High-Resolution Characterization of a Chlorinated Solvent Impacted Aquifer Using a Passive Profiler

A direct-drive high-resolution passive profiler (HRPP) was developed to quantify and delineate concentrations of chlorinated volatile organic compounds (CVOCs), geochemical indicators and CVOC-degrading microorganisms/genes, as well as to perform compound-specific stable isotope analysis (CSIA) of CVOCs and estimate interstitial velocity at <30-cm resolution. The profilers can be coupled together to provide a continuous sample interval and advanced to depths up to approximately 9 m below-ground surface (bgs) within saturated media where direct-push techniques are feasible. The HRPP was field tested in a previous dense nonaqueous phase liquid (DNAPL) source zone at the former Naval Air Station in Alameda, CA. HRPP data sets were compared to the following traditional groundwater data sets: CVOC and anion concentrations in standard and multilevel monitoring well water samples, CVOC concentrations in soil core samples, qualitative contaminant profiles delineated with a membrane interface probe (MIP), microbial community and CSIA profiles from Bio-Traps® deployed in wells, groundwater velocity from passive flux meters (PFMs), lithologic profiles correlated with MIP electrical conductivity (EC), and velocity estimates based on permeability profiles measured with a Geoprobe hydraulic profiling tool (HPT). In some cases, the HRPP data were equivalent to traditional techniques and, in other cases, the HRPP data were more representative of local variability rather than bulk aquifer conditions. Overall the results support the use of the HRPP to provide high-resolution data on concentrations, velocity, and microbial activity in temporary direct-push deployments without well installation, providing a new tool to better assess source zones and contaminated groundwater plumes, even in low permeability media, and to increase the fidelity of site transport models.     

Empirical Assessment of Ground Water–to-Indoor Air Attenuation Factors for the CDOT-MTL Denver Site

The area surrounding the Colorado Department of Transportation Materials Testing Laboratory in Denver was the subject of intense investigation, involving the collection of thousands of ground water, soil-gas, and indoor air samples in order to investigate indoor air impacts associated with a subsurface release of chlorinated solvents. The preremediation portion of that data set is analyzed and reduced in this work to ground water–to-indoor air attenuation factors (α_gw= the ratio of the measured indoor air concentration to the soil-gas concentration predicted to be in equilibrium with the local ground water concentration). The empirical α_gw values for this site range from about 10⁻⁶ to 10⁻⁴ with an overall average of 3 × 10⁻⁵ (μg/L indoor air)/(μg/L soil gas). The analysis of this data set highlights the need for a thorough data review and data screening when using large data sets to derive empirical relationships between subsurface concentrations and indoor air. More specifically, it is necessary to identify those parts of the data that contain a strong vapor intrusion pathway signal, which generally will require concentrations well above reported detection levels combined with spatial or temporal correlation of subsurface and indoor concentrations.     

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.     

Development and Testing of a Field Screening Method Based on Bubbling Extraction and Photoionization Detection for Measurement of Benzene and Total VOCs

A field screening method was developed for rapid measurement of benzene and gasoline range total petroleum hydrocarbons (TPHg) concentrations in groundwater. The method is based on collecting photoionization detector (PID) measurements from vapor samples. The vapor samples are collected by bubbling air through groundwater samples (air sparging) with a constant volume, temperature and sparging rate. The level of accuracy, sensitivity, precision, and statistical significance of the estimated concentrations, derived from the screening method, are comparable to conventional laboratory analytical results at concentrations equal to or greater than 150 µg/L for benzene and greater than 50 µg/L for TPHg. The method's concentration estimations can assist in making real‐time decisions regarding location of dissolved plumes and light nonaqueous phase liquid (LNAPL) source zones at many fuel release sites. The screening method was tested in the laboratory and in the field with 208 and 107 samples, respectively. The study concludes that the screening method can be used as a tool to aid in completing a site conceptual model as well as analyzing groundwater from monitoring wells.     

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.     

Review of Quantitative Surveys of the Length and Stability of MTBE,TBA, and Benzene Plumes in Groundwater at UST Sites

Quantitative information regarding the length and stability condition of groundwater plumes of benzene, methyl tert‐butyl ether (MTBE), and tert‐butyl alcohol (TBA) has been compiled from thousands of underground storage tank (UST) sites in the United States where gasoline fuel releases have occurred. This paper presents a review and summary of 13 published scientific surveys, of which 10 address benzene and/or MTBE plumes only, and 3 address benzene, MTBE, and TBA plumes. These data show the observed lengths of benzene and MTBE plumes to be relatively consistent among various regions and hydrogeologic settings, with median lengths at a delineation limit of 10 µg/L falling into relatively narrow ranges from 101 to 185 feet for benzene and 110 to 178 feet for MTBE. The observed statistical distributions of MTBE and benzene plumes show the two plume types to be of comparable lengths, with 90th percentile MTBE plume lengths moderately exceeding benzene plume lengths by 16% at a 10‐µg/L delineation limit (400 feet vs. 345 feet) and 25% at a 5‐µg/L delineation limit (530 feet vs. 425 feet). Stability analyses for benzene and MTBE plumes found 94 and 93% of these plumes, respectively, to be in a nonexpanding condition, and over 91% of individual monitoring wells to exhibit nonincreasing concentration trends. Three published studies addressing TBA found TBA plumes to be of comparable length to MTBE and benzene plumes, with 86% of wells in one study showing nonincreasing concentration trends.     

Identification of Multiple Sources of Groundwater Contamination by Dual Isotopes

Chlorinated solvents are one of the most commonly detected groundwater contaminants in industrial areas. Identification of polluters and allocation of contaminant sources are important concerns in the evaluation of complex subsurface contamination with multiple sources. In recent years, compound‐specific isotope analyses (CSIA) have been employed to discriminate among different contaminant sources and to better understand the fate of contaminants in field‐site studies. In this study, the usefulness of dual isotopes (carbon and chlorine) was shown in assessments of groundwater contamination at an industrial complex in Wonju, Korea, where groundwater contamination with chlorinated solvents such as trichloroethene (TCE) and carbon tetrachloride (CT) was observed. In November 2009, the detected TCE concentrations at the study site ranged between nondetected and 10,066 µg/L, and the CT concentrations ranged between nondetected and 985 µg/L. In the upgradient area, TCE and CT metabolites were detected, whereas only TCE metabolites were detected in the downgradient area. The study revealed the presence of separate small but concentrated TCE pockets in the downgradient area, suggesting the possibility of multiple contaminant sources that created multiple comingling plumes. Furthermore, the variation of the isotopic (δ¹³C and δ³⁷Cl) TCE values between the upgradient and downgradient areas lends support to the idea of multiple contamination sources even in the presence of detectable biodegradation. This case study found it useful to apply a spatial distribution of contaminants coupled with their dual isotopic values for evaluation of the contaminated sites and identification of the presence of multiple sources in the study area.     

The Utility of Multiple-Completion Monitoring Wells for Describing a Solvent Plume

At a study site in the midwestern United States, multiple-completion wells demonstrated that a vertical hydraulic gradient was responsible for the contamination pattern exhibited by chlorinated solvent plumes. The typical pattern consisted of little or no contamination in the upper portion of the aquifer with concentrations increasing with depth. When ground water contamination was discovered in an unexpected portion of the site, water level elevations and contaminant distribution data obtained from multiple-completion wells resulted in identification of the source location. The well eventually determined to be located in the source area displayed contaminant levels much higher in the upper zone of the aquifer — the opposite contamination pattern of other on-site wells. Such results indicated that the spill had occurred near this location and that solvent residing along the capillary fringe was continuing to contaminate the aquifer.     

Soil Gas Screening for Chlorinated Solvents at Three Contaminated Karst Sites in Tennessee

Soil gas was sampled using active sampling techniques and passive collectors at three sites in Tennessee to evaluate the effectiveness of these techniques for locating chlorinated solvent sources and flowpaths in karst aquifers. Actively collected soil gas samples were analyzed in the field with a portable gas chromatograph, and the passive soil gas collectors were analyzed in the lab with gas chromatography/mass spectrometry. Results of the sampling indicate that the effectiveness of both techniques is highly dependent on the distribution of the contaminants in the subsurface, the geomorphic and hydrogeologic characteristics of the site, and, in one case, on seasonal conditions. Both active and passive techniques identified areas of elevated subsurface chlorinated solvent concentrations at a landfill site where contamination remains concentrated in the regolith. Neither technique detected chlorinated solvents known to be moving in the bedrock at a manufacturing site characterized by thick regolith and an absence of surficial karst features. Passive soil gas sampling had varied success detecting flowpaths for chloroform in the bedrock at a train derailment site characterized by shallow regolith and abundant surficial karst features. At the train derailment site, delineation of the contaminant flowpath through passive soil gas sampling was stronger and more detailed under winter conditions than summer.     

Temporal Variations of Chlorinated Solvents in Abstraction Wells

Data obtained during an organic water quality survey of abstraction (pumping) wells in the Triassic Sandstone Aquifer of Birmingham (U.K.) indicate that there are important variations of chlorinated solvent concentrations with time. Short-term observation of solvent concentrations with elapsed pumping time indicates widely differing well responses; such observations are important in establishing good sampling protocols. Long-term monitoring indicates that solvent concentrations, particularly trichloroethene, are often stable with time. When large solvent variations do occur, these are shown to be due to the variation in the abstraction history of the well or significant migration of solvent plumes during the monitoring period. The latter effect is particularly exemplified by rising trends in 1,1,1-trichlroethane concentrations. The changes observed in solvent concentrations during long-term monitoring of the Birmingham Aquifer are slow to occur, but often large.     

Investigation of Ground Water Contamination by Fenamiphos and Atrazine in a Residential Area: Source and Distribution of Contamination

Ground water in a residential area of Perth. Western Australia, was contaminated with fenamiphos and atrazine. probably as a result of the storage and handling of these chemicals at a residential properly. Sampling of existing wells indicated that atrazine and fenamiphos concentrations in ground water beneath a neighboring property were 2000 μg/L and 1000 μg/L, respectively. Fenamiphos concentrations were sufficiently high to be toxic on prolonged skin contact, and contamination posed a public health threat to nearby residents with private wells. Management of the contamination problem included restricting ground water use in the area and using a recovery well to pump contaminated ground water.     

Occurrence of MTBE in Heating Oil and Diesel Fuel in Connecticut

The objective of this study was to confirm if MTBE, which is not intentionally added to fuels other than gasoline, is a contaminant in heating oil and diesel fuel. The study entailed conducting a statewide sampling program of heating oil and diesel fuel in Connecticut. An analytical method was developed to conduct analyses of heating oil and diesel fuel for MTBE in the milligram per liter (mg/L) range. The method involved equilibrating product with water to extract MTBE followed by static head-space analysis on aliquots of the water. Analyses were conducted using a gas chromatograph with a MTBE specific column. The statewide sampling program confirmed the widespread occurrence of MTBE in heating oil and diesel fuel. MTBE was detected in all samples collected during our sampling program at concentrations ranging from 9.7 to 906 mg/L in heating oil (26 samples), and from 74 to 120 mg/L in diesel fuel (five samples). Based on these ranges. MTBE concentrations in ground water in the vicinity of heating oil and diesel fuel releases could exceed thousands of micrograms per liter. Our analysis would suggest that the levels of heating oil and diesel fuel contamination observed could result from the commingling of only a few parts gasoline with thousands of parts of these fuels. The extent to which MTBE occurs in heating oil and diesel fuel nationwide is not known, but our data suggests that it may be widespread.     

Joint interpretation of geoelectrical and volatile organic compounds data: a case study in a hydrocarbons contaminated urban site

As a result of a gasoline spill in an urban area, Electrical Resistivity Tomography (ERT), Electromagnetic Profiling (EMP) and Volatile Organic Compounds (VOC) methods were used in order to define the contamination plume and to optimize the drilling and soil sampling activities. The VOC anomalies (recent contamination) indicated that a gas station located at the study site is an active contamination source. The mature contaminated zones defined by ERT and EMP methods corresponded with low resistivity anomalies due to degradation process of the hydrocarbons contaminants. The ERT, EMP and VOC results were integrated on a map, allowing the final configuration of contamination plumes and the optimization of drilling and soil/free-product sampling. Laboratory analyses of free-product samples suggest the existence of more than one contamination event in the site, with the presence of recent and degraded-hydrocarbon contaminants classified in the gasoline range. This study shows the advantages of joint application of ERT, EMP and VOC methods in sites with active contamination source, where the existence of recent and mature contaminants in subsoil is assumed.     

Phytoscreening for Vinyl Chloride in Groundwater Discharging to a Stream

This study applies an optimized phytoscreening method to locate a chlorinated ethene plume discharging into a stream. To evaluate the conditions most suitable for successful phytoscreening, trees along the stream bank were monitored through different seasons with different environmental conditions and hence different uptake/loss scenarios. Vinyl chloride (VC) as well as cis‐dichloroethylene (cis‐DCE), trichloroethylene (TCE), and tetrachloroethylene (PCE) were detected in the trees, documenting that phytoscreening is a viable method to locate chlorinated ethene plumes, including VC, discharging to streams. The results reveal, that phytoscreening for VC is more sensitive to environmental conditions affecting transpiration than for the other chlorinated ethenes detected. Conditions leading to higher groundwater uptake by transpiration than contaminant loss by diffusion from the tree trunks are optimal (e.g., low relative humidity, plentiful hours of sunshine and an intermediate air temperature). Additionally, low precipitation prior to the sampling event is beneficial, as uptake of infiltrating precipitation dilutes the concentration in the trees. All chlorinated ethenes were sensitive to dilution by clean precipitation and in some months, this resulted in no detection of contaminants in the trees at all. Under optimal environmental conditions the tree cores allowed detection of chlorinated solvents and their metabolites in the underlying groundwater. Whereas, for less ideal conditions there was a risk of no detection of the more volatile VC. This study is promising for the future applicability of phytoscreening to locate shallow groundwater contamination with the degradation products of chlorinated solvents.     

Levels of chlorinated hydrocarbons and trace metals in bivalves and nearshore sediments from the Dominican Republic

Bivalves (Crassostrea rizhophorae, Isognomon alatus, Codakia orbicularis Linné, and Tellina fausta) and sediment samples collected from 12 locations along the Dominican Republic coastline were used to assess the degree of nearshore contamination by selected chlorinated hydrocarbons and heavy metals. Concentrations of total chlordanes, DDTs and PCBs ranged from 0.51 to 7.47 ng/g, < MDL to 30.9 ng/g and 11.3 to 82.3 ng/g, and from < MDL to 1.73 ng/g, 0.21 to 12.5 ng/g and 0.46 to 41.9 ng/g in bivalves and surface sediments, respectively. The concentration ranges of predominantly anthropogenic Cu, Pb and Zn were 3.08–866 μg/g, 0.08–1.46 μg/g and 22.9–4380 μg/g in bivalve soft parts and 1.01–111 mg/g, 0.420–134 μg/g and 1.96–277 μg/g in surface sediments, respectively. Mercury concentrations ranged from 0.290 to 7.02 μg/g and from 0.096 to 0.565 μg/g in both matrices. The relatively high Hg concentrations found in bivalves from two stations in Bahia Samana, near to a known source of past Hg contamination in the sediments, require a more in-depth survey of the area. In general the concentrations of selected chlorinated hydrocarbons and trace metals, compared with those reported for the same matrices in the Caribbean and west Atlantic coastal areas, show at present the existence of only very localized contamination problems in the Dominican Republic.     

Comparison of Downhole and Surface Sampling for the Determination of Volatile Organic Compounds (VOCs) in Ground Water

The relative precision and accuracy of sampling and analysis methods for the determination of trace concentrations of volatile organic compounds (VOCs) in ground water were compared. Samples were collected from a well containing nanogram-per-liter (ng/L) to microgram-per-liter (μg/L) levels of VOCs. A Keck helical rotor submersible pump was used to collect samples at the surface for analysis by purge and trap (P&T) and for analysis by adsorption/thermal desorption (ATD). Downhole samples were collected by passing water through an ATD cartridge. Although slight spontaneous bubble outgassing occurred when the water was brought to the surface, the relative precisions and comparabilities of the surface and downhole methods were generally found to be equivalent from a statistical point of view. A main conclusion of this study is that bringing sample water to the surface for placement in VOC vials (and subsequent analysis by P&T) can be done reliably under many circumstances. However, care must still be taken to prevent adsorption losses and cross contamination. Samples subject to strong bubble outgassing will need to be handled in a special fashion (e.g., by downhole ATD) to minimize volatilization losses. Additionally, the higher sensitivity of the ATD method allows lower detection limits than are possible with P&T. For example, several compounds present at the ng/L level could be determined with confidence by ATD, but not by P&T.     

A Study of Long-Term MTBE Attenuation in the Borden Aquifer, Ontario, Canada

In 1988 and 1989, a natural gradient tracer test was performed in the shallow, aerobic and aquifer at Canadian Forces Base (CFB) Borden. A mixture of ground water containing dissolved oxygenated gasoline was injected below the water table along with chloride (Cl-) as a conservative tracer. The migration of BTEX, MTBE, and Cl was monitored in detail for 16 moths. The mass of BTEX compounds in the plume diminished significantly with time due to intrinsic aerobic biodegradation, while MTBE showed only a small decrease in mass over the 16-month period. In 1995/96, a comprehensive ground water sampling program was undertaken to define the mass of MTBE still present in the aquifer. Since the plume had migrated into an unmonitored section of the Borden Aquifer, numerical modeling and geostatistical methods were applied to define an optimal sampling grid and to improve the level of confidence in the results. A drive point profiling system was used to obtain ground water samples. Numerical modeling with no consideration of degradation pedicted maximum concentrations in excess of 3000 μg/L; field sampling found maximum concentrations of less than 200 μg/L. A mass balance for the remaining MTBE mass in the aquifer eight years after injection showed that only 3% of the original mass remained. Sorption, volatilization, a biotic degradation, and plant uptake are not considered significant attenuation processes for the field conditions. Therefore, we suggest that biodegradation may have played a major role in the attenuation of MTBE within the Borden Aquifer.     

In Situ Measurement and Numerical Simulation of Oxygen Limited Biotransformation

Enhanced subsurface biorestoration is rapidly becoming recognized as a valuable tool for the restoration of hydrocarbon-contaminated aquifers and sediments. Previous field and laboratory studies at a former wood creosoting facility near Conroe, Texas, have indicated that insufficient oxygen is the primary factor limiting the biotransformation of polynuclear aromatics (PNAs) in sediments and ground water at this site. A series of laboratory experiments and field push-pull injection tests were performed as part of this project to: (1) study the effect of low oxygen concentrations on the biotransformation of PNAs; (2) identify the minimum concentration of PNAs that could be achieved through the addition of oxygen alone; (3) confirm that enhanced subsurface biorestoration is feasible at this site; and (4) test an existing numerical model of the biotransformation process (BIOPLUME). The laboratory studies demonstrated that biotransformation of the PNAs was not inhibited at dissolved oxygen concentrations as low as 0.7 mg/L although this work did suggest that there may be a minimum PNA concentration of 30 to 70 μg/L total PNAs below which biotransformation was inhibited. The field push-pull tests confirmed that addition of oxygen was effective in enhancing the subsurface biodegradation of the PNAs. The minimum concentration achieved using oxygen alone was approximately 60 μg/L total PNAs. Minimal biotransformation of these compounds was observed without oxygen addition. The numerical model BIOPLUME was tested against monitoring data from the field experiments and appears to provide a good approximation of the biodegradation process.     

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.     

Geochemical Distribution of Trace Elements in Groundwater from the North Mara Large‐Scale Gold Mining Area of Tanzania

The influence of large‐scale mining operations on groundwater quality was investigated in this study. Trace element concentrations in groundwater samples from the North Mara mining area of northern Tanzania were analyzed. Statistical analyses for relationships between elemental concentrations in the samples and distance of a sampling site from the mine tailings dam were also conducted. Eleven trace elements (Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) were determined, and averages of Fe and Al concentrations were higher than levels accepted by the Tanzanian drinking water guideline. Levels of Pb in three samples were higher than the World Health Organization (WHO) and United States Environmental Protection Agency (USEPA) drinking water guidelines of 10 and 15 µg/L, respectively. One sample contained a higher As level than the WHO and USEPA guideline of 10 µg/L. The correlation between element concentrations and distance from the mine tailings dam was examined using the hierarchical agglomeration cluster analysis method. A significant difference in the elemental concentration existed depending on the distance from the mine tailings dam. Mann–Whitney U‐test post hoc analysis confirmed a relationship between element concentration and distance of a sampling site from the mine tailings dam. This relationship raises concerns about the increased risks of trace elements to people and ecosystem health. A metal pollution index also suggested a relationship between elemental concentrations in the groundwater and the sampling sites’ proximity from the mine tailings dam.