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Effects of surface applications of biosolids on soil, crops, ground water, and streambed sediment near Deer Trail, Colorado, 1999-2003

The U.S. Geological Survey, in cooperation with Metro Wastewater Reclamation District and North Kiowa Bijou Groundwater Management District, studied natural geochemical effects and the effects of biosolids applications to the Metro Wastewater Reclamation District properties near Deer Trail, Colorado, during 1999 through 2003 because of public concern about potential contamination of soil, crops, ground water, and surface water from biosolids applications. Parameters analyzed for each monitoring component included arsenic, cadmium, copper, lead, mercury, molybdenum, nickel, selenium, and zinc (the nine trace elements regulated by Colorado for biosolids), gross alpha and gross beta radioactivity, and plutonium, as well as other parameters. Concentrations of the nine regulated trace elements in biosolids were relatively uniform and did not exceed applicable regulatory standards. All plutonium concentrations in biosolids were below the minimum detectable level and were near zero. The most soluble elements in biosolids were arsenic, molybdenum, nickel, phosphorus, and selenium. Elevated concentrations of bismuth, mercury, phosphorus, and silver would be the most likely inorganic biosolids signature to indicate that soil or streambed sediment has been affected by biosolids. Molybdenum and tungsten, and to a lesser degree antimony, cadmium, cobalt, copper, mercury, nickel, phosphorus, and selenium, would be the most likely inorganic 'biosolids signature' to indicate ground water or surface water has been affected by biosolids. Soil data indicate that biosolids have had no measurable effect on the concentration of the constituents monitored. Arsenic concentrations in soil of both Arapahoe and Elbert County monitoring sites (like soil from all parts of Colorado) exceed the Colorado soil remediation objectives and soil cleanup standards, which were determined by back-calculating a soil concentration equivalent to a one-in-a-million cumulative cancer risk. Lead concentrations in soil slightly exceed the U.S. Environmental Protection Agency toxicity-derived ecological soil-screening levels for avian wildlife. Plutonium concentration in the soil was near zero. Wheat-grain data were insufficient to determine any measurable effects from biosolids. Comparison with similar data from other parts of North America where biosolids were not applied indicates similar concentrations. However, the Deer Trail study area had higher nickel concentrations in wheat from both the biosolids-applied fields and the control fields. Plutonium content of the wheat was near zero. Ground-water levels generally declined at most wells during 1999 through 2003. Ground-water quality did not correlate with ground-water levels. Vertical ground-water gradients during 1999 through 2003 indicate that bedrock ground-water resources downgradient from the biosolids-applied areas are not likely to be contaminated by biosolids applications unless the gradients change as a result of pumping. Ground-water quality throughout the study area varied over time at each site and from site to site at the same time, but plutonium concentrations in the ground water always were near zero. Inorganic concentrations at well D6 were relatively high compared to other ground-water sites studied. Ground-water pH and concentrations of fluoride, nitrite, aluminum, arsenic, barium, chromium, cobalt, copper, lead, mercury, nickel, silver, zinc, and plutonium in the ground water of the study area met Colorado standards. Concentrations of chloride, sulfate, nitrate, boron, iron, manganese, and selenium exceeded Colorado ground-water standards at one or more wells. Nitrate concentrations at well D6 significantly (alpha = 0.05) exceeded the Colorado regulatory standard. Concentrations of arsenic, cadmium, chromium, lead, mercury, nickel, and zinc in ground water had no significant (alpha = 0.05) upward trends. During 1999-2003, concentrations of nitrate, copper, molybdenum, and selenium

Scientific Investigations Report

Reinterpreting the importance of oxygen-based biodegradation in chloroethene-contaminated groundwater

Chlororespiration is common in shallow aquifer systems under conditions nominally identified as anoxic. Consequently, chlororespiration is a key component of remediation at many chloroethene-contaminated sites. In some instances, limited accumulation of reductive dechlorination daughter products is interpreted as evidence that natural attenuation is not adequate for site remediation. This conclusion is justified when evidence for parent compound (tetrachloroethene, PCE, or trichloroethene, TCE) degradation is lacking. For many chloroethene-contaminated shallow aquifer systems, however, nonconservative losses of the parent compounds are clear but the mass balance between parent compound attenuation and accumulation of reductive dechlorination daughter products is incomplete. Incomplete mass balance indicates a failure to account for important contaminant attenuation mechanisms and is consistent with contaminant degradation to nondiagnostic mineralization products like CO 2 . While anoxic mineralization of chloroethene compounds has been proposed previously, recent results suggest that oxygen-based mineralization of chloroethenes also can be significant at dissolved oxygen concentrations below the currently accepted field standard for nominally anoxic conditions. Thus, reassessment of the role and potential importance of low concentrations of oxygen in chloroethene biodegradation are needed, because mischaracterization of operant biodegradation processes can lead to expensive and ineffective remedial actions. A modified interpretive framework is provided for assessing the potential for chloroethene biodegradation under different redox conditions and the probable role of oxygen in chloroethene biodegradation.

Ground Water Monitoring and Remediation

Relative vulnerability of public supply wells to VOC contamination in hydrologically distinct regional aquifers

A process-based methodology was used to compare the vulnerability of public supply wells tapping seven study areas in four hydrologically distinct regional aquifers to volatile organic compound (VOC) contamination. This method considers (1) contributing areas and travel times of groundwater flowpaths converging at individual supply wells, (2) the oxic and/or anoxic conditions encountered along each flowpath, and (3) the combined effects of hydrodynamic dispersion and contaminant- and oxic/anoxic-specific biodegradation. Contributing areas and travel times were assessed using particle tracks generated from calibrated regional groundwater flow models. These results were then used to estimate VOC concentrations relative to an unspecified initial concentration (C/C0) at individual public supply wells. The results show that the vulnerability of public supply wells to VOC contamination varies widely between different regional aquifers. Low-recharge rates, long travel times, and the predominantly oxic conditions characteristic of Basin and Range aquifers in the western United States leads to lower vulnerability to VOCs, particularly to petroleum hydrocarbons such as benzene and toluene. On the other hand, high recharge rates and short residence times characteristic of the glacial aquifers of the eastern United States leads to greater vulnerability to VOCs. These differences lead to distinct patterns of C/C0 values estimated for public supply wells characteristic of each aquifer, information that can be used by resource managers to develop monitoring plans based on relative vulnerability, to locate new public supply wells, or to make land-use management decisions.

Ground Water Monitoring and Remediation

Microbial mineralization of dichloroethene and vinyl chloride under hypoxic conditions

Mineralization of 14C-radiolabled vinyl chloride ([1,2-14C] VC) and cis-dichloroethene ([1,2-14C] cis-DCE) under hypoxic (initial dissolved oxygen (DO) concentrations about 0.1 mg/L) and nominally anoxic (DO minimum detection limit = 0.01 mg/L) was examined in chloroethene-exposed sediments from two groundwater and two surface water sites. The results show significant VC and dichloroethene (DCE) mineralization under hypoxic conditions. All the sample treatments exhibited pseudo-first-order kinetics for DCE and VC mineralization over an extended range of substrate concentrations. First-order rates for VC mineralization were approximately 1 to 2 orders of magnitude higher in hypoxic groundwater sediment treatments and at least three times higher in hypoxic surface water sediment treatments than in the respective anoxic treatments. For VC, oxygen-linked processes accounted for 65 to 85% of mineralization at DO concentrations below 0.1 mg/L, and 14CO2 was the only degradation product observed in VC treatments under hypoxic conditions. Because the lower detection limit for DO concentrations measured in the field is typically 0.1 to 0.5 mg/L, these results indicate that oxygen-linked VC and DCE biodegradation can be significant under field conditions that appear anoxic. Furthermore, because rates of VC mineralization exceeded rates of DCE mineralization under hypoxic conditions, DCE accumulation without concomitant accumulation of VC may not be evidence of a DCE degradative “stall” in chloroethene plumes. Significantly, mineralization of VC above the level that could reasonably be attributed to residual DO contamination was also observed in several nominally anoxic (DO minimum detection limit = 0.01 mg/L) microcosm treatments.

Georgia

National water summary 1986: Hydrologic events and ground-water quality

Ground water is one of the most important natural resources of the United States and degradation of its quality could have a major effect on the welfare of the Nation. Currently (1985), ground water is the source of drinking water for 53 percent of the Nation's population and for more than 97 percent of its rural population. It is the source of about 40 percent of the Nation's public water supply, 33 percent of water for irrigation, and 17 percent of freshwater for selfsupplied industries. Ground water also is the source of about 40 percent of the average annual streamflow in the United States, although during long periods of little or no precipitation, ground-water discharges provide nearly all of the base streamflow. This hydraulic connection between aquifers and streams implies that if a persistent pollutant gets into an aquifer, it eventually could discharge into a stream. Information presented in the 1986 National Water Summary clearly shows that the United States has very large amounts of potable ground water available for use. Although naturally occurring constituents, such as nitrate, and human-induced substances, such as synthetic organic chemicals, frequently are detected in ground water, their concentrations usually do not exceed existing Federal or State standards or guidelines for maximum concentrations in drinking water. Troublesome contamination of ground water falls into two basic categories related to the source or sources of the contamination. Locally, high concentrations of a variety of toxic metals, organic chemicals, and petroleum products have been detected in ground water associated with point sources such as wastedisposal sites, storage-tank leaks, and hazardous chemical spills. These types of local problems commonly occur in densely populated urban areas and industrialized areas. Larger, multicounty areas also have been identified where contamination frequently is found in shallow wells. These areas generally are associated with broad-scale, or nonpoint, sources of contamination such as agricultural activities or highdensity domestic waste disposal (septic systems) in urban centers. At present, only a very small percentage of the total volume of potable ground water in the United States is contaminated from both point and nonpoint sources; however, available data, especially data about the occurrence of synthetic organic and toxic substances, generally are inadequate to determine the full extent of ground-water contamination in the Nation's aquifers or to define trends in groundwater quality. Most information about the occurrence of these substances has come from the study of individual sites or areas where contamination had already been detected or suspected. Management and protection of ground water present a major challenge to the Nation. Current and projected costs of detection and cleanup of existing ground-water contamination are staggering and, even so, complete removal of pollutants from ground water in the vicinity of some waste sites might not be technically feasible. At all levels of government, the task of protecting the resource for its most beneficial uses is difficult and controversial. Despite increasing awareness that some of the Nation's ground water is contaminated with a variety of toxic metals, synthetic organic chemicals, radionuclides, pesticides, and other contaminants that might present a long-term risk to human health, public policy towards ground-water protection is still in the formative stages. Despite increasing efforts devoted to ground-water protection by State and Federal regulatory and resource-management agencies, the extent of ground-water contamination is likely to appear to increase over the next few years because more agencies will be searching for evidence of contamination, and they will be using increasingly sensitive analytical procedures. Increased technology and expanded monitoring activities probably will detect the effects of past contamination and land uses on water quality. The significant time lag between a waterquality change in one part of an aquifer system and the effects of that change at a downgradient site, such as a well, results from the generally slow movement of ground water. This lag between cause and observed effect needs to be considered in evaluating the effectiveness of current and future ground-water policies and remedial measures. Conclusive answers to questions about the location, extent, and severity of ground-water contamination, and about trends in ground-water quality, must await further collection and analysis of data from the Nation's aquifers. Generalizations, however, can be made, and the 1986 National Water Summary, which describes the natural quality of ground-water resources in each State and the major contamination problems that have been identified as of 1986, provides a national perspective of the ground-water-quality situation. The 1986 National Water Summary follows the format of previous volumes. It contains three parts, and the contents of each of these parts are highlighted below.

Water Supply Paper

Geochemistry and microbiology of groundwater and solids from extraction and monitoring wells and their relation to well efficiency at a Federally operated confined disposal facility, East Chicago, Indiana

In cooperation with the U.S. Army Corps of Engineers, Chicago District, the U.S. Geological Survey investigated the processes affecting water quality, geochemistry, and microbiology in representative extraction and monitoring wells at a confined disposal facility (CDF) in East Chicago, Indiana. The CDF is a 140-acre Federally-managed facility that was the former location of an oil refinery and is now used for the long-term disposal and storage of dredge material from the Indiana Harbor and Indiana Harbor Canal. Residual petroleum hydrocarbons and leachate from the CDF are contained within the facility by use of a groundwater cutoff wall. The wall consists of a soil-bentonite slurry and a gradient control system made up of an automated network of 96 extraction wells, 42 monitoring wells, and 2 ultrasonic sensors that maintain an inward hydraulic gradient at the site. The pumps in the extraction wells require vigilant maintenance and must be replaced when unable to withdraw water at a rate sufficient to maintain the required inward gradient. The wells are screened in the Calumet aquifer, a coarse-grained sand and gravel unit that extends approximately 35 feet below the land surface and is not utilized for drinking-water supply at the CDF or in the surrounding area. This study was initiated to identify the cause of decreased pump discharges and to identify potential mitigation strategies. For this study, the U.S. Geological Survey collected groundwater and solids from monitoring and extraction wells. Groundwater samples were collected during June 2014 for precautionary health screening and on four occasions during September 2014 through November 2014. Groundwater samples collected from two extraction wells during June 2014 were analyzed for concentrations of anthropogenic organic constituents. During September through November 2014, groundwater samples were collected from one additional extraction well, and samples from three monitoring wells were analyzed for concentrations of inorganic and organic constituents, dissolved gases, and bacterial abundance and diversity. Solid samples were collected during April 2014, during September 2014 through November 2014, and during November 2016. Solid samples were collected from the exterior of extraction-well pumps and as flocculent from water samples. Solid samples were collected from 10 wells, including 1 extraction well and 3 monitoring wells sampled for water quality. Solid samples were analyzed for mineralogy, solid-phase habit, geochemistry, and organic composition. The following is a list of observations that were made during this study: (1) the water quality is substantially variable among the six well locations sampled as part of this study—lower (more negative) redox values and higher concentrations of many constituents (including calcium, magnesium, sodium, and sulfate) and properties (including dissolved solids, hardness, and turbidity) were detected in sampled wells located near the extraction wells with the highest frequency of failure; (2) water-level drawdown is variable between extraction wells—wells with the greatest drawdown may pull deeper groundwater into the borehole; (3) dissolved gas results indicate reducing oxidation-reduction processes in the aquifer material that can feasibly contribute iron, carbon dioxide, and other byproducts from hydrocarbon degradation to precipitates and solids that accumulate on and impair pump operation; (4) crystalline and amorphous solid-phase minerals are precipitating in the borehole; (5) several types of bacteria are present in water pumped from extraction wells and are likely responsible for bonding mineral and microbiologic matter to the pump (and other well components); and (6) bacteria may create microenvironments that facilitate precipitation of solids or inhibit dissolution of unstable minerals once the bacteria adhere to biofilm attached to the pump. Results of the study indicate that bacteria may be accumulating and entrapping solid material on the exterior of pumps. This accumulation reduces heat transfer and water discharge from the pump and may lead to decreased efficiency or mechanical failure. Observations could not be made on the well screen, gravel pack, or surrounding geologic formation; therefore, mitigating measures in the borehole may not solve well-productivity issues. Remedies for the pump fouling problems were derived from the review and interpretation of data collected during this study and from information documented in other sources about groundwater well fouling. Potential remedies to problems associated with pump fouling at the CDF may include the following: (1) reducing attractiveness of the extraction wells for microbiological growth by modifying the chemical or physical environment of the well, (2) modifying the pump exterior to decrease microbiological adherence, (3) changing the pumping regime to control the chemistry of water entering the well from the surrounding aquifer material, (4) modifying the pumps to be less physically and thermally attractive, and (5) removing hydrocarbons from groundwater and the aquifer material surrounding the wells or adding surfactants to make them more mobile. Pilot scale testing may be necessary to identify the most effective treatment or combination of treatments.

Indiana

Numerical simulation of groundwater flow at Puget Sound Naval Shipyard, Naval Base Kitsap, Bremerton, Washington

Information about groundwater-flow paths and locations where groundwater discharges at and near Puget Sound Naval Shipyard is necessary for understanding the potential migration of subsurface contaminants by groundwater at the shipyard. The design of some remediation alternatives would be aided by knowledge of whether groundwater flowing at specific locations beneath the shipyard will eventually discharge directly to Sinclair Inlet of Puget Sound, or if it will discharge to the drainage system of one of the six dry docks located in the shipyard. A 1997 numerical (finite difference) groundwater-flow model of the shipyard and surrounding area was constructed to help evaluate the potential for groundwater discharge to Puget Sound. That steady-state, multilayer numerical model with homogeneous hydraulic characteristics indicated that groundwater flowing beneath nearly all of the shipyard discharges to the dry-dock drainage systems, and only shallow groundwater flowing beneath the western end of the shipyard discharges directly to Sinclair Inlet. Updated information from a 2016 regional groundwater-flow model constructed for the greater Kitsap Peninsula was used to update the 1997 groundwater model of the Puget Sound Naval Shipyard. That information included a new interpretation of the hydrogeologic units underlying the area, as well as improved recharge estimates. Other updates to the 1997 model included finer discretization of the finite-difference model grid into more layers, rows, and columns, all with reduced dimensions. This updated Puget Sound Naval Shipyard model was calibrated to 2001–2005 measured water levels, and hydraulic characteristics of the model layers representing different hydrogeologic units were estimated with the aid of state-of-the-art parameter optimization techniques. The flow directions and discharge locations predicted by this updated model generally match the 1997 model despite refinements and other changes. In the updated model, most groundwater discharge recharged within the boundaries of the shipyard is to the dry docks; only at the western end of the shipyard does groundwater discharge directly to Puget Sound. Particle tracking for the existing long-term monitoring well network suggests that only a few wells intercept groundwater that originates as recharge within the shipyard boundary.

Washington

Contamination movement around a permeable reactive barrier at Solid Waste Management Unit 12, Naval Weapons Station Charleston, North Charleston, South Carolina, 2009

The U.S. Geological Survey and the Naval Facilities Engineering Command Southeast investigated natural and engineered remediation of chlorinated volatile organic compound groundwater contamination at Solid Waste Management Unit 12 at the Naval Weapons Station Charleston, North Charleston, South Carolina, beginning in 2000. In early 2004, groundwater contaminants began moving around the southern end of a permeable reactive barrier (PRB) installed by a consultant in December 2002. The PRB is a 130-foot-long and 3-foot-wide barrier consisting of varying amounts of zero-valent iron with or without sand mixture. Contamination moving around the PRB probably has been transported at least 75 feet downgradient from the PRB at a rate of about 15 to 29 feet per year. The diversion of contamination around the southern end of the PRB may be due to construction difficulties associated with the PRB installation or to reduced permeability in the PRB. An event that took place during installation of the PRB, which may have caused permeability loss, was the collapse and subsequent abandonment of a 110-foot-long trench originally designed to be the PRB on November 11, 2002, approximately 25 feet upgradient (west) from the final PRB. Guar gum with antimicrobial preservative in a polymer slurry had been used to stabilize the abandoned trench prior to collapse and was only partially recovered. Residual guar gum can cause permeability reduction in a PRB. It also is possible that permeability reduction took place within the PRB by slow degradation of the guar gum slurry or mineral precipitation. Despite the likely permeability reduction in and near the PRB immediately following installation, there is evidence that contaminants moved through the PRB and were degraded, consistent with the planned purpose of the PRB. Volatile organic compound contamination in groundwater downgradient from the PRB is subject to attenuation by phytovolatilization, sorption, and biodegradation. Pulses of contamination increases have been observed in some monitoring wells downgradient from the PRB. The pulses may reflect downgradient transport of contaminant pulses; however, lateral shifting of the plume is a more likely explanation for the concentration changes at well 12MW-12S. The ability to monitor the fate and behavior of the plume in the forest is severely limited because the present axis of maximum contamination in that area bypasses all but one of the existing monitoring wells (12MW-12S). Moreover, the 2009 data indicate that there are no optimally placed sentinel wells in the probable path of contaminant transport. Thus the monitoring network is no longer adequate to monitor the groundwater contamination downgradient from the PRB.

South Carolina

Examining the extraction efficiency of petroleum-derived dissolved organic matter in contaminated groundwater plumes

The extraction efficiency of petroleum-derived dissolved organic matter (DOM) was examined for groundwater samples from an aquifer contaminated with crude oil. Four different types of extraction were used to determine which method is best suited for the analysis of potentially toxic petroleum-derived DOM. The four types were a liquid-liquid extraction (LLE) with dichloromethane (EPA method 3510C), and three solid-phase extraction (SPE) stationary phases that are routinely used for extraction of polar analytes from water. For the LLE, that is selective for non-polar compounds, the extraction efficiency of petroleum-derived DOM decreased downgradient as the petroleum-derived DOM becomes increasingly polar due to biodegradation. In contrast, the average extraction efficiency by the SPE methods was greater than 65 % across the gradient. The results showed that SPE is more efficient for extracting petroleum-derived DOM at hydrocarbon-contaminated sites. The use of a method with greater extraction efficiency for partially-oxidized hydrocarbons may prove useful in determining relationships between their composition and structure and potential for risks to human health or the environment.

Ground Water Monitoring and Remediation

Tidal flushing of mercury from the Bremerton Naval Complex through the PSNS015 stormwater drain system to Sinclair Inlet, Kitsap County, Washington, 2011 -12

The sediments of Sinclair Inlet, in Puget Sound, Washington, have elevated levels of contaminants including mercury. The Bremerton Naval Complex is adjacent to Sinclair Inlet, and has known areas of historical soil mercury contamination. The U.S. Geological Survey, in cooperation with the U.S. Navy, has been investigating the potential for mercury sources on the Bremerton Naval Complex to recontaminate recently remediated marine sediment. In 2011–12, the U.S. Geological Survey conducted three tidal- related sampling campaigns to characterize mercury dynamics in the largest stormwater drain system on the Bremerton Naval Complex, which passes through the soils of an area known as Site 2 that has elevated soil mercury concentrations. The sampling campaigns confirmed that the stormwater drain system, PSNS015, serves as a conduit for seawater transport more than 250 m landward of the contaminated soils that subsequently facilitates mercury transport to Sinclair Inlet. During the December 2011 reconnaissance sampling campaign, no freshwater source of mercury to PSNS015 was identified. There was heavy precipitation preceding and stormwater runoff generated during the reconnaissance survey, which suggests that the primary source of mercury in PSNS015 is not precipitation-induced. During the May 2012 spring-tide sampling campaign, the water in PSNS015 drained to Sinclair Inlet during a negative low tide, and the highest filtered total mercury concentration in the stormwater drain system (60 ng/L) was measured during the lower-low tide in the freshwater flowing into the seaward-most stormwater drain vault from either up-pipe or local groundwater intrusion. Similar conditions were not observed during the June 2012 companion neap-tide sampling campaign, when the water-level elevation of the positive low tide in Sinclair Inlet dropped only slightly below the stormwater drain vault elevation, the water in the seaward-most stormwater vault was brackish rather than fresh, and the filtered total mercury concentration never exceeded 24 ng/L. Particulate total mercury concentrations and dynamics during the spring- and neap-tide sampling campaigns were variable, with higher concentrations (as much as 133 ng/L) measured throughout the neap-tide study compared to those measured during the spring-tide study (as much as 4.34 ng/L). The highest filtered total mercury concentration of all sampling campaigns (1,140 ng/L) was measured during ebb tide in a nearshore monitoring well that represents groundwater discharging from the contaminated soils directly to Sinclair Inlet along an unwalled part of the shoreline. The results suggest that mercury extracted from Site 2 soils can be carried to Sinclair Inlet during ebb tides by at least two mechanisms: (1) through groundwater directly to Sinclair Inlet along an unwalled part of the shoreline or (2) through the stormwater drain system when the water level in Sinclair Inlet drops below the water level in the stormwater drain system. The data can be used to guide future modifications to the seawall and stormwater drain system that aim to hydraulically disconnect the stormwater drain system from the surrounding contaminated soils.

Washington

Completion summary for Borehole TAN-2336 at Test Area North, Idaho National Laboratory, Idaho

In 2021, the U.S. Geological Survey, in cooperation with the U.S. Department of Energy, drilled and constructed borehole TAN-2336 for stratigraphic framework analyses and long-term groundwater monitoring of the eastern Snake River Plain aquifer at the Idaho National Laboratory in southeastern Idaho. Borehole TAN-2336 initially was cored from the depths of 34.0–255.8 ft below land surface (BLS) to collect continuous geologic data and then redrilled to complete construction as a monitoring well completed to about 255 ft BLS. Three sediment layers are described in geophysical data, but only one was recovered in core and described as fine sand with evidence of ash (pumice) near 203 ft BLS. Basalt texture for borehole TAN-2336 generally was described as aphanitic, phaneritic, diktytaxitic, and porphyritic. Basalt flows varied from highly fractured to dense with high to low vesiculation. Geophysical data were examined with photographed core material to make lithologic descriptions as well as suggest zones where groundwater flow was anticipated. Primary pathways for groundwater, fractured basalt, occur in two areas with the first occurrence near 232.0 ft BLS and the second occurrence near 248.6 ft BLS in borehole TAN-2336. The first occurrence was identified near the top of the water column (232.0 ft BLS) and is more pronounced than the bottom interval (248.6 ft BLS). The location of these fractures in borehole TAN-2336 appear to impact the aquifer tests that were conducted following final well construction. Single-well aquifer tests were completed July 14, 2021, to provide estimates of transmissivity and hydraulic conductivity. Estimates for transmissivity and hydraulic conductivity during aquifer test 1 were 1.24×103 feet squared per day (ft 2 /d) and 1.76 feet per day (ft/d), respectively. Estimates for transmissivity and hydraulic conductivity during aquifer test 2 were 1.22×103 ft 2 /d and 1.75 ft/d, respectively. The transmissivity and hydraulic conductivity estimates for well TAN-2336 were within range of those considered from previous aquifer tests in other wells near Test Area North. Water-quality samples were analyzed for cations, anions, metals, nutrients, volatile organic compounds, stable isotopes, and radionuclides. Water samples for select inorganic constituents showed concentrations consistent with signatures from regional groundwater. Water-quality samples analyzed for stable isotopes of oxygen and hydrogen are consistent with signatures from irrigation and agricultural recharge inputs to the aquifer. Results for trichloroethene, vinyl chloride, and strontium-90 were all measured above their respective maximum contaminant levels (MCLs) for public drinking water supplies. The nutrient concentration results are likely being impacted by the remediation amendment introduced to the aquifer to address trichloroethylene concentrations from past waste-disposal activities. These waste-disposal activities have resulted in volatile organic compound and radiochemical detections in groundwater samples collected at well TAN-2336.

Idaho

Accuracy of flowmeters measuring horizontal groundwater flow in an unconsolidated aquifer simulator.

Borehole flowmeters that measure horizontal flow velocity and direction of groundwater flow are being increasingly applied to a wide variety of environmental problems. This study was carried out to evaluate the measurement accuracy of several types of flowmeters in an unconsolidated aquifer simulator. Flowmeter response to hydraulic gradient, aquifer properties, and well-screen construction was measured during 2003 and 2005 at the U.S. Geological Survey Hydrologic Instrumentation Facility in Bay St. Louis, Mississippi. The flowmeters tested included a commercially available heat-pulse flowmeter, an acoustic Doppler flowmeter, a scanning colloidal borescope flowmeter, and a fluid-conductivity logging system. Results of the study indicated that at least one flowmeter was capable of measuring borehole flow velocity and direction in most simulated conditions. The mean error in direction measurements ranged from 15.1 degrees to 23.5 degrees and the directional accuracy of all tested flowmeters improved with increasing hydraulic gradient. The range of Darcy velocities examined in this study ranged 4.3 to 155 ft/d. For many plots comparing the simulated and measured Darcy velocity, the squared correlation coefficient (r 2 ) exceeded 0.92. The accuracy of velocity measurements varied with well construction and velocity magnitude. The use of horizontal flowmeters in environmental studies appears promising but applications may require more than one type of flowmeter to span the range of conditions encountered in the field. Interpreting flowmeter data from field settings may be complicated by geologic heterogeneity, preferential flow, vertical flow, constricted screen openings, and nonoptimal screen orientation.

Ground Water Monitoring and Remediation

Groundwater quality, age, and susceptibility and vulnerability to nitrate contamination with linkages to land use and groundwater flow, Upper Black Squirrel Creek Basin, Colorado, 2013

The Upper Black Squirrel Creek Basin is located about 25 kilometers east of Colorado Springs, Colorado. The primary aquifer is a productive section of unconsolidated deposits that overlies bedrock units of the Denver Basin and is a critical resource for local water needs, including irrigation, domestic, and commercial use. The primary aquifer also serves an important regional role by the export of water to nearby communities in the Colorado Springs area. Changes in land use and development over the last decade, which includes substantial growth of subdivisions in the Upper Black Squirrel Creek Basin, have led to uncertainty regarding the potential effects to water quality throughout the basin. In response, the U.S. Geological Survey, in cooperation with Cherokee Metropolitan District, El Paso County, Meridian Service Metropolitan District, Mountain View Electric Association, Upper Black Squirrel Creek Groundwater Management District, Woodmen Hills Metropolitan District, Colorado State Land Board, and Colorado Water Conservation Board, and the stakeholders represented in the Groundwater Quality Study Committee of El Paso County conducted an assessment of groundwater quality and groundwater age with an emphasis on characterizing nitrate in the groundwater. Groundwater-quality samples were collected from 50 randomly selected wells between May and June 2013. The samples were analyzed for major ions, nutrients, dissolved gases, tritium ( 3 H), chlorofluorocarbons (CFC-11, CFC-12, and CFC-113), and fuel products (such as benzene, toluene, ethylbenzene, and xylenes). None of the groundwater samples exceeded the U.S. Environmental Protection Agency (EPA) National Primary Drinking Water Regulations for primary maximum contaminant levels (MCL) for major ions. Secondary maximum contaminant levels, which are not health concerns and affect mainly taste, color, or odor of the water, were observed in rare instances for pH (2 samples), chloride (1 sample), iron (3 samples), and manganese (8 samples). The secondary maximum contaminant level for total dissolved solids was also exceeded for two samples. Nitrate (nitrite plus nitrate as nitrogen in groundwater) was elevated above the estimated background concentration of natural recharge waters of 1 milligram per liter (mg/L) in 44 of the 50 wells sampled and showed a median concentration of 5.4 mg/L. Nitrate concentrations were above the MCL of 10 mg/L in 5 of the 50 wells sampled and above half of the EPA MCL (5 mg/L) in 27 of the 50 wells sampled, which included samples above the MCL. Dissolved-oxygen concentrations exceeded 0.5 mg/L in 95 percent of reported values (40 of 42 samples) and exceeded 2.0 mg/L in 90 percent of reported values (38 of 42 samples). The oxidized conditions observed in most areas indicate that nitrate from fertilizers and animal or human waste was geochemically stable and could persist in the groundwater for decades or perhaps longer. A historical analysis of median nitrate concentrations over nearly three decades showed an increase in nitrate of approximately 1 mg/L from 4.3 to 5.4 mg/L, although the increase was not determined to be significantly different using nonparametric statistical methods. Major-ion data indicate that groundwater representative of the primary aquifer was classified as calcium-sodium bicarbonate type water. Other water samples from wells located mainly along the periphery of the primary aquifer had cation-anion compositions consistent with distinct water sources, including groundwater contributions from the underlying bedrock aquifers. The areas with differentiable water sources were located mainly where alluvial deposits were thin and geologic contacts to the underlying bedrock aquifers were relatively shallow. Nitrate concentrations in the groundwater were evaluated for relations to land use. An agricultural region was defined using a sequence of land satellite imagery. Groundwater flow directions interpreted from median water-table elevations measured from 2000 to 2013 were used in conjunction with cropland locations to define the agricultural region boundaries by encompassing potential pathways of nitrate transport in the groundwater from nitrogen-based fertilizers. A statistically significant higher median nitrate concentration was observed for areas inside the agricultural region (6.7 mg/L) compared to areas outside the agricultural region (2.3 mg/L), although median concentrations in both areas were below the MCL (10 mg/L). Median nitrate concentration was also significantly greater in land parcels with septic use (4.9 mg/L) compared to nonseptic parcels (1.7 mg/L). In general, agriculture or septic use was identified as the primary source of nitrate, depending on location, while commercial, county, grazing, and residential land uses were generally secondary sources of nitrate. Apparent groundwater ages were estimated from chlorofluorocarbons (CFC-11, CFC-12, and CFC-113) and tritium ( 3 H) data using models that assumed piston flow and binary mixing (dilution of a young component with old, tracer-free water). The mean and median groundwater ages were about 30 years and the standard deviation was 6 years, indicating that most groundwater in the primary aquifer was “young” water that had recharged to the aquifer over the last few decades (post-1950s). The median fraction of young water was about 71 percent, and the standard deviation was 29 percent. The remaining water predated the 1950s, which may have originated from deeper geologic formations or may represent slow moving groundwater within the primary aquifer. Some of the oldest groundwater ages (older than 30 years) were observed in the upper reaches of the aquifer to the northwest where the primary aquifer is thin and intersects bedrock, supporting the hypothesis of geochemically distinct groundwater entering the primary aquifer from below. Groundwater that had reached the central part of the aquifer from upgradient areas of the basin was variable in age because of differences in flow paths and travel velocities. The groundwater age analysis showed that current (2013) land-use practices could affect water quality over decades to come, and that responses to remedial actions could be slow, especially for constituents, such as nitrate, that are stable under oxidized conditions. Fuel products (including acetone, benzene, diisopropyl ether, ethylbenzene, methyl acetate, methyl tertiary butyl ether (MTBE), methyl tert-pentyl ether, m- + p-xylene, o-xylene, tert-amyl alcohol, tert-butyl alcohol, tert-butyl ethyl ether, and toluene) were analyzed in groundwater from 49 of the 50 wells. Water from seven sites had detections for fuel compounds; all concentrations were below MCL. The results provided assurance of water quality and a valuable baseline to evaluate future trends of fuel constituents as the region is further developed. Probability maps were developed from logistic regression models to examine the likelihood that nitrate concentrations in groundwater exceeded specified levels. Susceptibility analysis examined relations between mid-level (5.0 mg/L) nitrate concentrations and climatic, hydrologic, and geologic variables; the significant variables were identified as depth to groundwater, soil organic matter, and soil water storage to 25-centimeter (cm) depth. The vulnerability assessments included natural factors driving susceptibility but also human factors related to land use and septic use. Vulnerability to low-level (2.5 mg/L) nitrate was related to depth to groundwater, septic zoning, and soil organic matter. The results highlighted that septic zoning affected low-level nitrate concentrations. Vulnerability to mid-level (5.0 mg/L) nitrate was examined using all 50 samples and also with two data outliers removed, which showed relatively high nitrate concentrations but also anomalous water chemistry or were located beyond the primary study area. Vulnerability to mid-level (5.0 mg/L) nitrate using all 50 samples was related to depth to groundwater, land use, septic use within a 500-meter (m) radius, soil water storage to a 25-cm depth, soil organic matter, and whether a location was within the agricultural region. The mid-level (5.0 mg/L) vulnerability model using 48 samples (two outliers removed) produced the best overall fit and was related to the same variables as when using all samples except septic use. The results for mid-level vulnerability provided additional support that septic use was associated with low levels of nitrate in the groundwater. Soil properties and land use were identified as the main drivers of moderate nitrate concentrations. Probabilities of exceeding low-level nitrate concentrations were high in most areas with the lowest probabilities usually to the northwest along thin geologic deposits in the upper part of the basin. The results of this investigation offer the foundational information needed for developing best management practices to mitigate nitrate contamination, basic concepts on water quality to aid public education, and information to guide regulatory measures if policy makers determine this is warranted. Science-based decision making will require continued monitoring and analysis of water quality in the future.

Colorado

Design and Performance of an Enhanced Bioremediation Pilot Test in a Tidal Wetland Seep, West Branch Canal Creek, Aberdeen Proving Ground, Maryland

Because of a lack of available in situ remediation methods for sensitive wetland environments where contaminated groundwater discharges, the U.S. Geological Survey, in cooperation with the U.S. Army Garrison, Aberdeen Proving Ground, Maryland, conceived, designed, and pilot tested a permeable reactive mat that can be placed horizontally at the groundwater/surface-water interface. Development of the reactive mat was part of an enhanced bioremediation study in a tidal wetland area along West Branch Canal Creek at Aberdeen Proving Ground, where localized areas of preferential discharge (seeps) transport groundwater contaminated with carbon tetrachloride, chloroform, tetrachloroethene, trichloroethene, and 1,1,2,2-tetrachloroethane from the Canal Creek aquifer to land surface. The reactive mat consisted of a mixture of commercially available organic- and nutrient-rich peat and compost that was bioaugmented with a dechlorinating microbial consortium, WBC-2, developed for this study. Due to elevated chlorinated methane concentrations in the pilot test site, a layer of zero-valent iron mixed with the peat and compost was added at the base of the reactive mat to promote simultaneous abiotic and biotic degradation. The reactive mat for the pilot test area was designed to optimize chlorinated volatile organic compound degradation efficiency without altering the geotechnical and hydraulic characteristics, or creating undesirable water quality in the surrounding wetland area, which is referred to in this report as achieving geotechnical, hydraulic, and water-quality compatibility. Optimization of degradation efficiency was achieved through the selection of a sustainable organic reactive matrix, electron donor, and bioaugmentation method. Consideration of geotechnical compatibility through design calculations of bearing capacity, settlement, and geotextile selection showed that a 2- to 3-feet tolerable thickness of the mat was possible, with 0.17 feet settlement predicted for unconsolidated sediments between 1.5 and 6 years following installation of the reactive mat. To ensure hydraulic compatibility in the mat design, mat materials that had a hydraulic conductivity greater than the surrounding wetland sediments were selected, and the mixture was optimized to consist of 1.5 parts compost, 1.5 parts peat and 1 part sand as a safeguard against fluidization. Sediment and matrix properties also indicated that a nonwoven geotextile with a cross-plane flow greater than that of the native sediments was suitable as the base of the reactive mat. Another nonwoven geotextile was selected for installation between the iron mix and organic zones of the mat to create more laminar flow conditions within the mat. Total metals and sequential extraction procedure analyses of mat materials, which were conducted to evaluate water-quality compatibility of the mat materials, showed that concentrations of metals in the compost ranged from one-half to one order of magnitude below consensus-based probable effect concentrations in sediment. A 22-inch-thick reactive mat, containing 0.5 percent WBC-2 by volume, was constructed at seep area 3-4W and monitored from October 2004 through October 2005 for the pilot test. No local, immediate failure of the mat or of wetland sediments was observed during mat installation, indicating that design estimates of bearing capacity and geotextile textile selection ensured the integrity of the mat and wetland sediments during and following installation. Measurements of surface elevation of the mat showed an average settlement of the mat surface of approximately 0.25 feet after 10 months, which was near the predicted settlement for unconsolidated sediment. Monitoring showed rapid establishment and sustainment throughout the year of methanogenic conditions conducive to anaerobic biodegradation and efficient dechlorination activity by WBC-2. The median mass removal of chloromethanes and total chloroethenes and ethane during the

Scientific Investigations Report