Natural Attenuation: A Feasible Approach to Remediation of Ground Water Pollution at Landfills?

Remediation of ground water pollution at old landfills with no engineered leachate collection system is a demanding and costly operation. It requires control of the landfill body, since the majority of the pollutants are still present in the landfilled waste for decades after the site has been closed. However removing the source is an attractive approach to managing leachate plumes. Natural attenuation has been implemented for petroleum hydrocarbon plumes and chorinated solvent plumes, primarily in the United States. Natural attenuation has not yet gained a foothold with respect to leachate plumes, however. Based on the experience gained from 10 years of research on two Danish landfills, it is suggested that natural attenuation is a feasible approach but is more complicated and demanding than in the case of petroleum hydrocarbons and chlorinated solvent.     

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.     

Emerging Contaminants at a Closed and an Operating Landfill in Oklahoma

Landfills are the final depositories for a wide range of solid waste from both residential and commercial sources, and therefore have the potential to produce leachate containing many organic compounds found in consumer products such as pharmaceuticals, plasticizers, disinfectants, cleaning agents, fire retardants, flavorings, and preservatives, known as emerging contaminants (ECs). Landfill leachate was sampled from landfill cells of three different age ranges from two landfills in Central Oklahoma. Samples were collected from an old cell containing solid waste greater than 25 years old, an intermediate age cell with solid waste between 16 and 3 years old, and operating cell with solid waste less than 5 years old to investigate the chemical variability and persistence of selected ECs in landfill leachate of differing age sources. Twenty‐eight of 69 analyzed ECs were detected in one or more samples from the three leachate sources. Detected ECs ranged in concentration from 0.11 to 114 μg/L and included 4 fecal and plant sterols, 13 household\industrial, 7 hydrocarbon, and 4 pesticide compounds. Four ECs were solely detected in the oldest leachate sample, two ECs were solely detected in the intermediate leachate sample, and no ECs were solely detected in the youngest leachate sample. Eleven ECs were commonly detected in all three leachate samples and are an indication of the contents of solid waste deposited over several decades and the relative resistance of some ECs to natural attenuation processes in and near landfills.     

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.     

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.     

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.     

Design of Lysimeter Leak Detector Networks for Surface Impoundments and Landfills

Sampling of soil pore moisture in the vadose zone underneath land disposal facilities (landfills and surface impoundments) for hazardous waste has been suggested as an "early warning system" to detect leakage from these facilities. Some states require vadose zone moisture sampling at such sites. Given a leak of a particular size, mathematical models can estimate the necessary moisture sample volume collection times and lysimeter spacings to guarantee detection of the leak in a homogeneous medium. Examination of 47 hazardous waste sites existing in 1984 indicated the most were located in areas with water tables too shallow to permit vadose zone detection monitoring. Several of the 47 sites had soils that could be described as loamy sand, silt loam or silty clay. Using these three soils as examples, the process of lysimeter leak-detector network design has been illustrated. For a particular loamy sand with a saturates hydraulic conductivity of 10^-6 cm/ sec, the maximum ceramic lysimeter spacing is 15.5 feet at a depth of 30 feet to collec a moisture sample of 10 mL in one week from a 1 ft2 leak. For a silt loam, maximum lysimeter spacing would be 17 feet at depth of 15 feet. For silty clays, the maximum lysimeter spacing is 7 feet at a depth of 2 feet; maximum emplacement depth is about 9 feet. Calculations show that in some soils, suction lysimeters will not be able to collect usable moisture samples. Since soil properties vary widely and lysimeter spacing is strongly dependent on soil-moisture characteristics appropriate soil measurements and modeling must be performed at each disposal facility to estimate lysimete performance and to select locations for emplacement.     

Statistical Comparison of Leachate from Hazardous, Codisposal, and Municipal Solid Waste Landfills

There has been considerable debate regarding the chemical characterization of landfill leachate in general and the comparison of various types of landfill leachate (e.g., hazardous, codisposal, and municipal) in particular. For example, the preamble to the U.S. EPA Subtitle D regulation (40 CFR Parts 257 and 258) suggests that there are no significant differences between the number and concentration of toxic constituents in hazardous versus municipal solid waste landfill leachate. The purpose of this paper is to statistically test this hypothesis in a large leachate database comprising 1490 leachate samples from 283 sample points (i.e., monitoring location such as a leachate sump) in 93 landfill waste cells (i.e., a section of a facility that took a specific waste slream or collection of similar waste streams) from 48 sites with municipal, codisposal, or hazardous waste site histories. Results of the analysis reveal clear differention between landfill leachate types, both in terms of constituents detected and their concentrations. The result of the analysis is a classification function that can estimate the probability that new leachate or ground water sample was produced by the disposal of municipal, codisposal, or hazardous waste. This type of computation is illustrated, and applications of the model to Superfund cost-allocation problems are discussed.     

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

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

Nitrogen Removal from Landfill Leachate Using an Infiltration Bed Coupled with a Denitrification Barrier

Treatment of nitrogen in landfill leachate has received considerable attention recently because of the relatively low levels at which some nitrogen species (i.e., NH3) can be toxic to aquatic life forms. This study reports on the results of a three-year, pilot-scale field trial demonstrating the use of infiltration bed and nitrate barrier technology to achieve nitrogen removal in landfill leachate. The infiltration bed comprises an unsaturated sand layer overlying a saturated layer of waste cellulose solids (sawdust), which acts as a carbon source for heterotrophic denitrification. When loaded at a rate of 1 to 3 cm/day, the infiltration bed was successful at lowering leachate inorganic nitrogen (NH₄⁺+ NO₃^-) levels averaging 24.8 mg/L N by 89%, including 96% in the third year of operation. The surface water discharge criteria for un-ionized ammonia (NH3) were met on all occasions in the treated leachate during the second and third years of operation. Nitrogen attenuation is presumed to occur by a two-step process in which leachate NH₄⁺ is first oxidized to NO₃^- in the unsaturated sand layer and then is converted to nitrogen gas (N₂) by denitrification occurring in the underlying sawdust layer. Mass balance calculations suggest that the sawdust layer has sufficient carbon to allow denitrification to proceed for long periods (1.0 to 30 years) without replenishment. Because this technology is simple to construct and is relatively maintenance free, it should be attractive for use at smaller landfills where the installation of conventional treatment plants may not be feasible.     

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.     

A Risk-Based Approach for Managing Hazardous Waste

In 1992, the U.S. Environmental Protection Agency (EPA) proposed risk-based management of hazardous waste. A major component of the proposed rule is the determination of non-site- specific screening concentration levels from waste leachate. Ground water at a downgradient exposure point must not exceed those screening levels, or more stringent requirements would apply.
The screening concentration level is determined with verified models and equations that simulate the transport and attenuation of chemicals as they travel from the source area to the exposure point. A consortium of screening levels is determined in this paper by considering varying physical, chemical, and biological conditions. In addition, a method is developed for multi component leaching from contaminated soils in a landfill to determine the time-dependent behavior of a finite source. Finally, this paper discusses infiltration rate through the clay liner.     

Mass and flux distributions from DNAPL zones in sandy aquifers

At three industrial sites in Ontario, New Hampshire, and Florida, tetrachloroethylene (PCE) and trichloroethylene (TCE), released decades ago as dense nonaqueous phase liquids (DNAPLs), now form persistent source zones for dissolved contaminant plumes. These zones are suspended below the water table and above the bottoms of their respective, moderately homogeneous, unconfined sandy aquifers. Exceptionally detailed, depth-discrete, ground water sampling was performed using a direct-push sampler along cross sections of the dissolved-phase plumes, immediately downgradient of these DNAPL source zones. The total plume PCE or TCE mass-discharge through each cross section ranged between 15 and 31 kg/year. Vertical ground water sample spacing as small as 15 cm and lateral spacing typically between 1 and 3 m revealed small zones where maximum concentrations were between 1% and 61% of solubility. These local maxima are surrounded by much lower concentration zones. A spacing no larger than 15 to 30 cm was needed at some locations to identify high concentration zones, and aqueous VOC concentrations varied as much as four orders of magnitude across 30 cm vertical intervals. High-resolution sampling at these sites showed that three-quarters of the mass-discharge occurs within 5% to 10% of the plume cross sectional areas. The extreme spatial variability of the mass-discharge occurs even though the sand aquifers are nearly hydraulically homogeneous. Depth-discrete field techniques such as those used in this study are essential for finding the small zones producing most of the mass-discharge, which is important for assessing natural attenuation and designing remedial options.     

Pharmaceuticals and Other Organic Waste Water Contaminants Within a Leachate Plume Downgradient of a Municipal Landfill

Ground water samples collected from the Norman Landfill research site in central Oklahoma were analyzed as part of the U.S. Geological Survey (USGS) Toxic Substances Hydrology Program's national reconnaissance of pharmaceuticals and other organic waste water contaminants (OWCs) in ground water. Five sites, four of which are located downgradient of the landfill, were sampled in 2000 and analyzed for 76 OWCs using four research methods developed by the USGS. OWCs were detected in water samples from all of the sites sampled, with 22 of the 76 OWCs being detected at least once. Cholesterol (a plant and animal steroid), was detected at all five sites and was the only compound detected in a well upgradient of the landfill. N,N-diethyltoluamide (DEBT used in insect repellent) and tri(2-chloroethyl) phosphate (fire-retardant) were detected in water samples from all four sites located within the landfill-derived leachate plume. The sites closest to the landfill had more detections and greater concentrations of each of the detected compounds than sites located farther away. Detection of multiple OWCs occurred in the four sites located within the leachate plume, with a minimum of four and a maximum of 17 OWCs detected. Because the landfill was established in the 1920s and closed in 1985, many compounds detected in the leachate plume were likely disposed of decades ago. These results indicate the potential for long-term persistence and transport of some OWCs in ground water.     

Artificial Sweeteners Identify Spatial Patterns of Historic Landfill Contaminated Groundwater Discharge in an Urban Stream

Leachate-contaminated groundwater from historical municipal landfills, typically lacking engineered liners and leachate collection systems, poses a threat to nearby urban streams, particularly to benthic ecosystems. Effective monitoring and assessment of such sites requires understanding of the spatial patterns (i.e., two-dimensional footprint) of contaminated groundwater discharge and associated controlling factors. However, discharges from groundwater contaminated by modern wastewater can complicate site assessments. The objectives of this study were to (1) demonstrate the use of artificial sweeteners (AS): saccharin (SAC), cyclamate (CYC), acesulfame (ACE), and sucralose (SUC), to distinguish groundwater discharge areas influenced by historic landfill leachate (elevated SAC and sometimes CYC; low ACE and SUC concentrations) from those influenced by wastewater (high ACE and SUC concentrations), and (2) investigate contaminant discharge patterns for two gaining urban stream reaches adjacent historic landfills at base flows. Contaminant discharge patterns revealed by the AS were strongly controlled by hyporheic flow (low AS concentrations), particularly for the straight reach, and stream sinuosity, particularly for the meandering reach. These patterns were different and the contaminant footprint coverage (<25% of streambed area) much less than most past studies (typically >50% coverage), likely due to the homogeneous streambed-aquifer conditions and shallow, narrow landfill plume in this setting.     

Using a Simple Soil Column Method to Evaluate Soil Phosphorus Leaching Risk

The impacts of soil P leaching on water eutrophication have widely been concerned. However, there is no dependable method to quantitatively estimate the P leaching risk of soils. In this study, a simple soil column method was developed using two calcareous Fluvisols, silt loam and loam. The soil column was 20 cm in length and 5 cm in diameter, and distilled water was continuously supplied from the top. The volume and dissolved reactive P (DRP) concentrations of leachate were measured. Results showed that DRP concentrations in leachate increased slowly for the low soil Olsen‐P levels but rapidly for the high Olsen‐P levels. According to these two‐phase changes in the DRP versus soil Olsen‐P contents, the thresholds of P leaching risk were estimated to be 41.1 and 62.3 mg P kg^?1 (Olsen‐P) for silt loam and loam, respectively. The P leaching intensity of soils increased by 3‐ to 540‐fold if the soil Olsen‐P contents accumulated from 6.6 to 155.5 mg P kg^?1. The outcomes derived from this study regarding the determination of P leaching threshold and intensity by the soil column method also need a further verification on more soils with a wide range of physical and chemical properties.     

Soil water movement and nutrient cycling in semi-arid rangeland: vegetation change and system resilience

Recent decades have seen rapid intensification of cattle production in semi-arid savannah ecosystems, increasingly on formalized ranch blocks. As a result, vegetation community changes have occurred, notably bush encroachment (increased bush dominance) in intensively grazed areas. The exact causes of this vegetation change remain widely debated. Previous studies have suggested: (i) increased leaching of water and nutrients into the subsoil in intensively grazed areas provides deeper rooting bush species with a competitive advantage for soil water and nutrients, and (ii) nutrient leaching may be exacerbated by nutrient inputs from cattle dung and urine. Our research in the Eastern Kalahari showed that in infertile sandy soils both the magnitude of soil water and concentration of soil nutrients leached into the subsoil is largely unaffected by the ecological and biochemical effects of increased cattle use. We found that despite the high soil hydraulic conductivity ( &greaterno;12 cm h⁻¹), relatively high subsoil moisture contents and the restriction of water movement to matrix flow pathways prevent leaching losses beyond the rooting zone of savannah grass species. No significant differences in patterns of soil water redistribution were noted between bush dominant and grass dominant sites. We also found that the low nutrient status of Kalahari soils and leachate movement as matrix flow combine to allow nutrient adsorption on to soil particles. Nutrient adsorption ensures that nitrogen and phosphorus cycling remains topsoil dominated even following the removal of vegetation and direct nutrient inputs in cattle dung and urine. This conclusion refutes environmental change models that portray increases in the leaching of soil water and available nitrogen as a major factor causing bush encroachment. This provides a possible explanation for the now widely cited, but hitherto unexplained, resilience of dryland soils. We suggest that infertile sandy soils appear resilient to changes in soil water distribution and nutrient availability caused by increased cattle use. Hence, soil characteristics contribute to the resilience to permanent ecological change that is increasingly recognized as an attribute of semi-arid rangelands. © 1998 John Wiley & Sons, Ltd.     

Characterization of a dismissed landfill via electrical resistivity tomography and mise-à-la-masse method

Electrical resistivity methods are widely used for environmental applications, and they are particularly useful for the characterization and monitoring of sites where the presence of contamination requires a thorough understanding of the location and movement of water, that can act as a carrier of solutes. One such application is landfill studies, where the strong electrical contrasts between waste, leachate and surrounding formations make electrical methods a nearly ideal tool for investigation. In spite of the advantages, however, electrical investigation of landfills poses also challenges, both logistical and interpretational. This paper presents the results of a study conducted on a dismissed landfill, close to the city of Corigliano d'Otranto, in the Apulia region (Southern Italy). The landfill is located in an abandoned quarry, that was subsequently re-utilized about thirty years ago as a site for urban waste disposal. The waste was thought to be more than 20 m thick, and the landfill bottom was expected to be confined with an HDPE (high-density poli-ethylene) liner. During the digging operations performed to build a nearby new landfill, leachate was found, triggering an in-depth investigation including also non-invasive methods. The principal goal was to verify whether the leachate is indeed confined, and to what extent, by the HDPE liner. We performed both surface electrical resistivity tomography (ERT) and mise-à-la-masse (MALM) surveys, facing the severe challenges posed by the rugged terrain of the abandoned quarry complex. A conductive body, probably associated with leachate, was found as deep as 40 m below the current landfill surface i.e. at a depth much larger than the expected 20 m thickness of waste. Given the logistical difficulties that limit the geometry of acquisition, we utilized synthetic forward modeling in order to confirm/dismiss interpretational hypotheses emerging from the ERT and MALM results. This integration between measurements and modeling helped narrow the alternative interpretations and strengthened the confidence in results, confirming the effectiveness of non-invasive methods in landfill investigation and the importance of modeling in the interpretation of geophysical results.     

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.