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Borehole‐scale testing of matrix diffusion for contaminated‐rock aquifers

A new method was developed to assess the effect of matrix diffusion on contaminant transport and remediation of groundwater in fractured rock. This method utilizes monitoring wells constructed of open boreholes in fractured rock to conduct backward diffusion experiments on chlorinated volatile organic compounds (CVOCs) in groundwater. The experiments are performed on relatively unfractured zones (called test zones) of the open boreholes over short intervals (approximately 1 meter) by physical isolation using straddle packers. The test zones were identified with a combination of borehole geophysical logging and chemical profiling of CVOCs with passive samplers in the open boreholes. To confirm the test zones are within inactive flow zones, they are subjected to a series of hydraulic tests. Afterwards, the test zones are air sparged with argon to volatilize the CVOCs from aqueous to air phase. Backward diffusion is then measured by periodic passive-sampling of water in the test zone to identify rebound. The passive (non-hydraulically stressed) sampling negates the need to extract water and potentially dewater the test zone. We also monitor active flowing zones of the borehole to assess trends in concentrations in other parts of the fractured rock by purge and passive sampling methods.

Remediation Journal

Assessment of contaminant trends in plumes and wells and monitoring network optimization at the Badger Army Ammunition Plant, Sauk County, Wisconsin

Soil and groundwater at the Badger Army Ammunition Plant (BAAP), Sauk County, Wisconsin, were affected by several contaminants as a result of production and waste disposal practices common during its operation from 1942 to 1975. Three distinct plumes of contaminated groundwater originate on BAAP property and extend off-site, as identified by previous studies. Routine sampling of groundwater quality from a network of monitoring wells and off-site private wells has been performed since 1990, although the number of wells monitored and the monitoring frequency have varied as the approved monitoring plan was modified. During the period of monitoring from 1990 to 2018, numerous site investigations and remedial actions were conducted to address the sources of contamination, contaminated soils, and groundwater. Concentrations of contaminants reportedly decreased between 2000 and 2012 within all three plumes. Five or six contaminants of concern (COCs) were identified for each of the three plumes. An independent assessment of the contaminant plumes and of the monitoring network was conducted using groundwater-quality data collected from more than 600 wells between 2000 and 2018. In a study conducted by the U.S. Geological Survey (USGS), in cooperation with the Army Environmental Command, a consistent data aggregation and interpolation scheme was applied to derive the likely maximum groundwater plume extents in four 3-year time periods between 2000 and 2018. The plume extent was defined by the Enforcement Standard for each COC and represents the maximum concentration observed in each 3-year time period. The plume boundary analysis shows that the spatial extent of groundwater contamination decreased for most COCs during the study period. Some plume boundaries are not well delineated by the existing monitoring network, particularly the downgradient edge of the Propellant Burning Ground plume. Maps identify the plume boundary in each time period, the sampling well network used to delineate the plume, and wells that were sampled in the 2010–12 period but not sampled in the 2015–18 period. A series of statistical analyses using the Monitoring and Remediation Optimization System, version 3.0, program were applied to the available COC concentration data for two distinct periods, 2000 to 2012 and 2013 to 2018, with the break between periods coinciding with changes to the monitoring network in 2013. Trends in the concentration of COCs in individual wells varied, although generally more wells had decreasing than had increasing concentrations for most COCs in both time periods. The exceptions were ethyl ether in the 2004–12 period and 2,6-dinitrotoluene in the 2013–18 period, for which more wells had an increasing trend. Spatial moment analysis of concentration data from the well network was used to assess the stability of each plume for the COCs. During the 2000–12 period, most of the contaminant plumes for which data were sufficient to complete the analysis were either decreasing or stable in mass and size. The exceptions were carbon tetrachloride (associated solely with the Propellant Burning Ground plume) and 2,4-dinitrotoluene and 2,6-dinitrotoluene (in the Deterrent Burning Ground plume), which showed an increasing trend in mass. No COCs showed an increasing trend in plume mass in the 2013–18 period. Some wells with increasing trends in concentration or with concentrations greater than the enforcement standard are near the tail of a plume, where increased monitoring may be of value to better define future plume boundaries. A spatial optimization analysis covering the 2013–18 period identified six wells that provided information redundant to that from other wells. A temporal optimization analysis identified optimal sampling frequencies for 125 wells. Remedial actions directed at the Propellant Burning Ground plume coincided with a general decrease in plume mass and size, although in specific areas and depths, the plume size for specific contaminants may still be increasing.

Wisconsin

Bioremediation in fractured rock: 2. Mobilization of chloroethene compounds from the rock matrix

A mass balance is formulated to evaluate the mobilization of chlorinated ethene compounds (CE) from the rock matrix of a fractured mudstone aquifer under pre- and postbioremediation conditions. The analysis relies on a sparse number of monitoring locations and is constrained by a detailed description of the groundwater flow regime. Groundwater flow modeling developed under the site characterization identified groundwater fluxes to formulate the CE mass balance in the rock volume exposed to the injected remediation amendments. Differences in the CE fluxes into and out of the rock volume identify the total CE mobilized from diffusion, desorption, and nonaqueous phase liquid dissolution under pre- and postinjection conditions. The initial CE mass in the rock matrix prior to remediation is estimated using analyses of CE in rock core. The CE mass mobilized per year under preinjection conditions is small relative to the total CE mass in the rock, indicating that current pump-and-treat and natural attenuation conditions are likely to require hundreds of years to achieve groundwater concentrations that meet regulatory guidelines. The postinjection CE mobilization rate increased by approximately an order of magnitude over the 5 years of monitoring after the amendment injection. This rate is likely to decrease and additional remediation applications over several decades would still be needed to reduce CE mass in the rock matrix to levels where groundwater concentrations in fractures achieve regulatory standards.

New Jersey

Natural attenuation of chlorinated solvents at Area 6, Dover Air Force Base: Groundwater biogeochemistry

Monitored natural attenuation (MNA) has recently emerged as a viable groundwater remediation technology in the United States. Area 6 at Dover Air Force Base (Dover, DE) was chosen as a test site to examine the potential for MNA of tetrachloroethene (PCE) and trichloroethene (TCE) in groundwater and aquifer sediments. A "lines of evidence" approach was used to document the occurrence of natural attenuation. Chlorinated hydrocarbon and biogeochemical data were used to develop a site-specific conceptual model where both anaerobic and aerobic biological processes are responsible for the destruction of PCE, TCE, and daughter metabolites. An examination of groundwater biogeochemical data showed a region of depleted dissolved oxygen with elevated dissolved methane and hydrogen concentrations. Reductive dechlorination likely dominated in the anaerobic portion of the aquifer where PCE and TCE levels were observed to decrease with a simultaneous increase in cis-1,2-dichloroethene (cis-DCE), vinyl chloride (VC), ethene, and dissolved chloride. Near the anaerobic/aerobic interface, concentrations of cis-DCE and VC decreased to below detection limits, presumably due to aerobic biotransformation processes. Therefore, the contaminant and daughter product plumes present at the site appear to have been naturally attenuated by a combination of active anaerobic and aerobic biotransformation processes. ?? 2002 Elsevier Science B.V. All rights reserved.

Journal of Contaminant Hydrology

Characterization of fractures and flow zones in a contaminated shale at the Watervliet Arsenal, Albany County, New York

Flow zones in a fractured shale in and near a plume of volatile organic compounds at the Watervliet Arsenal in Albany County, N. Y. were characterized through the integrated analysis of geophysical logs and single- and cross-hole flow tests. Information on the fracture-flow network at the site was needed to design an effective groundwater monitoring system, estimate offsite contaminant migration, and evaluate potential containment and remedial actions. Four newly drilled coreholes and four older monitoring wells were logged and tested to define the distribution and orientation of fractures that intersected a combined total of 500 feet of open hole. Analysis of borehole-wall image logs obtained with acoustic and optical televiewers indicated 79 subhorizontal to steeply dipping fractures with a wide range of dip directions. Analysis of fluid resistivity, temperature, and heat-pulse and electromagnetic flowmeter logs obtained under ambient and short-term stressed conditions identified 14 flow zones, which consist of one to several fractures and whose estimated transmissivity values range from 0.1 to more than 250 feet squared per day. Cross-hole flow tests, which were used to characterize the hydraulic connection between fracture-flow zones intersected by the boreholes, entailed (1) injection into or extraction from boreholes that penetrated a single fracture-flow zone or whose zones were isolated by an inflatable packer, and (2) measurement of the transient response of water levels and flow in surrounding boreholes. Results indicate a wellconnected fracture network with an estimated transmissivity of 80 to 250 feet squared per day that extends for at least 200 feet across the site. This interconnected fracture-flow network greatly affects the hydrology of the site and has important implications for contaminant monitoring and remedial actions.

New York

Use of electromagnetic induction methods to monitor remediation at the University of Connecticut landfill: 2004–2011

Time‐lapse geophysical surveys using frequency‐domain electromagnetics (FDEM) can indirectly measure time‐varying hydrologic parameters such as fluid saturation or solute concentration. Monitoring of these processes provides insight into aquifer properties and the effectiveness of constructed controls (such as leachate interceptor trenches), as well as aquifer responses to natural or induced stresses. At the University of Connecticut landfill, noninvasive, electromagnetic induction (EMI) methods were used to monitor changes in subsurface electrical conductivity that were related to the landfill‐closure activities. After the landfill was closed, EMI methods were used to monitor changes in water saturation and water quality. As part of a long‐term monitoring plan to observe changes associated with closure, redevelopment, and remediation of the former landfill, EMI data were collected to supplement information from groundwater samples collected in wells to the south and north of the landfill. In comparison to single‐point measurements that could have been collected by conventional installation of additional monitoring wells, the EMI methods provided increased spatial coverage, and were less invasive and therefore less destructive to the wetland north of the landfill. To monitor effects of closure activities on the subsurface conductivity, EMI measurements were collected from 2004 to 2011 along discrete transects north and south of the landfill prior to, during, and after the landfill closure. In general, the results indicated an overall decline in subsurface electrical conductivity with time and with distance from the former landfill. This decline in electrical conductivity indicated that the closure and remediation efforts reduced the amount of leachate that originated from the landfill and that entered the drainages to the north and south of the landfill.

Conference Paper

Assessment of the quality of groundwater and the Little Wind River in the area of a former uranium processing facility on the Wind River Reservation, Wyoming, 1987 through 2010

In 2010, the U.S Geological Survey (USGS), in cooperation with the Wind River Environmental Quality Commission (WREQC), began an assessment of the effectiveness of the existing monitoring network at the Riverton, Wyoming, Uranium Mill Tailings Remedial Action (UMTRA) site. The USGS used existing data supplied by the U.S. Department of Energy (DOE). The study was to determine (1) seasonal variations in the direction of groundwater flow in the area of the former uranium processing facility toward the Little Wind River, (2) the extent of contaminated groundwater among the aquifers and between the aquifers and the Little Wind River, (3) whether current monitoring is adequate to establish the effectiveness of natural attenuation for the contaminants of concern, and (4) the influence of groundwater discharged from the sulfuric-acid plant on water quality in the Little Wind River.

Wyoming

Groundwater chemistry, hydrogeologic properties, bioremediation potential, and three-dimensional numerical simulation of the sand and gravel aquifer at Naval Air Station Whiting Field, near Milton, Florida, 2015–20

The U.S. Geological Survey completed a study between 2015 and 2020 of groundwater contamination in the sand and gravel aquifer at a Superfund site in northwestern Florida. Groundwater-quality samples were collected from representative monitoring wells located along a groundwater-flow pathway and analyzed in the field and laboratory. In general, ambient groundwater in the sand and gravel aquifer is acidic, dilute, and oxic. Groundwater age-dating results indicate recharge to the contaminated parts of the aquifer occurred between the 1970s and 1980s. Natural gamma, electromagnetic induction, and borehole nuclear magnetic resonance logs indicated that aquifer hydraulic conductivities generally increased with depth as the aquifer formation material became coarser, characteristic of a prograding marginal-marine delta depositional environment. Aquifer formation material incubated with radiocarbon (carbon-14) cis -1,2-Dichloroethylene demonstrated biodegradation directly to carbon dioxide in contaminated and uncontaminated parts of the aquifer. A three-dimensional, numerical groundwater-flow MODFLOW model of the sand and gravel aquifer in the study area was constructed. The calibrated model reasonably reproduced measured groundwater heads and streamflows. Moreover, the model can be used to run simulations of outcomes of potential remedial strategies, such as monitored natural attenuation, as part of future feasibility studies in the area.

Florida

Potential environmental issues of CO 2 storage in deep saline aquifers: Geochemical results from the Frio-I Brine Pilot test, Texas, USA

Sedimentary basins in general, and deep saline aquifers in particular, are being investigated as possible repositories for large volumes of anthropogenic CO 2 that must be sequestered to mitigate global warming and related climate changes. To investigate the potential for the long-term storage of CO 2 in such aquifers, 1600 t of CO 2 were injected at 1500 m depth into a 24-m-thick "C" sandstone unit of the Frio Formation, a regional aquifer in the US Gulf Coast. Fluid samples obtained before CO 2 injection from the injection well and an observation well 30 m updip showed a Na–Ca–Cl type brine with ∼93,000 mg/L TDS at saturation with CH 4 at reservoir conditions; gas analyses showed that CH 4 comprised ∼95% of dissolved gas, but CO 2 was low at 0.3%. Following CO 2 breakthrough, 51 h after injection, samples showed sharp drops in pH (6.5–5.7), pronounced increases in alkalinity (100–3000 mg/L as HCO 3 ) and in Fe (30–1100 mg/L), a slug of very high DOC values, and significant shifts in the isotopic compositions of H 2 O, DIC, and CH 4 . These data, coupled with geochemical modeling, indicate corrosion of pipe and well casing as well as rapid dissolution of minerals, especially calcite and iron oxyhydroxides, both caused by lowered pH (initially ∼3.0 at subsurface conditions) of the brine in contact with supercritical CO 2 . These geochemical parameters, together with perfluorocarbon tracer gases (PFTs), were used to monitor migration of the injected CO 2 into the overlying Frio “B”, composed of a 4-m-thick sandstone and separated from the “C” by ∼15 m of shale and siltstone beds. Results obtained from the Frio “B” 6 months after injection gave chemical and isotopic markers that show significant CO 2 (2.9% compared with 0.3% CO 2 in dissolved gas) migration into the “B” sandstone. Results of samples collected 15 months after injection, however, are ambiguous, and can be interpreted to show no additional injected CO 2 in the “B” sandstone. The presence of injected CO 2 may indicate migration from “C” to “B” through the intervening beds or, more likely, a short-term leakage through the remedial cement around the casing of a 50-year old well. Results obtained to date from four shallow monitoring groundwater wells show no brine or CO 2 leakage through the Anahuac Formation, the regional cap rock.

Texas

Trace metal and phosphorus loading from groundwater seepage into South Fork Coeur d’Alene River after remediation at the Bunker Hill Superfund Site, northern Idaho, 2022

Widely dispersed waste products from historical mining in northern Idaho’s Coeur d’Alene mining district have long been a concern in the Coeur d’Alene River Basin in northern Idaho. The Central Impoundment Area (CIA), an unlined mining waste repository that is part of the Bunker Hill Superfund Site designated in 1983, is adjacent to the South Fork Coeur d’Alene River between Kellogg and Smelterville, Idaho. Previous studies, including a pre-remediation seepage study completed by the U.S. Geological Survey (USGS) in 2017, have identified groundwater seepage from beneath the CIA as a major contributor to trace-metal and nutrient loads (including zinc, cadmium, and phosphorus) in the South Fork Coeur d’Alene River. A major remediation project, led by the U.S. Environmental Protection Agency from late 2017 to 2021, specifically aimed to reduce groundwater loading to the river via a groundwater collection system (GWCS) at the CIA. In 2022, the USGS completed a post-remediation seepage study to quantify zinc, cadmium, and phosphorus loading from groundwater to the South Fork Coeur d’Alene River in the same reach as the 2017 pre-remediation study. Like in the previous USGS study, discharge measurements and water-quality samples were collected during base-flow conditions in the South Fork Coeur d’Alene River between Kellogg and Smelterville as well as in surface-water inputs to the reach. Results of this study show a reduction in groundwater loads of dissolved zinc, dissolved cadmium, and total phosphorus entering the South Fork Coeur d’Alene River compared to 2017. The largest reductions in groundwater loading to the South Fork Coeur d’Alene River occurred in a discrete section (the middle section) of the reach adjacent to the CIA where the GWCS was expected to have the biggest impact. In the South Fork Coeur d’Alene River middle section, loads from groundwater (presented as a mean plus or minus [±] standard deviation) of dissolved zinc decreased from 85 ± 9.3 kilograms per day (kg/d) in 2017 to 11.6 ± 19.2 kg/d in 2022 (86-percent reduction), dissolved cadmium decreased from 0.59 ± 0.10 kg/d in 2017 to 0.11 ± 0.06 kg/d in 2022 (81-percent reduction), and total phosphorus decreased from 6.5 ± 0.45 kg/d in 2017 to 0.79 ± 0.97 kg/d in 2022 (88-percent reduction). In addition to reduced groundwater loading, lower concentrations of dissolved zinc, dissolved cadmium, and total phosphorus were observed at the site farthest downstream from the GWCS. Furthermore, the ambient water-quality-criteria ratios decreased at all river monitoring sites in 2022, although zinc and cadmium concentrations still exceeded the site-specific criteria designated to protect aquatic life. This post-remediation study indicates that the GWCS at the CIA has reduced groundwater loading of trace metals and phosphorus to the South Fork Coeur d’Alene River. This reduction in trace metals and phosphorus in South Fork Coeur d’Alene River also has implications for water quality downstream in the main-stem Coeur d’Alene River and in Coeur d’Alene Lake.

Idaho

Selected Natural Attenuation Monitoring Data, Operable Unit 1, Naval Undersea Warfare Center, Division Keyport, Washington, 2007 and 2008

Previous investigations indicate that natural attenuation and biodegradation of chlorinated volatile organic compounds (VOCs) are substantial in groundwater beneath the 9-acre former landfill at Operable Unit 1 (OU 1), Naval Undersea Warfare Center, Division Keyport, Washington. Phytoremediation combined with on-going natural attenuation processes was the preferred remedy selected by the Navy, as specified in the Record of Decision for the site. The Navy planted two hybrid poplar plantations on the landfill in spring 1999 to remove and to control the migration of chlorinated VOCs in shallow groundwater. The U.S. Geological Survey (USGS) has continued to monitor groundwater geochemistry to ensure that conditions remain favorable for contaminant biodegradation as specified in the Record of Decision. In this report are groundwater geochemical and selected VOC data collected at OU 1 by the USGS during June 18-21, 2007, and June 16-18, 2008, in support of long-term monitoring for natural attenuation. For 2007 and 2008, strongly reducing conditions (sulfate reduction and methanogenesis) most favorable for reductive dechlorination of VOCs were inferred for 9 of 16 upper-aquifer wells and piezometers in the northern and southern phytoremediation plantations. Predominant redox conditions in groundwater from the intermediate aquifer just downgradient from the landfill remained mildly reducing and somewhat favorable for reductive dechlorination of VOCs. Dissolved hydrogen (H2) concentrations measured in the upper aquifer during 2007 and 2008 generally have been lower than H2 concentrations measured before 2002. However, widespread and relatively high methane and sulfide concentrations indicate that the lower H2 concentrations measured do not support a trend from strongly to mildly reducing redox conditions because no widespread changes in groundwater redox conditions were identified that should result in less favorable conditions for the reductive dechlorination of the chlorinated VOCs. For the upper aquifer beneath the northern phytoremediation plantation, chlorinated VOC concentrations in 2007 and 2008 at most piezometers were similar to or slightly less than chlorinated VOC concentrations measured in previous years. The only chlorinated VOC positively detected at piezometers P1-1 and P1-5 was cis-1,2-dichloroethene (cis-DCE); most chlorinated VOC concentrations at piezometer P1-3 were at the lowest levels since monitoring began in 1999. Most VOC concentrations at piezometer P1-4 were similar to VOC concentrations measured in previous years except that vinyl chloride (VC) concentrations inexplicably increased from 280 micrograms per liter (ug/L) in June 2007 to 750 ug/L in June 2008. In 2008, measurement of the sum of concentrations of ethane and ethene, reductive dechlorination byproducts, was at the highest level at most northern plantation wells and piezometers, which is evidence of reductive dechlorination of chlorinated VOCs. For the upper aquifer beneath the southern phytoremediation plantation, chlorinated VOC concentrations in 2007 and 2008 at the piezometers were most often extremely high and they continued to vary considerable over space and between years. At piezometer P1-6, the total chlorinated VOC concentration increased from 380 ug/L in 2007 to more than 20,000 ug/L in 2008. At piezometer P1-7 in 2008, the concentrations of trichloroethene, cis-DCE, and VC were the highest to date, but total chlorinated VOC concentrations at piezometers P1-8, P1-9, and P1-10 in 2008 were relatively low compared to historical levels. The magnitude and persistence of chlorinated VOC concentrations indicate that non-aqueous phase liquid chloroethenes likely are beneath the southern plantation, and the temporal variability in concentrations likely is a result of variations in precipitation and groundwater levels interacting with the non-aqueous phase liquid. The reductive dechlorination byproducts ethane and ethene were detected at

Open-File Report

Interaction of a legacy groundwater contaminant plume with the Little Wind River from 2015 through 2017, Riverton Processing site, Wyoming

The Riverton Processing site was a uranium mill 4 kilometers southwest of Riverton, Wyoming, that prepared uranium ore for nuclear reactors and weapons from 1958 to 1963. The U.S. Department of Energy completed surface remediation of the uranium tailings in 1989; however, groundwater below and downgradient from the tailings site and nearby Little Wind River was not remediated. Beginning in 2010, a series of floods along the Little Wind River began to mobilize contaminants in the unsaturated zone, resulting in substantial increases of uranium and other contaminants of concern in monitoring wells completed inside the contaminant plume. In 2011, the U.S. Department of Energy started a series of university and Government agency retrospective and field investigations to understand the processes controlling contaminant increases in the groundwater plume. The goals of the field investigations described in this report were to (1) identify and quantify the contaminant flux and potential associated biological effects from groundwater associated with the legacy plume as it enters a perennial stream reach, and (2) assess chemical exposure and potential effects to biological receptors from the interaction of the contaminant plume and the river. Field investigations along the Little Wind River were completed by the U.S. Geological Survey during 2015–17 in cooperation with the U.S. Department of Energy Office of Legacy Management to characterize: (1) seepage areas and seepage rates; (2) pore-water and bed sediment chemistry and hyporheic exchange and reactive loss; and (3) exposure pathways and biological receptors. All data collected during the study are contained in two U.S. Geological Survey data releases, available at https://doi.org/10.5066/F7BR8QX4 and https://doi.org/10.5066/P9J9VJBR . A variety of tools and methods were used during the field characterizations. Streambed temperature mapping, electrical resistivity tomography, electromagnetic induction, fiber-optic distributed temperature sensing, tube seepage meters, vertical thermal sensor arrays, and an environmental tracer (radon) were used to identify areas of groundwater seepage and associated seepage rates along specific sections of the study reach of the river. Drive points, minipiezometers, diffusive equilibrium in thin-film/diffusive gradients in thin-film probes, bed-sediment samples, and equal discharge increment sampling methods were used to characterize pore-water chemistry, estimate hyporheic exchange and reactive loss of selected chemical constituents, and quantify contaminant loadings entering the study reach. Sampling and analysis of surface sediments, filamentous algae, periphytic algae, and macroinvertebrates were used to characterize biological exposure pathways, metal uptake, and receptors. Areas of focused groundwater discharge identified by the fiber-optic distributed temperature sensing surveys corresponded closely with areas of elevated electrical conductivity identified by the electromagnetic induction survey results in the top 5 meters of sediment. During three monitoring periods in 2016, the mean vertical seepage rate measured with tube seepage meters was 0.45 meter per day, ranging from −0.02 to 1.55 meters per day. Five of the 11 locations where vertical thermal profile data were collected along the study reach during August 2017 indicated mean upwelling values ranging from 0.11 to 0.23 meter per day. Radon data collected from the Little Wind River during June, July, and August 2016 indicated a consistent inflow of groundwater to the central part of the study reach, in the area congruous with the center of the previously mapped groundwater plume discharge zone. During August 2017, the greatest attenuation of uranium from reactive loss in pore-water samples was observed at three locations along the study reach, at depths between 6 and 15 centimeters, and similar trends in molybdenum attenuation were also observed. Bed-sediment concentration profiles collected during 2017 also indicated attenuation of uranium and molybdenum from groundwater during hyporheic mixing of surface water with the legacy plume during groundwater upwelling into the river. Streamflow measurements combined with equal discharge increment water sampling along the study reach indicated an increase in dissolved uranium concentrations in the downstream direction during 2016 and 2017. Net uranium load entering the Little Wind River study reach was about 290 and 435 grams per day during 2016 and 2017, respectively. Biological samples indicated that low levels of uranium and molybdenum exposure were confined to the benthos in the Little Wind River within and immediately downstream from the perimeter of the groundwater plume. Concentrations of molybdenum and uranium in filamentous algae were consistently low at all sites in the study reach with no indication of increased exposure of dissolved bioavailable molybdenum or uranium at sites next to or downstream from the groundwater plume. Comparison of the August 2017 results from electromagnetic induction, tube seepage meters, vertical thermal profiling, and pore-water chemistry surveys were in general agreement in identifying areas with upwelling groundwater conditions along the study reach. However, the electroconductivity values measured with electromagnetic induction in the top 100 centimeters of sediment did not agree with sodium concentrations measured in pore-water samples collected at similar streambed depths. Differences and similarities between multiple methods can result in additional insights into hydrologic and biogeochemical processes that may be occurring along a reach of a river system interacting with shallow groundwater inputs. It may be advantageous to apply a variety of geophysical, geochemical, hydrologic, and biological tools at other Uranium Mill Tailings Remedial Action ( https://www.energy.gov/sites/prod/files/2014/10/f19/UMTRCA.pdf ) sites during the investigation of legacy contaminant plume interactions with surface-water systems.

Wyoming

Investigations of groundwater system and simulation of regional groundwater flow for North Penn Area 7 Superfund site, Montgomery County, Pennsylvania

Groundwater in the vicinity of several industrial facilities in Upper Gwynedd Township and vicinity, Montgomery County, in southeast Pennsylvania has been shown to be contaminated with volatile organic compounds (VOCs), the most common of which is the solvent trichloroethylene (TCE). The 2-square-mile area was placed on the National Priorities List as the North Penn Area 7 Superfund site by the U.S. Environmental Protection Agency (USEPA) in 1989. The U.S. Geological Survey (USGS) conducted geophysical logging, aquifer testing, and water-level monitoring, and measured streamflows in and near North Penn Area 7 from fall 2000 through fall 2006 in a technical assistance study for the USEPA to develop an understanding of the hydrogeologic framework in the area as part of the USEPA Remedial Investigation. In addition, the USGS developed a groundwater-flow computer model based on the hydrogeologic framework to simulate regional groundwater flow and to estimate directions of groundwater flow and pathways of groundwater contaminants. The study area is underlain by Triassic- and Jurassic-age sandstones and shales of the Lockatong Formation and Brunswick Group in the Mesozoic Newark Basin. Regionally, these rocks strike northeast and dip to the northwest. The sequence of rocks form a fractured-sedimentary-rock aquifer that acts as a set of confined to partially confined layers of differing permeabilities. Depth to competent bedrock typically is less than 20 ft below land surface. The aquifer layers are recharged locally by precipitation and discharge locally to streams. The general configuration of the potentiometric surface in the aquifer is similar to topography, except in areas affected by pumping. The headwaters of Wissahickon Creek are nearby, and the stream flows southwest, parallel to strike, to bisect North Penn Area 7. Groundwater is pumped in the vicinity of North Penn Area 7 for industrial use, public supply, and residential supply. Results of field investigations by USGS at the site and results from other studies support, and are consistent with, a conceptual model of a layered leaky aquifer where the dip of the beds has a strong control on hydraulic connections in the groundwater system. Connections within and (or) parallel to bedding tend to be greater than across bedding. Transmissivities of aquifer intervals isolated by packers ranged over three orders of magnitude [from about 2.8 to 2,290 square feet per day (ft 2 /d) or 0.26 to 213 square meters per day (m 2 /d)], did not appear to differ much by mapped geologic unit, but showed some relation to depth being relatively smaller in the shallowest and deepest intervals (0 to 50 ft and more than 250 ft below land surface, respectively) compared to the intermediate depth intervals (50 to 250 ft below land surface) tested. Transmissivities estimated from multiple-observation well aquifer tests ranged from about 700 to 2,300 ft 2 /d (65 to 214 m 2 /d). Results of chemical analyses of water from isolated intervals or monitoring wells open to short sections of the aquifer show vertical differences in concentrations; chloride and silica concentrations generally were greater in shallow intervals than in deeper intervals. Chloride concentrations greater than 100 milligrams per liter (mg/L), combined with distinctive chloride/bromide ratios, indicate a different source of chloride in the western part of North Penn Area 7 than elsewhere in the site. Groundwater flow at a regional scale under steady-state conditions was simulated by use of a numerical model (MODFLOW-2000) for North Penn Area 7 with different layers representing saprolite/highly weathered rock near the surface and unweathered competent bedrock. The sedimentary formations that underlie the study area were modeled using dipping model layers for intermediate and deep zones of unweathered, fractured rock. Horizontal cell model size was 100 meters (m) by 100 meters (328 ft by 328 ft), and model layer thickness ranged from 6 m (19.7 ft) representing shallow weathered rock and saprolite up to 200 m (656 ft) representing deeper dipping bedrock. The model did not include detailed structure to account for local-scale differences in hydraulic properties, with the result that local-scale groundwater flow may not be well simulated. Additional detailed multi-well aquifer tests would be needed to establish the extent of interconnection between intervals at the local scale to address remediation of contamination at each source area. This regional groundwater-flow model was calibrated against measured groundwater levels (1996, 2000, and 2005) and base flow estimated from selected streamflow measurements by use of nonlinear-regression parameter-estimation algorithms to determine hydraulic conductivity and anisotropy of hydraulic conductivity, streambed hydraulic conductivity, and recharge during calibration periods. Results of the simulation using the calibrated regional model indicate that the aquifer appears to be anisotropic where hydraulic conductivity is greatest parallel to the orientation of bedding of the formations underlying the area and least in the cross-bed direction. The maximum hydraulic conductivity is aligned with the average regional strike of the formations, which is “subhorizontal” in the model because the altitudes of the beds and model cells vary in the strike, as well as dip, direction. Estimated subhorizontal hydraulic conductivities (in strike direction parallel to dipping beds) range from 0.001 to 1.67 meters per day (0.0032 to 5.5 feet per day). The ratio of minimum (dip direction) to maximum (strike direction) subhorizontal hydraulic conductivity ranges from 1/3.1 to 1/8.6, and the ratio of vertical to horizontal hydraulic conductivity ranges from 1/1 to 1/478. However, limited available field data precluded rigorous calibration of vertical anisotropy in the model. Estimated recharge rates corresponding to calibration periods in 1996, 2000, and 2005 are 150, 109, and 124 millimeters per year (5.9, 4.3, and 4.9 inches per year), respectively. The calibrated groundwater-flow model was used to simulate groundwater flow under steady-state conditions during periods of relatively high withdrawals (pumpage) (1990) and relatively low withdrawals (2000 and 2005). Groundwater-flow paths originating from recharge areas near known areas of soil contamination (sources) were simulated. Pumped industrial and production wells captured more groundwater from several of these sources during 1990 than after 1990 when pumping declined or ceased and greater amounts of contaminated groundwater moved away from North Penn Area 7 Superfund site to surrounding areas. Uncertainty in simulated groundwater-flow paths from contaminant sources and contributing areas, resulting from uncertainty in estimated hydraulic properties of the model, was illustrated through Monte Carlo simulations. The effect of uncertainty in the vertical anisotropy was not included in the Monte Carlo simulations. Contributing areas indicating the general configuration of groundwater flow towards production well MG-202 (L-22) in the study area also were simulated for the different time periods; as simulated, the flow paths do not pass through any identified contaminant source in North Penn Area 7. However, contributing areas to wells, such as MG-202, located near many pumped wells are particularly complex and, in some cases, include areas that contribute flow to streams that subsequently recharge the aquifer through stream loss. In these cases, water-quality constituents, including contaminants that are present in surface water may be drawn into the aquifer to nearby pumped wells. Results of a simulated shutdown of well MG-202 under steady-state 2005 conditions showed that the area contributing recharge for nearby production well MG-76 (L-17), when MG-202 is not pumping, shifts downstream and is similar to the area contributing recharge for MG-202 when both wells are pumping. Concentrations of constituents in groundwater samples collected in fall 2005 or spring 2006 were compared to simulated groundwater-flow paths for the year 2005 to provide a qualitative assessment of model results. The observed spatial distribution of selected constituents, including TCE, CFC-11, and CFC-113 in groundwater in 2005 and the chloride/bromide mass ratios in 2006, generally were consistent with the model results of the simulated 2005 groundwater-flow paths at North Penn Area 7, indicating the presence of several separate sources of contaminants within North Penn Area 7.

Pennsylvania

In situ stimulation of groundwater denitrification with formate to remediate nitrate contamination

In situ stimulation of denitrification has been proposed as a mechanism to remediate groundwater nitrate contamination. In this study, sodium formate was added to a sand and gravel aquifer on Cape Cod, MA, to test whether formate could serve as a potential electron donor for subsurface denitrification. During 16- and 10-day trials, groundwater from an anoxic nitrate-containing zone (0.5-1.5 mM) was continuously withdrawn, amended with formate and bromide, and pumped back into the aquifer. Concentrations of groundwater constituents were monitored in multilevel samplers after up to 15 m of transport by natural gradient flow. Nitrate and formate concentrations were decreased 80-100% and 60-70%, respectively, with time and subsequent travel distance, while nitrite concentrations inversely increased. The field experiment breakthrough curves were simulated with a two-dimensional site-specific model that included transport, denitrification, and microbial growth. Initial values for model parameters were obtained from laboratory incubations with aquifer core material and then refined to fit field breakthrough curves. The model and the lab results indicated that formate-enhanced nitrite reduction was nearly 4-fold slower than nitrate reduction, but in the lab, nitrite was completely consumed with sufficient exposure time. Results of this study suggest that a long-term injection of formate is necessary to test the remediation potential of this approach for nitrate contamination and that adaptation to nitrite accumulation will be a key determinative factor.In situ stimulation of denitrification has been proposed as a mechanism to remediate groundwater nitrate contamination. In this study, sodium formate was added to a sand and gravel aquifer on Cape Cod, MA, to test whether formate could serve as a potential electron donor for subsurface denitrification. During 16- and 10-day trials, groundwater from an anoxic nitrate-containing zone (0.5-1.5 mM) was continuously withdrawn, amended with formate and bromide, and pumped back into the aquifer. Concentrations of groundwater constituents were monitored in multilevel samplers after up to 15 m of transport by natural gradient flow. Nitrate and formate concentrations were decreased 80-100% and 60-70%, respectively, with time and subsequent travel distance, while nitrite concentrations inversely increased. The field experiment breakthrough curves were simulated with a two-dimensional site-specific model that included transport, denitrification, and microbial growth. Initial values for model parameters were obtained from laboratory incubations with aquifer core material and then refined to fit field breakthrough curves. The model and the lab results indicated that formate-enhanced nitrite reduction was nearly 4-fold slower than nitrate reduction, but in the lab, nitrite was completely consumed with sufficient exposure time. Results of this study suggest that a long-term injection of formate is necessary to test the remediation potential of this approach for nitrate contamination and that adaptation to nitrite accumulation will be a key determinative factor.

Environmental Science & Technology

Methodology for estimating times of remediation associated with monitored natural attenuation

Natural attenuation processes combine to disperse, immobilize, and biologically transform anthropogenic contaminants, such as petroleum hydrocarbons and chlorinated ethenes, in ground-water systems. The time required for these processes to lower contaminant concentrations to levels protective of human health and the environment, however, varies widely between different hydrologic systems, different chemical contaminants, and varying amounts of contaminants. This report outlines a method for estimating timeframes required for natural attenuation processes, such as dispersion, sorption, and biodegradation, to lower contaminant concentrations and mass to predetermined regulatory goals in groundwater systems. The time-of-remediation (TOR) problem described in this report is formulated as three interactive components: (1) estimating the length of a contaminant plume once it has achieved a steady-state configuration from a source area of constant contaminant concentration, (2) estimating the time required for a plume to shrink to a smaller, regulatoryacceptable configuration when source-area contaminant concentrations are lowered by engineered methods, and (3) estimating the time needed for nonaqueous phase liquid (NAPL) contaminants to dissolve, disperse, and biodegrade below predetermined levels in contaminant source areas. This conceptualization was used to develop Natural Attenuation Software (NAS), an interactive computer aquifers. NAS was designed as a screening tool and requires the input of detailed site information about hydrogeology, redox conditions, and the distribution of contaminants. Because NAS is based on numerous simplifications of hydrologic, microbial, and geochemical processes, the program may introduce unacceptable errors for highly heterogeneous hydrologic systems. In such cases, application of the TOR framework outlined in this report may require more detailed, site-specific digital modeling. The NAS software may be downloaded from the Web site http://www.cee.vt.edu/NAS/ Application of NAS illustrates several general characteristics shared by all TOR problems. First, the distance of stabilization of a contaminant plume is strongly dependent on the natural attenuation capacity of particular ground-water systems. The time that it takes a plume to reach a steady-state configuration, however, is independent of natural attenuation capacity. Rather, the time of stabilization is most strongly affected by the sorptive capacity of the aquifer, which is dependent on the organic matter content of the aquifer sediments, as well as the sorptive properties of individual contaminants. As a general rule, a high sorptive capacity retards a plume.s growth or shrinkage, and increases the time of stabilization. Finally, the time of NAPL dissolution depends largely on NAPL mass, composition, geometry, and hydrologic factors, such as ground-water flow rates. An example TOR analysis for petroleum hydrocarbon NAPL was performed for the Laurel Bay site in South Carolina. About 500 to 1,000 pounds of gasoline leaked into the aquifer at this site in 1991, and the NAS simulations suggested that TOR would be on the order of 10 years for soluble and poorly sorbed compounds, such as benzene and methyl tertiary-butyl ether (MTBE). Conversely, TOR would be on the order of 40 years for less soluble, more strongly sorbed compounds, such as toluene, ethylbenzene, and xylenes (TEX). These TOR estimates are roughly consistent with contaminant concentrations observed over 10 years of monitoring at this site where benzene and MTBE concentrations were observed to decrease rapidly and are approaching regulatory maximum concentration limits, whereas toluene, ethylbenzene, and xylene concentrations decreased at a slower rate and have remained relatively high. An example TOR analysis for petroleum hydrocarbon NAPL was performed for the Laurel Bay site in South Carolina.

South Carolina

Case studies in groundwater contaminant fate and transport

A case study of groundwater contamination is a detailed study of a single site contaminated with a chemical or mixture that is known to be a problem at many sites. The goal of case studies is to provide insights into the physical, chemical, and biological processes controlling migration, natural attenuation, or remediation of common groundwater contaminants. Ideally, processes occurring at a case study site are representative of other sites so that knowledge gained from these intensive studies can be applied at thousands of sites where fewer data are available. Several characteristics of case studies contribute to their value. First, they may have tens to hundreds of monitoring wells, compared to fewer than ten wells at some contaminated sites. Second, some case studies continue for many years or even decades, providing insights into temporal progression of slow processes. Third, analytical methods prohibitively expensive for routine use or under development may be tested at case study sites. Finally, the ongoing characterization typical of case study sites builds a foundation of knowledge that facilitates sophisticated experimental design and testing of new methods. This article is divided into sections based on the contaminant type because the chemical and biological processes required for remediation vary for each contaminant. Most importantly, some contaminants can be biodegraded whereas metals and radionuclides cannot be destroyed but can be immobilized or rendered less toxic. The emphasis is on case studies of natural processes that control the fate and transport of contaminants in groundwater rather than on active remediation methods. The principles learned from these studies may form the basis for design of remedial strategies. The organic contaminants are divided into: petroleum hydrocarbons, fuel oxygenates, coal tar and wastes from manufactured gas plants, and chlorinated solvents. The inorganic contaminants covered are metals and radionuclides, arsenic, and nitrate. Case studies of mixed waste plumes from landfills are also described. Experimental sites where contaminants have been introduced into an aquifer as an emplaced source or a controlled release may not meet the above definition of case studies, but some are included because the overall goal is to impart lessons learned from detailed field studies. It is impossible to cover all case studies in this short format. Conversely, focusing on one or two does not convey the breadth of research results in entire range of case studies. Instead, the strategy is to describe the evolution of knowledge for each contaminant class while providing citations of relevant case studies. Much of the progress in understanding of the fate of contaminants in groundwater is based on laboratory studies; thus whenever possible, papers that included both field and laboratory results have been included among the citations. Two topics of growing importance have not been covered. These are the fate of pharmaceuticals in groundwater and discharge of contaminant plumes to surface water. These topics merit coverage in the future as knowledge grows and case studies increase in number.

Environmental Science

Geochemical, isotopic, and dissolved gas characteristics of groundwater in a fractured crystalline-rock aquifer, Savage Municipal Well Superfund site, Milford, New Hampshire, 2011

Tetrachloroethylene (PCE), a volatile organic compound, was detected in groundwater from deep (more than (>) 300 feet (ft) below land surface) fractures in monitoring wells tapping a crystalline-rock aquifer beneath operable unit 1 (OU1) of the Savage Municipal Well Superfund site (Weston, Inc., 2010). Operable units define remedial areas of contaminant concern. PCE contamination within the fractured-rock aquifer has been designated as a separate operable unit, operable unit 3 (OU3; Weston, Inc., 2010). PCE contamination was previously detected in the overlying glacial sand and gravel deposits and basal till, hereafter termed the Milford-Souhegan glacial-drift (MSGD) aquifer (Harte, 2004, 2006). Operable units 1 and 2 encompass areas within the MSGD aquifer, whereas the extent of the underlying OU3 has yet to be defined. The primary original source of contamination has been identified as a former manufacturing facility—the OK Tool manufacturing facility; hence OU1 sometimes has been referred to as the OK Tool Source Area (New Hampshire Department of Environmental Services, undated). A residential neighborhood of 30 to 40 houses is located in close proximity (one-quarter of a mile) from the PCE-contaminated monitoring wells. Each house has its own water-supply well installed in similar rocks as those of the monitoring wells, as indicated by the New Hampshire State geologic map (Lyons and others, 1997). An investigation was initiated in 2010 by the U.S. Environmental Protection Agency (USEPA) region 1, and the New Hampshire Department of Environmental Services (NHDES) to assess the potential for PCE transport from known contaminant locations (monitoring wells) to the residential wells. The U.S. Geological Survey (USGS) and the NHDES entered into a cooperative agreement in 2011 to assist in the evaluation of PCE transport in the fractured-rock aquifer. Periodic sampling over the last decade by the USEPA and NHDES has yet to detect PCE in groundwater from the residential-supply wells (as of 2012). However, part of assessing the potential for PCE transport involves understanding the origin of the groundwater in the monitoring and residential wells. One of the tools in delineating the movement of groundwater to wells, particularly in complex, highly heterogeneous fractured-rock aquifers, is the understanding of the geochemical and isotopic composition of groundwater (Lipfert and Reeve, 2004; Harte and others, 2012). This report summarizes findings from analyses of geochemical, isotopic, and dissolved gas characteristics of groundwater. Samples of groundwater were collected in 2011 from monitoring wells and nearby residential-supply wells in proximity to OU1.

New Hampshire

Geological considerations in hazardous waste disposal

Present regulations assume that long-term isolation of hazardous wastes - including toxic chemical, biological, radioactive, flammable and explosive wastes - may be effected by disposal in landfills that have liners of very low hydraulic conductivity. In reality, total isolation of wastes in humid areas is not possible; some migration of leachate from wastes buried in the gound will always occur. Regulations should provide performance standards applicable on a site-by-site basis rather than rigid criteria for site selection and design. The performance standards should take into account several factors: (1) the categories, segregation, degradation and toxicity of the wastes; (2) the site hydrogeology, which governs the direction and rate of contaminant transport; (3) the attenuation of contaminants by geochemical interactions with geologic materials; and (4) the release rate of unattenuated pollutants to surface or groundwater. An adequate monitoring system is essential. The system should both test the extent to which the operation of the site meets performance standards and provide sufficient warning of pollution problems to allow implementation of remedial measures. In recent years there has been a trend away from numerous, small disposal sites toward fewer and larger sites. The size of a disposal site should be based on the attenuation capacity of the geologic material, which has a finite, though generally not well-defined, limit. For slowly degradable wastes, engineered sites with leachate-collection systems appear to be only a temporary solution since the leachate collected will also require final disposal.

Journal of Hydrology