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.     

The Geochemistry of Boron in a Landfill Monitoring Program

Ground water monitoring data collected during the past eight years at a permitted municipal solid waste (MSW) disposal facility located in the midwestern United States indicated fluctuations in typical leachate indicator parameter concentrations. Apparent trends in the data inferred leachate outbreak, generating suspicion as to the integrity of the landfill liner. Eight ground water monitoring wells were installed in three distinct geologic units at the landfill facility, including glacial drift, silurian dolomite, and a post-glacial peat fen, which is downgradient from the landfill. Piezometer nests were used to define ground water gradients at the site. Using boron as an indicator, the occurrence of analytes of concern in the downgradient monitoring wells were shown to be indicative of the natural geochemistry of site ground water. This work emphasizes the importance of understanding site hydrogeology during the interpretation of ground water quality data.     

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.     

Subsurface Transport of Inorganic and Organic Solutes from Experimental Road Spreading of Oil-Field Brine

A study designed to evaluate ground water quality changes resulting from spreading oil-field brine on roads for ice and dust control was conducted using a gravel roadbed that received weekly applications of brine eight times during the winter phase and 11 times during the summer phase of the study. A network of 11 monitoring wells and five pressure-vacuum lysimeters was installed to obtain ground water and soil water samples. Thirteen sets of water- quality samples were collected and analyzed for major ions, trace metals, and volatile organic compounds. Two sets of samples were taken prior to brine spreading, four sets during winter-phase spreading, five sets during summer- phase spreading, and two sets during the interim between the winter and summer phases. A brine plume delineated by elevated specific-conductance values and elevated chloride concentrations developed downgradient of the roadbed during both the winter and summer phases. The brine plume caused chloride concentrations in ground water samples to exceed U.S. EPA public drinking-water standards by two-fold during the winter phase and five-fold during the summer phase. No other major ions, trace metals, or volatile organic compounds exceeded the standards during the winter or summer phases. More than 99 percent dilution of the solutes in the brine occurred between the roadbed surface and the local ground water flow system. Further attenuation of calcium, sodium, potassium, and strontium resulted from adsorption, whereas further attenuation of benzene resulted from volatilization and adsorption.     

The Detection of Naturally Occurring BTX During a Hydrogeologic Investigation

Benzene, toluene and xylenes (BTX) were detected in ground water during a contaminant hydrogeological investigation of a landfill site. The landfill site was situated on approximately 10m (33 ft) of clay and glacial till overburden soils, which were underlain by a shaly limestone bedrock. The top part of the bedrock was the regional aquifer in the study area. Initial thoughts were that the landfill was the source of the BTX. However, the BTX was detected in ground water a considerable distance from the known extent of the leachate plume. Subsequent detailed analysis of rock cores showed the BTX could be leached from bituminous layers of shale that were interbedded in limestone. Rock core testing included gas chromatograph (GC) analysis of organic free reagent water used for leaching tests, flame ionization detection on a solvent used for leaching tests and thermal desorption analysis of the solid rock. The naturally occurring BTX, along with the presence of brackish ground water in the shaly bedrock, made it difficult to identify ground water contamination emanating from the landfill. Thus, the presence of BTX should not be considered definitive evidence of ground water contamination in certain sedimentary rock aquifers.     

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.     

Detection of Contaminant Plumes by Borehole Geophysical Logging

Two borehole geophysical methods—electromagnetic induction and natural gamma radiation logs—were used to vertically delineate landfill leachate plumes in a glacial aquifer. Geophysical logs of monitoring wells near two land-fills in a glacial aquifer in west-central Vermont show that borehole geophysical methods can aid in interpretation of geologic logs and placement of monitoring well screens to sample landfill leachate plumes.
Zones of high electrical conductance were delineated from the electromagnetic log in wells near two landfills. Some of these zones were found to correlate with silt and clay units on the basis of drilling and gamma logs. Monitoring wells were screened specifically in zones of high electrical conductivity that did not correlate to a silt or clay unit. Zones of high electrical conductivity that did not correlate to a silt or clay unit were caused by the presence of ground water with a high specific conductance, generally from 1000 to 2370 μS/cm (microsiemens per centimeter at 25 degrees Celsius). Ambient ground water in the study area has a specific conductance of approximately 200 to 400 μS/cm. Landfill leachate plumes were found to be approximately 5 to 20 feet thick and to be near the water table surface.     

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.     

Cone Penetrometer Tests and HydroPunch® Sampling: A Screening Technique for Plume Definition

Cone penetrometer tests and HydroPunch® sampling were used to define the extent of volatile organic compounds in ground water. The investigation indicated that the combination of these techniques is effective for obtaining ground water samples for preliminary plume definition. HydroPunch samples can be collected in unconsolidated sediments and the analytical results obtained from these samples are comparable to those obtained from adjacent monitoring wells. This sampling method is a rapid and cost-effective screening technique for characterizing the extent of contaminant plumes in soft sediment environments. Use of this screening technique allowed monitoring wells to be located at the plume boundary, thereby reducing the number of wells installed and the overall cost of the plume definition program.     

Utilization of Shallow Geophysical Sensing at Two Abandoned Municipal/Industrial Waste Landfills on the Missouri River Floodplain

In the past 30 to 40 years, floodplain areas of large rivers, such as the Missouri River, have been extensively used for large industrial and municipal landfills. Many of these sites are now causing varying degrees of ground water contamination. Rapid geophysical characterization techniques have proven useful for delineation of anomalous areas indicative of potential contaminant plumes. These methods have also resulted in a cost effective approach to the location and number of monitoring wells.
An effective technique to initially characterize ground water contamination at such landfills along the Missouri River in northwestern Missouri involved a combination of electrical resistivity and electromagnetic conductivity methods. Resistivity was used to obtain soundings of the alluvium by using a modified Wenner array and to corroborate shallow electromagnetic conductivity measurements by using short Wenner array electrode spacings.
Upon confirmation of similar measurements of the upper soils for the two methods, numerous electromagnetic conductivity traverses were made at each landfill site. The data generated from these surveys were graphed and contoured to delineate anomalous areas. Based on the geophysical study, a ground water monitoring well network was then designed for each landfill.
As a result, a minimal number of wells were required to initially characterize the ground water quality at these two sites. In general, analysis of water samples from these wells displayed good correlation with the geophysical results.     

The use of GPR and VES in delineating a contamination plume in a landfill site: a case study in SE Brazil

This paper presents the results of the application of the Ground Penetrating Radar (GPR) method, or Georadar, in outlining a zone of contamination due to solid residues at the waste burial site of Rio Claro in the state of São Paulo, SE Brazil. A total of eight GPR profiles with 50- and 100-MHz antennae were surveyed. Six profiles were located within the landfill site and the remaining two were outside. The main objective of the GPR survey was to evaluate the side extension of contamination. A Vertical Electric Sounding (VES) survey was performed at four points within the site in order to investigate the vertical extent of the contamination plume and to define the bottom of the landfill. Two additional VESs were done outside the landfill with the purpose of determining the top of the ground water table and the geoelectric stratigraphy of the background. From the interpretation of the GPR profiles, it was possible to locate the top of the contamination plume and to infer that it was migrating laterally beyond the limits of the waste disposal site. This was observed along the profile situated close to the highway SP-127, which was about 20 m from the limit of the site. The signature of the contaminant appears as a discontinuous reflector that is believed to be a shallow ground water table. The discontinuity is marked by a shadow zone, which is characteristic of conductive contaminant residues. The contamination did not move far enough to reach a sugar cane plantation located at approximately 100 m from the border of the site. In the regions free from contamination, the ground water table was mapped at approximately 10 m of depth, and it was characterized by a strong and continuous reflector. The radar signal penetrated deep enough and enabled the identification of a second reflector at approximately 14 m deep, interpreted as the contact between the Rio Claro and the Corumbataí formations. The contact is marked by the presence of gravel characterized by ferruginous concretes, which cause the strong amplitude reflection in the GPR profile. Within the landfill site, the quantitative interpretation of the VES results showed the contamination zone. The base of the landfill varies between 11 and 15 m deep. Outside the landfill site, the VES results showed no indication of contamination and allowed the determination of the top of the ground water table and the contact between the Rio Claro and the Corumbataí formations. The results of GPR and VES showed a good agreement and the integrated interpretations were supported by local geology and information from several boreholes, about 17 m depth, on average. The bottom of the landfill reaches a maximum of 14.5 m depth.     

The Disposable E-Log

A device was developed to make fine-scale in situ measurements of formation and ground water conductivity at depths up to 10 meters in unconsolidated shallow aquifers. It consists of a casing that is left in place ("disposable") and a probe that slides down the center of the casing making readings or taking water samples through screened slots. The device is inexpensive, designed to be jetted into place, and intended for use in monitoring situations where drilling rigs and wireline logs are impractical. It offers, in principle, 10cm resolution of the conductivities and the formation factor as a function of time.
Results from three of these units installed across a landfill plume near North Bay, Ontario, demonstrate the usefulness of these kinds of measurements in a monitoring study, and the problems that can be encountered in a highly contaminated environment.     

The Application of a Statistical Trend Analysis Model to Ground Water Monitoring Data from Solid Waste Landfills

A statistical trend methodology is used to compare ground water quality between eight landfill sites in western Michigan as a case study. Monitoring data were collected over a 15-year period on 36 parameters at an upgradient and downgradient well selected at each of the eight sites. This yielded a total of 576 monitoring data sets available for analysis. New trend and contamination indices are introduced that are used to compare ground water contamination between these eight sites. These indices are used to assess each landfill's relative potential for environmental harm.
Many questions remain unanswered, but what is demonstrated here is that this type of methodology has the potential to be used to assess trends of ground water chemistry concentrations at landfill sues in a region. A specific purpose of such an assessment could be to provide a quantified basis for the prioritization of funds allocated for cleanup of contaminated landfill sites. Having a technical capability to reduce large amounts of ground water monitoring data to appropriate summaries, which then can be used to assess environmental contamination between several sites, could also have important economic and health implications in other settings. Hopefully this paper will encourage further development of such technologies for these purposes.     

Ground water discharge and nitrate flux to the Gulf of Mexico

Ground water samples (37 to 186 m depth) from Baldwin County, Alabama, are used to define the hydrogeology of Gulf coastal aquifers and calculate the subsurface discharge of nutrients to the Gulf of Mexico. The ground water flow and nitrate flux have been determined by linking ground water concentrations to 3H/3He and 4He age dates. The middle aquifer (A2) is an active flow system characterized by postnuclear tritium levels, moderate vertical velocities, and high nitrate concentrations. Ground water discharge could be an unaccounted source for nutrients in the coastal oceans. The aquifers annually discharge 1.1 +/- 0.01 x 10(8) moles of nitrate to the Gulf of Mexico, or 50% and 0.8% of the annual contributions from the Mobile-Alabama River System and the Mississippi River System, respectively. In southern Baldwin County, south of Loxley, increasing reliance on ground water in the deeper A3 aquifer requires accurate estimates of safe ground water withdrawal. This aquifer, partially confined by Pliocene clay above and Pensacola Clay below, is tritium dead and contains elevated 4He concentrations with no nitrate and estimated ground water ages from 100 to 7000 years. The isotopic composition and concentration of natural gas diffusing from the Pensacola Clay into the A3 aquifer aids in defining the deep ground water discharge. The highest 4He and CH4 concentrations are found only in the deepest sample (Gulf State Park), indicating that ground water flow into the Gulf of Mexico suppresses the natural gas plume. Using the shape of the CH4-He plume and the accumulation of 4He rate (2.2 +/- 0.8 microcc/kg/1000 years), we estimate the natural submarine discharge and the replenishment rate for the A3 aquifer.     

Screened Auger Sampling: The Technique and Two Case Studies

The screened auger is a laser-slotted, hollow-stem auger through which a representative sample of ground water is pumped from an aquifer and tested for water-quality parameters by appropriate field-screening methods. Screened auger sampling can be applied to ground water quality remedial investigations, providing:(1) a mechanism for determining a monitoring well's optimal screen placement in a contaminant plume; and (2) data to define the three-dimensional configuration of the contaminant plume.
Screened auger sampling has provided an efficient method for investigating hexavalent chromium and volatile organic compound contamination in two sandy aquifers in Cadillac, Michigan. The aquifers approach 200 feet in thickness and more than 1 square mile in area. A series of screened auger borings and monitoring wells was installed, and ground water was collected at 10-foot intervals as the boreholes were advanced to define the horizontal and vertical distribution of the contaminant plumes. The ability of the screened auger to obtain representative ground water samples was supported by the statistical comparison of field screening results and subsequent laboratory analysis of ground water from installed monitoring wells.     

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.     

A Systematic Approach to Designing a Multiphase Unsaturated Zone Monitoring Network

A systematic approach is presented for the design of a multiphase vadose zone monitoring system recognizing that, as in ground water monitoring system design, complete subsurface coverage is not practical. The approach includes identification and prioritization of vulnerable areas: select ion of cost-effective indirect monitoring methods that will provide early warning of contaminant migration: selection of direct monitoring methods for diagnostic confirmation; identification of background monitoring locations; and identification of an appropriate temporal monitoring plan. An example of a monitoring system designed for a solid waste landfill is presented and utilized to illustrate the approach and provide details of system implementation. The example design described incorporates the use of neutron moisture probes deployed in both vertical and horizontal access tubes beneath the lcachate recovery collection system of the landfill. Early warning of gaseous phase contaminant migration is monitored utilizing whole-air active soil gas sampling points deployed in gravel- filled trenches beneath the subgrade. Diagnostic confirmation of contaminant migration is provided utilizing pore- liquid samplers. Conservative tracers can be used to distinguish between chemical species released by a landfill from those attributable to other (e.g. off-site) sources or present naturally in the subsurface. A discussion of background monitoring point location is also presented.     

Long-term changes in ground water chemistry at a phytoremediation demonstration site

A field-scale demonstration project was conducted to evaluate the capability of eastern cottonwood trees (Populus deltoides) to attenuate trichloroethene (TCE) contamination of ground water. By the middle of the sixth growing season, trees planted where depth to water was <3 m delivered enough dissolved organic carbon to the underlying aquifer to lower dissolved oxygen concentrations, to create iron-reducing conditions along the plume centerline and sulfate-reducing or methanogenic conditions in localized areas, and to initiate in situ reductive dechlorination of TCE. Apparent biodegradation rate constants for TCE along the centerline of the plume beneath the phytoremediation system increased from 0.0002/d to 0.02/d during the first six growing seasons. The corresponding increase in natural attenuation capacity of the aquifer along the plume centerline, from 0.0004/m to 0.024/m, is associated with a potential decrease in plume-stabilization distance from 9680 to 160 m. Demonstration results provide insight into the amount of vegetation and time that may be needed to achieve cleanup objectives at the field scale.     

Monitored Natural Attenuation of Manufactured Gas Plant Tar Mono- and Polycyclic Aromatic Hydrocarbons in Ground Water: A 14-Year Field Study

Site 24 was the subject of a 14-year (5110-day) study of a ground water plume created by the disposal of manufactured gas plant (MGP) tar into a shallow sandy aquifer approximately 25 years prior to the study. The ground water plume in 1988 extended from a well-defined source area to a distance of approximately 400 m down gradient. A system of monitoring wells was installed along six transects that ran perpendicular to the longitudinal axis of the plume centerline. The MGP tar source was removed from the site in 1991 and a 14-year ground water monitored natural attenuation (MNA) study commenced. The program measured the dissolved mono- and polycyclic aromatic hydrocarbons (MAHs and PAHs) periodically over time, which decreased significantly over the 14-year period. Naphthalene decreased to less than 99% of the original dissolved mass, with mass degradation rates of 0.30 per year (half-life 2.3 years). Bulk attenuation rate constants for plume centerline concentrations over time ranged from 0.33 ± 0.09 per year (half-life 2.3 ± 0.8 years) for toluene and 0.45 ± 0.06 per year (half-life 1.6 ± 0.2 years) for naphthalene. The hydrogeologic setting at Site 24, having a sandy aquifer, shallow water table, clay confining layer, and aerobic conditions, was ideal for demonstrating MNA. However, these results demonstrate that MNA is a viable remedial strategy for ground water at sites impacted by MAHs and PAHs after the original source is removed, stabilized, or contained.     

A Graphical Approach for Determining Dilution-Attenuation Factors: Basic Theory and Approach for Submerged Sources

The dilution attenuation factor (DAF) is a quantity used to relate the concentration of leachate leaving a source zone (e.g., landfill, impoundment, or contaminated soils) to its impact on down-gradient ground water quality. The DAF is of importance because it plays a key role in U.S. Environmental Protection Agency (EPA)'s methodologies for developing soil cleanup goals and for managing hazardous wastes. In this work, a simplistic graphically-based approach for determining site-specific and generic DAFs was developed. In this case the DAF is based on time-and vertically-averaged concentrations along the plume centerline, and the mathematical framework employs well-known analytical and semianalytical solutions for dissolved contaminant transport. Finite sources with a range of decay characteristics are allowed for. One unique feature of this work is that the graphical approach allows for varying levels of sitespecificity, and thus can be used when one has a little, or a lot, of site-specific information. The graphs visually indicate the sensitivity to various parameters, which is valuable information not easily gleaned from most numerical software simulators. This approach is, however, not applicable to very complex hydrogeologic settings (e.g., fractured geology), or to ground water flows that cannot be reasonably approximated as one-dimensional.