived components, particularly sulfate, increase in winter when the water table is above the regolith-bedrock interface and stream discharge consists primarily of shallow groundwater from the regolith. Tritium and chlorofluorocarbon (CFC) measurements suggest that the groundwater in these systems is young, with a residence time of less than several years. The results of this study have implications for the design of large-scale water-quality monitoring programs.     

Effects of bedrock groundwater discharge on spatial variability of dissolved carbon,nitrogen, and phosphorous concentrations in stream water within a forest headwater catchment

The quantitative evaluation of the effects of bedrock groundwater discharge on spatial variability of stream dissolved organic carbon (DOC), dissolved inorganic nitrogen (DIN) and dissolved inorganic phosphorous (DIP) concentrations has still been insufficient. We examined the relationships between stream DOC, DIN and DIP concentrations and bedrock groundwater contribution to stream water in forest headwater catchments in warm-humid climate zones. We sampled stream water and bedrock springs at multiple points in September and December 2013 in a 5 km² forest headwater catchment in Japan and sampled groundwater in soil layer in small hillslopes. We assumed that stream water consisted of four end members, groundwater in soil layer and three types of bedrock groundwater, and calculated the contributions of each end member to stream water from mineral-derived solute concentrations. DOC, DIN and DIP concentrations in stream water were compared with the calculated bedrock groundwater contribution. The bedrock groundwater contribution had significant negative linear correlation with stream DOC concentration, no significant correlation with stream DIN concentration, and significant positive linear correlation with stream DIP concentration. These results highlighted the importance of bedrock groundwater discharge in establishing stream DOC and DIP concentrations. In addition, stream DOC and DIP concentrations were higher and lower, respectively, than those expected from end member mixing of groundwater in soil layer and bedrock springs. Spatial heterogeneity of DOC and DIP concentrations in groundwater and/or in-stream DOC production and DIP uptake were the probable reasons for these discrepancies. Our results indicate that the relationships between spatial variability of stream DOC, DIN and DIP concentrations and bedrock groundwater contribution are useful for comparing the processes that affect stream DOC, DIN and DIP concentrations among catchments beyond the spatial heterogeneity of hydrological and biogeochemical processes within a catchment.     

Groundwater-derived contaminant fluxes along a channelized Coastal Plain stream

Recent studies in various settings across eastern North America have examined the movement of volatile organic compound (VOC) plumes from groundwater to streams, but few studies have addressed focused discharge of such plumes in unlithified sediments. From 1999 through 2002, we monitored concentrations of trichloroethene (TCE) and the non-volatile co-contaminant technetium-99 (⁹⁹Tc) along Little Bayou Creek, a first-order perennial stream in the Coastal Plain of western Kentucky. Spring flow contributed TCE and ⁹⁹Tc to the creek, and TCE concentrations tended to vary with ⁹⁹Tc in springs. Contaminant concentrations in stream water fluctuated seasonally, but not always synchronously with stream flow. However, contaminant influxes varied seasonally with stream flow and were dominated by a few springs. Concentrations of O₂, , and , values of δ³⁷Cl_DOCl in groundwater, and the lack of less-chlorinated ethenes in groundwater and stream water indicated that anaerobic biodegradation of TCE was unlikely. Losses of TCE along Little Bayou Creek resulted mainly from volatilization, in contrast to streams receiving diffuse contaminated discharge, where intrinsic bioremediation of VOCs appears to be prevalent.     

Natural attenuation of volatile organic compounds (VOCs) in the leachate plume of a municipal landfill: using alkylbenzenes as process probes

More than 70 individual VOCs were identified in the leachate plume of a closed municipal landfill. Concentrations were low when compared with data published for other landfills, and total VOCs accounted for less than 0.1% of the total dissolved organic carbon. The VOC concentrations in the core of the anoxic leachate plume are variable, but in all cases they were found to be near or below detection limits within 200 m of the landfill. In contrast to the VOCs, the distributions of chloride ion, a conservative tracer, and nonvolatile dissolved organic carbon, indicate little dilution over the same distance. Thus, natural attenuation processes are effectively limiting migration of the VOC plume. The distribution of C2-3-benzenes, paired on the basis of their octanol-water partition coefficients and Henry's law constants, were systematically evaluated to assess the relative importance of volatilization, sorption, and biodegradation as attenuation mechanisms. Based on our data, biodegradation appears to be the process primarily responsible for the observed attenuation of VOCs at this site. We believe that the alkylbenzenes are powerful process probes that can and should be exploited in studies of natural attenuation in contaminated ground water systems.